EUR 23015 EN - 2007

Project HORIZONTAL Validation Reporton Kjeldahl nitrogen

Validation of a horizontal standard for the determination of Kjeldahl nitrogen in soils sludges and treated biowaste

in a European Intercomparison Exercise

E Sobiecka H van der Sloot E Janssen B M Gawlik

The mission of the Institute for Environment and Sustainability is to provide scientific-technical support to the European Unionrsquos Policies for the protection and sustainable development of the European and global environment European Commission Joint Research Centre Institute for Environment and Sustainability Contact information Address Via Enrico Fermi 2749 21027 Ispra (VA) Italy E-mail berndgawlikjrcit Tel +39 0332 789487 Fax +39 0332 789158 httpiesjrceceuropaeu httpwwwjrceceuropaeu Legal Notice Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of this publication A great deal of additional information on the European Union is available on the Internet It can be accessed through the Europa server httpeuropaeu JRC 40205 EUR 23015 EN ISBN 978-92-79-07443-1 ISSN 1018-5593 DOI 10278848254 Luxembourg Office for Official Publications of the European Communities copy European Communities 2007 Reproduction is authorised provided the source is acknowledged Printed in Luxemburg

Project HORIZONTAL Validation Report Validation of a horizontal standard for the determination of Kjeldahl nitrogen in soils sludge and treated biowaste in a European Intercomparison Exercise E Sobiecka H Van der Sloot E Janssen B M Gawlik Elzbieta Sobiecka Bernd Manfred Gawlik European Commission Joint Research Centre Institute for Environment and Sustainability Via Enrico Fermi 21020 Ispra - Italy

Hans van der Sloot ECN Emission Characterisation and Reduction Westerduinweg 3 PO Box 1 1755 ZG Petten The Netherlands

Enno Janssen Hessisches Landeslabor Am Versuchsfeld 1 - 13 34128 Kassel Germany

to whom correspondence should be sent

by email to berndgawlikjrcit

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

MILC Measure Interlaboratory Comparison

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for Kjeldahl nitrogen 8 121 Samples dispatched for the validation of Kjeldahl nitrogen 8 122 Draft standards to be followed 8 123 Analytical program 8 124 Timing and Submission of data 9 125 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of Kjeldahl nitrogen are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the Kjeldahl nitrogen draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material1 (3 per bottle) using the respective draft standard methods The 6 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for Kjeldahl nitrogen

121 Samples dispatched for the validation of Kjeldahl nitrogen After a preliminary rough screening the following materials were used for the validation round of Kjeldahl nitrogen

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalKjeldahl_N_Standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

The mission of the Institute for Environment and Sustainability is to provide scientific-technical support to the European Unionrsquos Policies for the protection and sustainable development of the European and global environment European Commission Joint Research Centre Institute for Environment and Sustainability Contact information Address Via Enrico Fermi 2749 21027 Ispra (VA) Italy E-mail berndgawlikjrcit Tel +39 0332 789487 Fax +39 0332 789158 httpiesjrceceuropaeu httpwwwjrceceuropaeu Legal Notice Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of this publication A great deal of additional information on the European Union is available on the Internet It can be accessed through the Europa server httpeuropaeu JRC 40205 EUR 23015 EN ISBN 978-92-79-07443-1 ISSN 1018-5593 DOI 10278848254 Luxembourg Office for Official Publications of the European Communities copy European Communities 2007 Reproduction is authorised provided the source is acknowledged Printed in Luxemburg

Project HORIZONTAL Validation Report Validation of a horizontal standard for the determination of Kjeldahl nitrogen in soils sludge and treated biowaste in a European Intercomparison Exercise E Sobiecka H Van der Sloot E Janssen B M Gawlik Elzbieta Sobiecka Bernd Manfred Gawlik European Commission Joint Research Centre Institute for Environment and Sustainability Via Enrico Fermi 21020 Ispra - Italy

Hans van der Sloot ECN Emission Characterisation and Reduction Westerduinweg 3 PO Box 1 1755 ZG Petten The Netherlands

Enno Janssen Hessisches Landeslabor Am Versuchsfeld 1 - 13 34128 Kassel Germany

to whom correspondence should be sent

by email to berndgawlikjrcit

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

MILC Measure Interlaboratory Comparison

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for Kjeldahl nitrogen 8 121 Samples dispatched for the validation of Kjeldahl nitrogen 8 122 Draft standards to be followed 8 123 Analytical program 8 124 Timing and Submission of data 9 125 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of Kjeldahl nitrogen are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the Kjeldahl nitrogen draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material1 (3 per bottle) using the respective draft standard methods The 6 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for Kjeldahl nitrogen

121 Samples dispatched for the validation of Kjeldahl nitrogen After a preliminary rough screening the following materials were used for the validation round of Kjeldahl nitrogen

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalKjeldahl_N_Standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Project HORIZONTAL Validation Report Validation of a horizontal standard for the determination of Kjeldahl nitrogen in soils sludge and treated biowaste in a European Intercomparison Exercise E Sobiecka H Van der Sloot E Janssen B M Gawlik Elzbieta Sobiecka Bernd Manfred Gawlik European Commission Joint Research Centre Institute for Environment and Sustainability Via Enrico Fermi 21020 Ispra - Italy

Hans van der Sloot ECN Emission Characterisation and Reduction Westerduinweg 3 PO Box 1 1755 ZG Petten The Netherlands

Enno Janssen Hessisches Landeslabor Am Versuchsfeld 1 - 13 34128 Kassel Germany

to whom correspondence should be sent

by email to berndgawlikjrcit

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

MILC Measure Interlaboratory Comparison

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for Kjeldahl nitrogen 8 121 Samples dispatched for the validation of Kjeldahl nitrogen 8 122 Draft standards to be followed 8 123 Analytical program 8 124 Timing and Submission of data 9 125 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of Kjeldahl nitrogen are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the Kjeldahl nitrogen draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material1 (3 per bottle) using the respective draft standard methods The 6 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for Kjeldahl nitrogen

121 Samples dispatched for the validation of Kjeldahl nitrogen After a preliminary rough screening the following materials were used for the validation round of Kjeldahl nitrogen

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalKjeldahl_N_Standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

MILC Measure Interlaboratory Comparison

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for Kjeldahl nitrogen 8 121 Samples dispatched for the validation of Kjeldahl nitrogen 8 122 Draft standards to be followed 8 123 Analytical program 8 124 Timing and Submission of data 9 125 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of Kjeldahl nitrogen are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the Kjeldahl nitrogen draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material1 (3 per bottle) using the respective draft standard methods The 6 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for Kjeldahl nitrogen

121 Samples dispatched for the validation of Kjeldahl nitrogen After a preliminary rough screening the following materials were used for the validation round of Kjeldahl nitrogen

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalKjeldahl_N_Standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

MILC Measure Interlaboratory Comparison

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for Kjeldahl nitrogen 8 121 Samples dispatched for the validation of Kjeldahl nitrogen 8 122 Draft standards to be followed 8 123 Analytical program 8 124 Timing and Submission of data 9 125 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of Kjeldahl nitrogen are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the Kjeldahl nitrogen draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material1 (3 per bottle) using the respective draft standard methods The 6 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for Kjeldahl nitrogen

121 Samples dispatched for the validation of Kjeldahl nitrogen After a preliminary rough screening the following materials were used for the validation round of Kjeldahl nitrogen

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalKjeldahl_N_Standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for Kjeldahl nitrogen 8 121 Samples dispatched for the validation of Kjeldahl nitrogen 8 122 Draft standards to be followed 8 123 Analytical program 8 124 Timing and Submission of data 9 125 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of Kjeldahl nitrogen are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the Kjeldahl nitrogen draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material1 (3 per bottle) using the respective draft standard methods The 6 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for Kjeldahl nitrogen

121 Samples dispatched for the validation of Kjeldahl nitrogen After a preliminary rough screening the following materials were used for the validation round of Kjeldahl nitrogen

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalKjeldahl_N_Standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of Kjeldahl nitrogen are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the Kjeldahl nitrogen draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material1 (3 per bottle) using the respective draft standard methods The 6 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for Kjeldahl nitrogen

121 Samples dispatched for the validation of Kjeldahl nitrogen After a preliminary rough screening the following materials were used for the validation round of Kjeldahl nitrogen

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalKjeldahl_N_Standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the Kjeldahl nitrogen draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material1 (3 per bottle) using the respective draft standard methods The 6 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for Kjeldahl nitrogen

121 Samples dispatched for the validation of Kjeldahl nitrogen After a preliminary rough screening the following materials were used for the validation round of Kjeldahl nitrogen

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalKjeldahl_N_Standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the Kjeldahl nitrogen draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material1 (3 per bottle) using the respective draft standard methods The 6 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for Kjeldahl nitrogen

121 Samples dispatched for the validation of Kjeldahl nitrogen After a preliminary rough screening the following materials were used for the validation round of Kjeldahl nitrogen

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalKjeldahl_N_Standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for Kjeldahl nitrogen

121 Samples dispatched for the validation of Kjeldahl nitrogen After a preliminary rough screening the following materials were used for the validation round of Kjeldahl nitrogen

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalKjeldahl_N_Standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

9

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for Kjeldahl nitrogen to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal Kjeldahl nitrogen standard

bull Austria o Amt der Steirmaumlrkischen Landesregierung o barbara - Engineering Consulting Research amp Service GmbH o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o Umweltbundesamt o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit

bull Belgium o VITO

bull Czech Republic o Central Institute for Supervising and Testing in Agriculture (UKZUZ)

bull France o CEMAGREF - UR QELY o Institut Pasteur de Lille - Dep Eaux et Environnement o SAS Laboratoire

bull Germany o Hessisches Landeslabor

bull Hungary o Central Laboratory of National Institute for Agricultural Quality Control o Chemical Laboratory Mertcontrol Ltd

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

12

Table 1 - Results of the interlaboratory comparison studies of Kjeldahl nitrogen in treated biowaste sludge and soil All concentrations are expressed in gkg dm

Matrix Parameter Mean sr sR r R p Outliers Used number of data

Number of data reported below detection

Total no of data reported

Sludge 1 Kjeldahl 3802 141 436 1499 4638 8 1 42 0 48Sludge 2 Kjeldahl 3527 124 618 1221 6100 9 1 48 0 54Compost 1 Kjeldahl 1622 215 155 0978 7043 9 2 42 0 54Compost 2 Kjeldahl 1268 450 164 1597 5839 10 1 54 0 58Soil 4 Kjeldahl 162 719 243 0327 1107 11 0 44 0 44Soil 5 Kjeldahl 183 442 166 0226 0852 9 1 46 0 52

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

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Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

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Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

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ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

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Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

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Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

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ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

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Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

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Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

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Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

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17L

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31L

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Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

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Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

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Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

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Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

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40L

45L

17L

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29L

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Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

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Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

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22L

31L

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61L

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Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

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31L

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61L

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Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

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Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

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Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

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Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

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Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

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Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

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Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

16

Annex 3

Statistical calculations

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Labo

rato

ries

Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

rato

ries

Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

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Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

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Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

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ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

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Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

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Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Unit mgg

Mandels k statistics(Compost 1 - Kjeldahl)Mandels h statistics(Compost 1 - Kjeldahl)

Sample Compost 1 Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

Element Kjeldahl

General calcparmT1= 687787E+02T2= 114931E+04T3= 42T4= 214T5= 40239E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean29L 109050 0290 4 -187 052 Fail 109050 02901 4 3 -53161L 115665 1206 6 -162 218 Fail - - 61L - - -46515L 138195 0264 6 -078 048 Fail 138195 02640 6 5 -24030L 158667 0351 3 -001 063 158667 03512 3 2 -03517L 164100 0071 2 019 013 164100 00707 2 1 01946L 170000 4 041 Fail 170000 4 3 0789L 170000 0179 6 041 032 Fail 170000 01789 6 5 078

40L 174217 0998 6 057 180 Fail - - 40L - - 12022L 176267 0473 6 064 085 Fail 176267 04729 6 5 14145L 184517 0566 6 095 102 Fail 184517 05659 6 5 22331L 188720 0270 5 111 049 Fail 188720 02701 5 4 266

Totgem 15904 0424 mgg 1-level 222 (174) 9 162168 (40L 61L) 9 8Totstd= 2672 0374 5-level 182 (151) 2

54RESULTS Mean = 1621683 mgg

Repeatability variance S2r = 012194Repeatability std Sr = 034919 --gt 215 r = 09777Between lab variance S2L = 620586Reproducibility var S2R = 632780Reproducibility std SR = 251551 --gt 1551 R = 70434Remarks 2 Labs rejected (40L 61L)

000 050 100 150 200 250

k-values

29L

61L

15L

30L

17L

46L

9L

40L

22L

45L

31L

Mandels k statistics(Compost 1 - Kjeldahl)

-60 -50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

29L

61L

15L

30L

17L

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40L

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Compost 1 - Kjeldahl -- Mean PARM = 1622 [mgg]

-200 -100 000 100 200

h-values

29L

61L

15L

30L

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Mandels h statistics(Compost 1 - Kjeldahl)

Compost 1-Kjeldahl

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

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Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

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Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

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61L

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Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

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9L

19L

40L

22L

31L

45L

61L

Labo

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Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

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19L

9L

46L

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22L

31L

45L

61L

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Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

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Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

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Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

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31L

46L

45L

19L

30L

Labo

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Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

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17L

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9L

31L

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Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

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Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Unit mgg

Mandels k statistics(Compost 2 - Kjeldahl)Mandels h statistics(Compost 2 - Kjeldahl)

Sample Compost 2 Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

Element Kjeldahl

General calcparmT1= 679812E+02T2= 875546E+03T3= 54T4= 308T5= 14309E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

61L 80274 1050 6 -149 198 Fail 80274 10501 6 5 -46515L 110115 0194 6 -070 036 Fail 110115 01936 6 5 -16746L 125000 0577 4 -031 109 Fail 125000 05774 4 3 -01819L 127697 0426 6 -024 080 Fail 127697 04257 6 5 0099L 128833 0488 6 -021 092 Fail 128833 04875 6 5 02122L 130500 0596 6 -017 112 Fail 130500 05958 6 5 03740L 137950 0613 6 003 116 137950 06133 6 5 11245L 138100 0457 6 003 086 138100 04574 6 5 11317L 139500 0325 2 007 061 139500 03253 2 1 12731L 149717 0376 6 034 071 Fail 149717 03759 6 5 22929L 237200 0128 4 264 024 Fail - - 29L - - 1104

Totgem 13681 0475 mgg 1-level 222 (174) 10 126769 (29L) 10 9Totstd= 3807 0247 5-level 182 (151) 1

58RESULTS Mean = 1267686 mgg

Repeatability variance S2r = 032521Repeatability std Sr = 057027 --gt 450 r = 15968Between lab variance S2L = 402333Reproducibility var S2R = 434855Reproducibility std SR = 208532 --gt 1645 R = 58389Remarks 1 Lab rejected (29L)

000 050 100 150 200

k-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Mandels k statistics(Compost 2 - Kjeldahl)

-60 -40 -20 00 20 40 60 80 100 120

Deviation from Mean

61L

15L

46L

19L

9L

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40L

45L

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Compost 2 - Kjeldahl -- Mean PARM = 1268 [mgg]

-200 -100 000 100 200 300

h-values

61L

15L

46L

19L

9L

22L

40L

45L

17L

31L

29L

Labo

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Mandels h statistics(Compost 2 - Kjeldahl)

Compost 2-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

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Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

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Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Unit mgg

Mandels k statistics(Sludge 1 - Kjeldahl)Mandels h statistics(Sludge 1 - Kjeldahl)

Sample Sludge 1 Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

Element Kjeldahl

General calcparmT1= 159799E+03T2= 608905E+04T3= 42T4= 236T5= 97418E+00

n= variabelp= 8

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 351812 0626 6 -168 089 Fail 351812 06265 6 5 -28417L 369800 0325 2 -076 046 Fail 369800 03253 2 1 -1049L 370667 0489 6 -071 069 Fail 370667 04885 6 5 -09519L 379817 0529 6 -024 075 379817 05294 6 5 -00440L 387717 0565 6 016 080 387717 05650 6 5 07522L 388650 0716 6 021 101 388650 07156 6 5 08431L 395500 0526 4 056 075 Fail 395500 05260 4 3 15345L 397717 0136 6 067 019 Fail 397717 01356 6 5 17561L 419730 1530 6 180 217 Fail - - 61L - - 395

Totgem 38460 0605 mgg 1-level 213 (173) 8 380210 (61L) 8 7Totstd= 1956 0386 5-level 178 (15) 1

48RESULTS Mean = 3802098 mgg

Repeatability variance S2r = 028652Repeatability std Sr = 053528 --gt 141 r = 14988Between lab variance S2L = 245705Reproducibility var S2R = 274357Reproducibility std SR = 165637 --gt 436 R = 46378Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 1 - Kjeldahl)

-30 -20 -10 00 10 20 30 40

Deviation from Mean

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

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ries

Sludge 1 - Kjeldahl -- Mean PARM = 3802 [mgg]

-200 -100 000 100 200

h-values

15L

17L

9L

19L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Kjeldahl)

Sludge 1-Kjeldahl

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Unit mgg

Mandels k statistics(Sludge 2 - Kjeldahl)Mandels h statistics(Sludge 2 - Kjeldahl)

Sample Sludge 2 Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

Element Kjeldahl

General calcparmT1= 169616E+03T2= 601313E+04T3= 48T4= 272T5= 74118E+00

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 304925 0225 6 -245 041 Fail 304925 02245 6 5 -47817L 344050 0177 2 -054 033 Fail 344050 01768 2 1 -08719L 348398 0298 6 -033 055 Fail 348398 02981 6 5 -0439L 351833 0376 6 -016 069 351833 03764 6 5 -00946L 355000 0577 4 000 106 355000 05774 4 3 02340L 363983 0579 6 044 107 Fail 363983 05792 6 5 11222L 366667 0486 6 057 090 Fail 366667 04863 6 5 13931L 369833 0549 6 072 101 Fail 369833 05492 6 5 17145L 369950 0349 6 073 064 Fail 369950 03486 6 5 17261L 375979 1141 6 102 210 Fail - - 61L - - 232

Totgem 35506 0476 mgg 1-level 218 (174) 9 352738 (61L) 9 8Totstd= 2050 0275 5-level 180 (15) 1

54RESULTS Mean = 3527378 mgg

Repeatability variance S2r = 019005Repeatability std Sr = 043594 --gt 124 r = 12206Between lab variance S2L = 455636Reproducibility var S2R = 474640Reproducibility std SR = 217862 --gt 618 R = 61001Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Mandels k statistics(Sludge 2 - Kjeldahl)

-50 -40 -30 -20 -10 00 10 20 30

Deviation from Mean

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Sludge 2 - Kjeldahl -- Mean PARM = 3527 [mgg]

-300 -200 -100 000 100 200

h-values

15L

17L

19L

9L

46L

40L

22L

31L

45L

61L

Labo

rato

ries

Mandels h statistics(Sludge 2 - Kjeldahl)

Sludge 2-Kjeldahl

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Unit mgg

Mandels k statistics(Soil 4 - Kjeldahl)Mandels h statistics(Soil 4 - Kjeldahl)

Sample Soil 4 Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

Element Kjeldahl

General calcparmT1= 697604E+01T2= 116386E+02T3= 44T4= 194T5= 44967E-01

n= variabelp= 11

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

15L 09896 0025 5 -178 023 Fail 09896 00249 5 4 -06340L 10120 0101 5 -172 092 Fail 10120 01006 5 4 -06161L 13245 0192 5 -084 177 Fail 13245 01922 5 4 -03017L 16000 - 1 -007 16000 - 1 -0029L 17600 0152 5 038 139 17600 01517 5 4 01422L 17725 0022 4 042 020 Fail 17725 00222 4 3 01531L 17800 0025 5 044 023 Fail 17800 00255 5 4 01646L 18000 3 049 Fail 18000 3 2 01845L 18833 0040 3 073 037 Fail 18833 00404 3 2 02619L 19380 0187 5 088 172 Fail 19380 01868 5 4 03130L 20000 0100 3 106 092 Fail 20000 01000 3 2 038

Totgem 1624 0084 mgg 1-level 222 (184) 11 16236 () 11 10Totstd= 0356 0072 5-level 182 (157)

44RESULTS Mean = 162363 mgg

Repeatability variance S2r = 001363Repeatability std Sr = 011673 --gt 719 r = 03269Between lab variance S2L = 014263Reproducibility var S2R = 015625Reproducibility std SR = 039529 --gt 2435 R = 11068Remarks none

000 050 100 150 200

k-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Mandels k statistics(Soil 4 - Kjeldahl)

-08 -06 -04 -02 00 02 04

Deviation from Mean

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Soil 4 - Kjeldahl -- Mean PARM = 162 [mgg]

-200 -100 000 100 200

h-values

15L

40L

61L

17L

9L

22L

31L

46L

45L

19L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - Kjeldahl)

Soil 4-Kjeldahl

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Unit mgg

Mandels k statistics(Soil 5 - Kjeldahl)Mandels h statistics(Soil 5 - Kjeldahl)

Sample Soil 5 Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

Element Kjeldahl

General calcparmT1= 838970E+01T2= 156556E+02T3= 46T4= 252T5= 24188E-01

n= variabelp= 9

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

40L 13617 0056 6 -149 053 Fail 13617 00556 6 5 -04761L 14234 0232 6 -127 223 Fail - - 61L - - -04115L 14437 0105 6 -120 101 Fail 14437 01053 6 5 -03917L 18300 0057 2 014 054 18300 00566 2 1 00045L 18650 0082 6 026 078 18650 00817 6 5 00346L 18750 0096 4 029 092 18750 00957 4 3 0049L 19000 0000 6 038 000 19000 00000 6 5 00731L 19600 0024 4 059 024 Fail 19600 00245 4 3 01319L 19975 0041 6 072 039 Fail 19975 00410 6 5 01722L 22483 0139 6 159 133 Fail 22483 01391 6 5 042

Totgem 1790 0083 mgg 1-level 218 (174) 9 18312 (61L) 9 8Totstd= 0288 0066 5-level 180 (15) 1

52RESULTS Mean = 183124 mgg

Repeatability variance S2r = 000654Repeatability std Sr = 008085 --gt 442 r = 02264Between lab variance S2L = 008608Reproducibility var S2R = 009262Reproducibility std SR = 030434 --gt 1662 R = 08521Remarks 1 Lab rejected (61L)

000 050 100 150 200 250

k-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Mandels k statistics(Soil 5 - Kjeldahl)

-05 -04 -03 -02 -01 00 01 02 03 04 05

Deviation from Mean

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Soil 5 - Kjeldahl -- Mean PARM = 183 [mgg]

-200 -100 000 100 200

h-values

40L

61L

15L

17L

45L

46L

9L

31L

19L

22L

Labo

rato

ries

Mandels h statistics(Soil 5 - Kjeldahl)

Soil 5-Kjeldahl

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 1408 15L 1119 15L 360315L 1405 15L 1118 15L 357015L 1402 15L 1109 15L 354315L 1374 15L 1099 15L 348315L 1353 15L 1093 15L 346115L 1350 15L 1068 15L 345017L 1646 17L 1418 17L 372117L 1636 17L 1372 17L 367522L 1830 19L 1335 19L 385222L 1780 19L 1305 19L 384322L 1780 19L 1298 19L 381322L 1770 19L 1257 19L 380522L 1711 19L 1247 19L 376722L 1705 19L 1221 19L 370929L 1118 22L 1380 22L 396029L 1113 22L 1360 22L 394929L 1068 22L 1320 22L 391029L 1063 22L 1290 22L 389030L 1620 22L 1250 22L 384030L 1590 22L 1230 22L 377030L 1550 29L 2383 31L 400031L 1918 29L 2379 31L 398031L 1912 29L 2372 31L 396031L 1877 29L 2354 31L 388031L 1875 31L 1563 40L 398131L 1854 31L 1504 40L 389640L 1880 31L 1502 40L 387140L 1840 31L 1488 40L 385040L 1753 31L 1474 40L 383840L 1679 31L 1452 40L 382740L 1663 40L 1461 45L 400040L 1638 40L 1417 45L 398645L 1909 40L 1387 45L 397645L 1902 40L 1378 45L 396945L 1861 40L 1355 45L 396745L 1836 40L 1279 45L 396545L 1793 45L 1449 61L 448545L 1770 45L 1411 61L 424446L 1700 45L 1383 61L 416146L 1700 45L 1364 61L 412946L 1700 45L 1364 61L 408846L 1700 45L 1315 61L 407761L 1307 46L 1300 9L 374061L 1242 46L 1300 9L 374061L 1231 46L 1200 9L 372061L 1093 46L 1200 9L 372061L 1071 61L 978 9L 371061L 996 61L 858 9L 36109L 1730 61L 8049L 1710 61L 7739L 1700 61L 7079L 1690 61L 6969L 1690 9L 13409L 1680 9L 1330

9L 13209L 12709L 12509L 1220

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5[mgg] Element Kjeldahl [mgg] Element Kjeldahl [mgg] Element Kjeldahl

LAB PARM LAB PARM LAB PARM15L 3093 15L 102 15L 16315L 3050 15L 100 15L 14815L 3043 15L 100 15L 14415L 3043 15L 097 15L 13915L 3040 15L 096 15L 13715L 3028 17L 160 15L 13517L 3453 19L 226 17L 18717L 3428 19L 193 17L 17919L 3540 19L 185 19L 20619L 3484 19L 183 19L 20319L 3482 19L 182 19L 20019L 3478 22L 180 19L 19819L 3470 22L 178 19L 19719L 3450 22L 176 19L 19522L 3721 22L 175 22L 24122L 3715 30L 210 22L 23822L 3680 30L 200 22L 23122L 3657 30L 190 22L 22022L 3631 31L 181 22L 21022L 3596 31L 180 22L 20931L 3770 31L 178 31L 19831L 3730 31L 176 31L 19831L 3720 31L 175 31L 19531L 3680 40L 114 31L 19331L 3680 40L 104 40L 14631L 3610 40L 102 40L 13740L 3693 40L 100 40L 13740L 3689 40L 086 40L 13540L 3668 45L 193 40L 13240L 3633 45L 186 40L 13040L 3617 45L 186 45L 19540L 3539 46L 180 45L 19345L 3732 46L 180 45L 19045L 3731 46L 180 45L 18845L 3724 61L 158 45L 17845L 3693 61L 137 45L 17545L 3662 61L 136 46L 20045L 3655 61L 126 46L 19046L 3600 61L 105 46L 18046L 3600 9L 190 46L 18046L 3500 9L 190 61L 16346L 3500 9L 180 61L 16361L 3936 9L 160 61L 16361L 3841 9L 160 61L 13261L 3767 61L 12261L 3703 61L 11261L 3693 9L 19061L 3619 9L 1909L 3580 9L 1909L 3550 9L 1909L 3500 9L 1909L 3500 9L 1909L 34909L 3490

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

European Commission EUR 23015 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on Kjeldahl nitrogen Author(s) E Sobiecka H van der Sloot Enno Janssen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07443-1 Abstract standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of Kjeldahl nitrogen in soils sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23015-EN

-C