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N~RA-WixT.gr C^ualTfcy

Presented lo the 18lh Oclobcr 1994 meeting of the

Marine Pollution Monitoring Management Group

Report Prepared by: Dr. M. A. Jesscp Laboratory Manager, Nottingham Laboratory

National Rivers Authority, Chairman of the

National Co-ordinating Committee

Dr. A. Griffiths Principal Scientific Officer, Tidal Waters,

Forth River Purification Board.

REPORT ON THE

NATIONAL MARINE ANALYTICAL

QUALITY CONTROL SCHEME 1993/94

(MPMMG 94/6)

September 1994Jessep/A HG/LM

NATIONAL M ARINE ANALYTICAL QUALITY CONTROL SCHEME

SECOND YEAR REPORT

EXECUTIVE SUM M ARY

This is ihc sccond annual report of ihc NCC 10 MPMMG. It summarises and details the

actions taken during year 2 to further the aims and objectives of the scheme, describes the proposed

actions for year 3 and makes recommendations for considerations by MPMMG at the October 1994

meeting.

During year 2 of the NMAQC scheme the NCC has;

o Successfully maintained the scheme and ensured its continuity into and through year

3.

o Expanded the scope of the scheme in terms of NMP determinands from some 80%

to >90%, and reviewed the scope to include further determinands in year 3.

O Quantified the overall standards of accuracy achieved by the UK NMP laboratories.

Overseen a maintenance of the standards achieved in Year 1 and recorded

improvements in performance in some areas.

° Established and documented the overall approach for laboratory AQC; commenced the

collation of in-house AQC data.

° Through all its activities e.g. workshops, distributions, encouraged an overall QA

approach to managing laboratory analytical performance.

o Reponed on all its activities to MPMMG and participants in the scheme, through

distribution reports, annual report and the circulation of information,

o Established the levels of participation in the NMP and NMAQC schemes which will

allow MPMMG to audit data provided for the NMP.

It is proposed that NCC will, in year 3 of the scheme;

Pursue, in broad terms, the strategy adopted in year 1 through year 3. This will entail;

routine distribution of materials

running workshops

running special exercises for problem determinands

preparation of bulk reference materials for use in in-house AQC

ENVIRONMENT AGENCY

135363

EXECUTIVE SUMMARY (Cont.)

o Review the schcme finances, its membership and annual fee, to ensure continuity into

year 4 and beyond.

o Review NMP requirements and monitor participation in the NMAQC scheme versus

NMP requirements.

Co-ordinate the use of in-house AQC data and encourage NAMAS/BS 5750

accreditation.

o Continue to review the links with QUASIMEME in order to maximise mutual benefits

to both schemes.

To further improve performance in the NMAQC scheme and participation in NMP, the NCC

recommend that;

° MPMMG approves the overall strategy and proposed programmes of work for year

3 of the scheme.

o MPMMG encourages full participation in the NMAQC scheme to ensure NMP

determinands are covered and, in particular, pursue any non-participation already

identified e.g. mercury and chromium analyses in water.

o MPMMG seeks ways of enlisting additional full-memberships, to assist in ensuring

the longer-term viability of the scheme,

o MPMMG considers the options for securing funding for the scheme, whether national

or international, recommending as appropriate,

o MPMMG considers an alternative action programme for those determinands in the

NMP that are more suited to a single laboratory approach, namely;

PAHs in all matrices

PCP and its metabolites in shellfish

TBT in all matrices

INDEX OF CONTENTS

GLOSSARY OF TERMS PAGE NO.

1. INTRODUCTION 1

2. REPORT OF THE NATIONAL CO-ORDINATING COMMITTEE 22.1 Functions and Role of NCC and FRPB

2.2 Scope, Strategy and Development of the Scheme

2.3 Overview and 2nd Year strategy for external schcmc

2.4 Workshops

2.5 In-house AQC

2.6 NAMAS

2.7 QUASIMEME Links

2.8 Sampling and Sample Handling

2.9 Analytical Methods

2.10 Information

2.11 Confidentiality

3. MANAGEMENT OF THE AQC SCHEME - FRPB 9

3.1 Scheme Management

3.2 Membership

3.3 Contractor Review of Performance

3.4 Financial Arrangements

3.5 Published Reports

4. SUMMARY OF RESULTS FOR YEAR 2 OF EXTERNAL SCHEME 12

4.1 Introduction

4.2 Proficiency Tests

4.2.1 Summary of Performance for Individual Laboratories for

Year 2

4.3 Special Exercises

4.3.1 Ammonia and TON

4.3.2 Trace Metals in Water

4.3.3 Organochlorine Compounds

PAGE NO.

4.4 The Standard of Accuracy Achieved in Year 2 of the External

Distributions

4.4.1 Nutrients

4.4.2 Metals in Water

4.4.3 Organics in Water

4.4.4 Sediments

4.4.5 Biota

4.4.6 Levels of Participation

5. NATIONAL MONITORING PLAN RETURNS AND PARTICIPATION IN

THE NMAQC SCHEME

5.1 Introduction

5.2 NMAQC participation and NMP returns for Laboratories

5.3 Conclusions

31

6. CONCLUSIONS AND RECOMMENDATIONS ON FUTURE STRATEGY 45

7. DEFINITIONS AND EXPLANATIONS OF TERMINOLOGY 51

8. REFERENCES 54

APPENDICES

2 . 1.1

2 . 1.2

2 . 2.1

2.2.2

2.2.3

2.3.1

2.3.2

2.3.3

2.4.1

2.4.2

2 .6.1

2.7.1

2 . 10.1

3.2.1

3.2.2

3.3.1

3.4.1

3.4.2

3.4.3

4.2.1

4.2.2

4.2.3

4.2.4

4.2.5

4.3.2.1

4.3.2.2

4.3.3.1

4.3.3.2

5.1.1

6.1

Role of the National Co-ordinating Committee

Role of Scheme Manager (FRPB)

NMP March 1994: List of determinands

Framework for laboratory AQC scheme

Overview of the NMAQC scheme

(1) - (8) Detailed Plan and Schedule of Year 2

(1) - (5) Determinand Groups for Year 2

(1) - (5) NMAQC Scheme - Error Thresholds •

(1) - (4) Mercury Workshop

(1) - (2) Organics in Seawater Workshop

Current NAMAS/BS 5750 Status

Participation in QUASIMEME

Documents circulated to Participants

NMAQC Scheme, NCC

Participating laboratories in the NMAQC Scheme

Year 3 Programme

Financial Report Year 2

Projected Finances for Year 3 and 4

Organisation approached re: membership

(1) - (3) Description of materials in distribution 5

(1) - (3) Description of materials in distribution 6

(1) - (11) Summary' of Laboratory Results: distributions 5 and 6

(1) - (7) Performance in Proficiency Tests: Years 1 and 2

(1) - (6) Reference Concentrations of Test Samples

Performance in Special Exercise: Metals

(1) - (4) Recommendations to laboratories arising from special exercise for the

determination of trace metals in water

Performance in Special Exercise: Organochlorine compounds

(1) - (6) Recommendations to laboratories arising from special exercises for

the determination of organochlorine compounds in Water

(1) - (2) Participation in distributions 3, 4 and 5

Overall Performance in years 1 and 2

GLOSSARY OF TERMS

AQC

ICES

MPMMG

BCR

DoE

FRPB

NRA

NLS

MAFF

NCC

RPB

SOAFD

DANI

PML

IOSDL

DOENI

IRTU

Paris Commission (PARCOM)

Annex 1A

NAMAS

GCSDM

NSTF

NMP

QUASIMEME

TON

LOD

WRc

JMG

Analvlica) Quality Control

International Council for the Exploration of the Seas|

Marine Pollution Monitoring Management Grcup

Bureau of Community Reference

Department of the Environment

Forth River Purification Board

National Rivers Authority

National Laboratory Service (NRA)

Ministry of Agriculture, Fisheries and Food

National Co-ordinating Committee

(Scottish) River Purification Board

Scottish Office Agriculture and Fisheries DepaJ ment

Department of Agriculture Northern Ireland

Plymouth Marine Laboratory

Institute of Oceanographic Sciences Deacon La

Department of Environment Northern Ireland

Industrial Research and Technology Unit

The body who implement the Convention fc'

Marine Pollution from Land based sources.

Annex 1A of the Ministerial Declaration of tht jThird International

Conference on the Pollution of the North Sea, 1

1990.

National Measurement Accreditation Service

Group Co-ordinating Sea Disposal Monitoring

North Sea Task Force

National Monitoring Plan

Quality Assurance of Marine Environmental M nitoring in Europe.

Total Oxidized Nitrogen

Limit of Detection

Water Research Centre

Joint Monitoring Group of the Oslo and Parisl lommissions

oratory

the Prevention of

he Hague, 8 March

1. INTRODUCTION

The requirements for and ihc establishment of the National Marine AQC scheme have been

discussed in detail in the Interim Report (March 1993), which was presented to the April 1993 meeting

of the MPMMG. This report, the second annual report to MPMMG, summarises the activities and

progress achieved during the second full year of ihc NMAQC scheme. Il also outlines and discusses

the proposals for years 3 and 4, making recommendations as appropriate.

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2. REPO RT O F THE NATIONAL CO-ORDINATING COMMITTEE

2.1 Functions and Role of the NCC and FRPB

At the first meeting of the NCC on the 18ih February 1992, the requirement for a secretary

and chair was agreed and Dr. M. Roberts (DoE) and Dr. M. A. Jcssep (Nottingham Laboratory

NRA) were ejected to Lhcse posts for a period of 2 years. These arrangements were reviewed

at 6th and 7th meetings of the NCC; elected officers would continue in post for a further year.

The role of the NCC and FRPB were formally agreed at the 1st meeting of NCC. These arc

dciailcd in Appendices 2.1.1 and 2.1.2.

2.2 Scope, Strategy and Development of the Scheme

In year 1 of the scheme NCC had, as per terms of reference, used the NMP determinand list

(Appendix 2.2.1) as the focus of the scheme for all QA activities. Dr. M. Service (DAN1) left

the NCC to formally chair the co-ordinating group which would set up, operate and manage

the biological AQC scheme.

The strategy adopted in Year 1 of the scheme (see Appendixes 2.2.2 and 2.2.3) was continued

with some development and extension into year 2. Since its inception, the NCC has

considered that an overall approach to quality assurance was required. To this end the external

scheme has been continued and extended to cover further determinands, special exercises have

targeted problem areas and workshops have been organised.

In addition the NCC has required that the in-house AQC performance of laboratories be

assessed to provide information on their continuing performance, against the back drop of the

external snap-shot exercises.

In line with this overall approach to quality assurance membership of NAMAS and BS 5750

has been encouraged, as have the links with other international schemes e.g. QUASIMEME.

The NCC has produced a policy document on ihc "Approach to Analytical Quality Control”

which dcscribcs the procedures lo be adopted to ensure that analytical systems arc properly

controlled. NCC will coniinuc to seek to ensure that participants implement these procedures.

The NCC has also provided much useful information to participants, in order to promote

co-operation and contact between laboratories.

Overview and 2nd Year Strategy for External Scheme

The objectives of the National Marine AQC Scheme are

(i) to monitor (and to provide a demonstration of) the standard of accuracy

achieved in laboratories which contribute data to the NMP

(ii) to assist in achieving improved accuracy and comparability, where necessary.

These aims are addressed through three types of activity:

a) proficiency tests

They provide a continuing check on comparability for the full suite as far as

practicable of determinands and matrices required for the NMP;

b) special exercises for important or "problem’1 determinands

These are a series of interlaboratory tests which are intended to assist in the

development of laboratories’ systems and in achieving an improvement in performance

where accuracy falls short of that required.

c) training workshops

Training workshops are organised to exchange information concerning best analytical

practices. The workshops are co-ordinated with the programme of special exercises.

-4-

An overview of ihe schcmc operation is shown in Appendix 2.2.2. Options for the sccond

year were discussed in May 1993. when it was agreed that:

Biola matrix samples should be added to all routine circulations

Routine distributions should be reduced lo 2 per annum

Special exercises for tracc metals in water; ammonia and TON; organochlorine

compounds in water would take place.

Additional dctcnminands were added to reflect NMP changes e.g. organophosphorus

compounds, triazine herbicides.

The detailed plan for year 2 and schedule is shown in Appendix 2.3.1 (1) - (8) and the

groupings of determinands, together with proposed concentrations is shown in Appendix 2.3.2

(1) - (5).

The levels of interest and performance targets for accuracy and precision for each determinand

are listed in Appendix 2.3.3 (1) - (5). Some minor adjustment to the former were made to

bring concentrations in circulated samples closer to operating or required operating levels.

These levels will be reviewed further when year 3 performance data becomes available, and

when NMP data is summarised and reported.

2.4 Workshops

The establishment of ad-hoc groups to examine in detail particular intransigent problems was

delayed until the results of initial exercises could be assessed. At the 6th meeting of NCC the

need for such groups was identified and two areas of concern targeted (a) mercury analysis

at low levels and (b) Organics analysis in water samples.

The mercury and Organics workshop were run at MAFF, Burnham-on-Crouch and Clyde RPB,

East Kilbride on the 24th/25th November 1993 and 6th/7th June 1994, respectively.

The general consensus of participants in these two workshops was that they were extremely

useful in highlighting problem areas and providing an opportunity for open discussion for

finding possible solutions. In addition they provide the one-to-one contact between analysts

which the NCC feels is essential if information is to be disseminated and problems overcome.

-5-

Dciailcd summaries of these two workshops is given in Appendices 2.4.1 and 2.4.2.

In-house AQC

NCC has concluded lhat information on status and performance of "in-house" AQC should be

collated and presented to MPMMG as part of the annual report, since the information from

the operation of the internal schemes gives a continuing view on laboratory performance and

supplements Lhe single shot information obtained from the external schemes.

Information gathering on the status of in-house AQC schemes was delayed until the external

scheme had been established; in 1993 a questionnaire was circulated. A proforma has been

designed to improve collation of the in-house AQC information. This proforma has been

circulated to laboratories and the returns from this exercise are being collated. Discussions

arc on-going as to how best to present this information for interpretive purposes. In future

such outputs will be of use to NCC and MPMMG for providing confidence in the data

returns.

NAMAS

The NAMAS accreditation scheme, run by the National Physical Laboratory (NPL) was

thought to have an essential role in ensuring long term quality assurance within UK

laboratories. The scheme is also recogniscd within ihe EEC and is equivalent to EN 45000.

In view of the workload involved in achieving accreditation, no timetable was set by NCC.

However, some progress has been made; a current status report is included as Appendix 2.6.1.

It should be noted that not all laboratories listed as having achieved NAMAS accreditation are

currently accredited for the determinands of interest at a level thought relevant to NMP

purposes.

Some laboratories/organisations are considering BS 5750 or GLP as alternative/additional

quality assurance schemes.

Q U A S IM E M E Links

The NCC has rccogniscd ihc need to establish links wiih and slimulaie collaboration wiih

international inicr-comparison exercises. Dr. D. Wells (SOAFD) has therefore been tasked

with presenting lo NCC status reports regarding ihc BCR initiative - QUASIMEME, and

formally attends all NCC meetings.

Several of the laboratories participating in the UK national scheme participate in the

QUASIM EM E schcmc (see Appendix 2.7.1). This should ensure cross fertilisation of ideas,

facilitate solutions to problems and help in the development of standard reference materials

where required. QUASIMEME has focused, initially, on sediment and biota matrices, with

the UK national scheme in Year 1 putting the emphasis more on the aqueous phase.

Through specific ad-hoc liaison meetings NCC, QUASIMEME and the contractor (WRc) have

established programmes of work that allow direct substitution of sediment and biota materials

derived from QUASIM EM E into the routine distributions of the UK National Scheme making

belter use of materials and providing a wider reference base for the data.

The organisation of workshops has been timed to follow publication of QUASIMEME

information with should serve as a useful starting point for discussions.

The production of specific reference materials for use in in-house AQC procedures has also

been promoted.

Sampling & Sample Handling

Sampling and sample handling have long been recognised as major sources of concern in

achieving good quality chemical information; the lower the range of interest the more marked

are the concerns in these areas.

Although the NCC had recognised these problems, it was considered at early meetings that

their resolution would require considerable effort and that the input of this effort should be

delayed until the externa! scheme was operational.

-7-

A draft Standing Committee of Analysis publication on this topic has been circulatcd to all

participants lor ihcir information. It is also intended to tackle this topic at the next workshop

in September 1994, in the context of trace metals in scawalcr analyses.

2.9 Analytical Methods

Following discussions wiLh Dr. Davies (SOAFD), NCC agreed that rather than adopt a recipe

book approach to mcihods of analysis, il would:

List the range of detection required for each determinand/matrix in cach area.

Rccommcnd suitable methods for cach determinand.

Recommend AQC procedures for cach determinand.

However, to provide an accurate picture would require examination of the information on

methods gathered from questionnaire returns together with results from several exercises, and

il was therefore agreed that in the interim NCC would produce data for LODs for each

determinand/matrix and a provisional list of methods. The collated report was issued to all

participants.

Although in general, the NCC concluded that laboratories, should not be constrained to a

particular method, exceptions to this rule were accepted for those determinands/determinand

groups where the result would be dependent on the manner in which the sample was prepared

e.g. particle size fraction, method of digestion of sediments for metals analysis, where

hydrofluoric acid has been defined as the required approach.

Although there has been considerable discussion on methodology at NCC meetings and in

particular at the workshops - the accumulation of firm scientific evidence on which to base

recommendations has proved a slow process and the NCC is not therefore in a position at

present to make firm recommendations for all methods. Specific observations for particular

determinand groups are detailed in section 6.2. »

2.10 Information

A list of documents circulated to all participants in year 2 of the scheme is shown in Appendix

2 .10.1.

-8-

.11 Confidentiality

Il was agreed hy NCC al the outset that it would be of benefit for progression of the scheme

for the results of the cxcrciscs to be freely available to all participating laboratories. However,

the NCC felt that it was essential that the information remained confidential to the group.

In the Appendices of this report the laboratories arc therefore identified by number.

-9-

3. MANAGEMENT OF THE AQC SCHEME - FRPB

3.1 Scheme Management

The UK Marine Pollution Monitoring Group (MPMMG) endorsed the need for a national

schcme at its 27th meeting. Subsequent discussions resulted in the Forth River Purification

Board (FRPB) taking on the task of administering the scheme and its finances on behalf of

the consortium, subcontracting by tender for AQC management. These arrangements have

been agreed to continue for year three of the scheme. The nolc and schedule of work for

FRPB are described in Appendix 2.1.3. This scction describes the actions and decisions that

have been taken in the second year to implement and develop the scheme for the third and

subsequent years.

To dale the NCC has met 10 limes, 4 of these being in Year 2. In Year 2 two further ad-hoc

meetings with the contractor and the QUASIMEME representative have also been held to

promote and improve links between ihe two schemes.

Day-to-day management of the scheme and its implementation is carried out by the FRPB.

Further formal liaison with the contractor lakes place through attendance of Water Research

Centre (WRc) representatives at NCC meetings. All distributions, reports and one-off

exercises in year two have been completed on schedule and within the original contract price.

Reports on ihe two routine distributions and the special exercises have been issued to all

participants. Feedback is reported to NCC via ihe WRc and FRPB for subsequent actions.

This report, a first year report and interim report have been prepared for MPMMG.

Liaison between MPMMG and the NCC is provided by the Chairman of NCC attending one

MPMMG meeting per year. Links with the international AQC exercise, QUASIMEME, are

provided through Dr. D. Wells (SOAFD, Project Manager) and with the DoE by the continued

attendance of Dr. M. Roberts as secretary to ihe NCC.

-10-

3.2 Membership

During ihc year the membership of NCC (see Appendix 3.2.1) has changed as a rcsull of

rclircmcni due to ill health or substitution of existing members. The commiuec retains

representatives from NRA, RPB, MAFF, SOAFD, DoE, DANI, DoENI and BGS.

Participation in distributions of samples within ihe schcmc embraces laboratories from all these

organisations with the exception of DoE. A full list of the 17 panicipants is given in

Appendix 3.2.2. Membership fcil between year 1 and 2 as a result of the rationalisation of

the N RA ’s laboratory service and ihc withdrawal of two RPB laboratories.

3.3 Contractor Review of Performance

Ai ihc 9ih meeting of the NCC on ihc 24th March, il was formally decided that ihc contract

for year 3 would be awarded to WRc.

A discussion of the performance of WRc as ihe coniractor during year 2 against the criteria

listed in the first annual report (MPMMG 93/12) confirmed an unanimous view that

performance had been good and retendering would not be appropriate.

The contract was formally awarded to WRc for year 3 starting on 1st July, 1994 with the

programme as described in Appendix 3.3.1.

3.4 Financial Arrangements

The financial arrangements for year 1 were reported in Lhe first annual report to MPMMG.

The balance of monies transfcrcd to year 2 was £3,918.34.

The second year financial summary is shown in Appendix 3.4.1. The second year membership

fee was set at £3500 per participating laboratory. One further laboratory, BGS, which

participated at a level of less than four groups of determinands contibuted a fee of £500. DoE

pump priming for year 2 of the scheme was contracted aL £10,000, reducing to £5,000 in year

3 and zero in year 4. The outturn for year 2 will be a significant surplus of £14,222.53, when

all expenses have been paid, which will transfer to year 3.

The projected financial positions for years 3 and 4 of ihc schcmc arc shown in Appendix

3.4.2. In year 3 ihe falling contributions from the national laboratory service of ihc NRA,

together with thai from the DoE has driven the surplus down 10 around £6,000. Thus in year

4, assuming ihc scheme continues as presently consliiulcd, a deficit in ihc region of £10K is

projccicd.

The principal focus of ihc NMAQC schcmc has been on mcciing the quality assurance needs

of ihc NMP. Invitations lo other UK laboratories 10 join ihc schcmc has met with a nil

response, rcflcciing iheir different, typically more specific AQC requirements (see Appendix

3.4.3). In year 3 further efforts will be made to recruil new participants, without prejudicing

the overall objectives of the schcmc.

On the basis of these projections it is reasonable to conclude that either funding needs to

increase, with new membership or a contribution from DoE or International source; a

reduction in scope for the overall scheme in year 4, or increased fees.

These options are discussed more fully in section 6.2.

Published Reports

During the year articles were prepared for publication in the Water Bulletin and Marine

Pollution Bulletin in order to publicise the wider aspects of the scheme. Two enquiries aboul

membership have ensued from these articles. A report on the scheme was also prepared for

inclusion in the 5th MPMMG report.

-12-

4 SU M M A RY O F RESULTS FOR YEAR 2 OF THE EXTERNAL SCHEME

4.1 Introduction

The overall schcmc has been designed to assess ihc accuracy and comparability of analytical

data produced by laboratories monitoring ihc marine environment; in particular where data is

to be used in the NMP. The overall scope of the schcmc has'been discusscd earlier in section

2. This scction dcscribcs the approach and laboratory performance in the external schcmc for

year 2.

The first year of the schcmc established laboratory performance for aqueous, sediment and

bioia matrices for 80% of the determinands in the NMP. In the 2nd year this was increased

to >90%.

4.2 Proficiency Tests

Two proficiency tests, Distributions 5 and 6, were carried out in year 2. Each of these

covered the determinands of interest - nutrients, metals and organic substances in water, metals

and Organics in marine sediments and in biota. Distribution 5 included three fish oil samples

for the determination of Organics (Appendix 4.2.1). Distribution 6 incorporated several

sediment and biota sample prepared for QUASIMEME, the European interlaboratory test

programme (Appendix 4.2.2).

The performance for individual laboratories in distributions 5 and 6 are detailed in Appendices

4.2.3 (1) - (11).

Appendix 4.2.4 (1) - (7) summarises laboratory performance for Years 1 and 2 of the scheme.

Data for saline and estuarine nutrients are included in the summary for "aqueous nutrients".

Results for tracc metals, including mercury are summarised under the heading "aqueous

metals". A ll organic determinands have been included in "aqueous Organics". Similar

groupings have been used for sediment and biota. Ragged results refer to those in error by

more than the relevant error threshold described in Appendix 2.3.3.

-13-

A summary of the samples distributed and their respective determinand concentrations is given

in Appendix 4.2.5 (1) - (6). The notes below summarise participation in the Schcmc and the

performance achieved in the proficiency tests.

4.2.1 Summary of Performance for Individual Laboratories for Year 2

Laboratory 03

Aqueous Determinands

Rcccivcd samples for metals and all Organics apart from PCP. Did not lake part for volatilcs

in Distribution 5 and for organophosphorus compounds in Distribution 6. No data for mclals

for Distribution 6; good comparability for metals in Distribution 5 apart from mercury

(negative bias) and chromium (no data). No data for Organics apart from HCH and volatiles

in Distribution 5 (good comparability).

Sediment Determinands

Good comparability for metals in the single exercise reported here. No data for As and Al.

For Organics, results reported for most determinands (apart from Aldrin, Endrin and Isodrin)

with fair comparability.

Biota Determinands

No flagged results out of the four which were reported for metals (no data for As). Good

comparability for Organics (15 flagged results out of 65). No results for a and J3 HCH,

op’DDT and HCB.

Laboratory 04


Received samples for all determinands and reported data for all sample/determinand

combinations, apart from organophosphorus compounds. Excellent comparability for nutrients

and Organics - improved performance and participation compared with Year 1. Poor

comparability for metals; between a third and half of results were flagged.

-14-

Scdimcm Determinands

Good com parahilily for mclals in ihc single cxcrcisc rcporlcd here (positive bias for Cr). No

data for As and Al. For Distribution 5 Organics, no data for PCBs 28, 31 and 52 and op’DDT.

Otherwise fair comparability - tendency lo positive bias. No daia for Distribution 6.

Biota Determinands

No flagged results out of four for metals (no data for As). Fair comparability for Organics (20

flagged results out of 65). No results for a and (3 HCH, op’DDT and HCB.

Laboratory 05


Received samples for nutrient only. Full participation and excellent comparability.

Laboratory 07


Received samples for all determinands except volatiles. A full set of data reported. Good

comparability for nutrients (improved over Year 1) and Organics - improved performance and

participation compared with Year 1. Excellent comparability for the Organics apart from some

"less than" values for organochlorines. Comparability for the metals generally very good

(deterioration in accuracy for mercury - improved LOD required, no data for chromium).

Sedimeni Determinands

Good comparability for metals in the single exercise reported here. No data for As and Al.

Good performance for Organics. Out of 38 possible results, there were 6 failures to report,

Isodrin and PCB 31 and op’DDT (one less than), and 6 flagged values.

Biota Determinands

Good comparability for metals, no data for As. Good comparability for Organics - 16 flagged

values out of 74 resulLs. No data for Isodrin, op’DDT, HCBD and PCB 31.

Laboratory 08

Sediment Determinands'

Good comparability for mcials lor ihc single sample, apart from negative bias for cadmium.

No data for As and Al. No data for Organics.

Biota Determinands

One flagged result out of four for metals. No daui for Organics in Distribution 6. Good

comparability for ihc three fish oils of Distribution 5, but no data for PCBs 28, 31 and 52.

Laboratory 09


Received samples for all determinands for Distribution 6 (new responsibility for monitoring

in water). Reported data for marine nutrients (ammonia and nitriie only in estuarine samples);

good comparability. For mclals, no data reported for zinc and chromium; many "less than"

values for low concentration samples. Poorer comparability for metals data. Full participation

for Organics with generally good comparability. Some < lng/1 values for HCBD, Isodrin and

Endosulphan in ihe low concentration sample. No data for TCBs.

Sediment Dcicrminands

Good comparabilily for metals in the single exercise reported; no results for Organics.

Biota Determinands

Full sci of five results for meials. Positive bias for Al. No data for Organics.

Laboratory 10


No data for nutrients. Poor comparability for metals in Distribution 5. Better comparability

for Organics (did not take pan subsequently).


Good performance for sediment metals, no data for Hg and As.

-16-

Biota Determinands

One flagged value (lead) o f the three metals reported. No Organics data.

Laboratory 11


Received samples for marine nutrients (Distribution 5) and marine and estuarine nutrients

(Distribution 6) and for all organic determinands. No data reported for nutrients. Full

participation for Organics with excellent comparability. Some organochlorine compounds arc

reported as less than values, though this is less prevalent in Distribution 6 (< for y HCH,

Isodrin and Endosulphan). No data for [3 HCH for Distribution 6.


A full set of data for metals. Positive bias for Cd, Cr and Al. Good performance for

Organics. Out of 38 possible results, there were 4 failures to report, PCBs 28, 31 and 52 (two

no result and two less than values), and 5 flagged values.

Biota Determinands

Two flagged values (Hg and As) out of 5 results. Good comparability for Organics, 12 flagged

results out of 68 values.

Laboratory 12


Received samples for all determinands. A full set of data reported. Excellent comparability

for nutrients (maintained from Year 1) and metals (improved compared with Year 1).

Comparability for the Organics better in Distribution 6 than 5, but good overall, apart from a

tendency for positive bias for organochlorine compounds.


Good comparability for metals for ihe single sample considered here (small positive bias for

Cr and Ni suggests a more vigorous digestion than other labs). Organics data reported for

Distribution 6, apart from PCB 31, Endrin and op’DDT (less than values for the last two).

PCB 28 positively biased by an amount corresponding to PCB 31.

Biota Determinands

Two fla tbed values (Pb and As) out o f 5 results. For Organics, 31 (lagged resuits out o f 78

values.

Laboratory 14


Received samples for marine nutrients, organochlorines and PCP. Poorer comparability for

nutrients than for Year 1. Data for Organics for Distribution 6 only; poor comparability (large

positive bias) because of a reporting error.


Seven out of 17 results flagged for Organics in Distribution 6. Positive bias. No data for

Isodrin and Endrin.

Biota Determinands

Good comparability for Organics in fish oil for Distribution.6, 2 flagged values in 20. No

results for Aldrin, Isodrin and HCBD.

Laboratory 15


Received samples for all determinands. A full set of data reported, apart from less than results

for mercury. Excellent comparability for nutrients (maintained from Year 1) Comparability

for metals was good (improved in Distribution 6 compared w'ith 5 - corresponding to a

reduction in limits of detection). Excellent comparability for Organics (improved compared

with Year 1).


No data for metals. Full set of results for Organics, apart from 3 less than values for PCB52

and Isodrin. Only one result flagged out of 35.

Riota Determinands

Good com parab ility lor Organics in fish oil lor Distribution f>, 2 flagged values in 22. No

result lor PCB 3 1.

Laboratory 17

Aqueous Dcicrminands

Rcceivcd samples for all dcicrminands cxccpt voiatilcs, triazincs and orga nophosphorus

compounds. The majority of results reported for nulricnts; improved comparability for

Distribution 6, compared with 5. For metals, no data for chromium and mercury. Good

comparability achieved for metals in Distribution 6. Good comparability for organochlorines,

apart from some "less than” values for lower concentration samples.


Fair comparability for metals in the single exercise reported here. No data for Hg, As and Al,

bias for Cd and Cr.

Biota Determinands

Three results reported for metals, one of which was flagged.

Laboratory 18


Rcceivcd samples for all determinands for Distribution 5. A full set of data reported. Good

comparability for the nutrients and Organics (apart from large negative bias for the

organochlorines). Poor comparability for the metals.


Good comparability for metals in the single exercise reported here (positive bias for Cd). No

data for As and Al. A full set of results for Distribution 5 Organics - good comparability (5

flagged results out of 19).

Biota Determinands

No data lor metals. Excel lent performance lor Organics in fish oil (5 nagged results in 63).

Laboratory 19


Received samples for all determinands apart from mercury, iriazincs and organophosphorus

compounds (these last two groups of dcicrminands were taken on a irial basis in Distribution

6, but no results were reported). A full scl of data was reponcd. Excellent comparability for

the nuiricnis. Good comparability for ihc mciats and Organics.


Good comparabilily for metals in ihc single exercise reported here (positive bias for Cr). No

data for As and Al. For Organics, data only for PCBs (not 31) with good comparability for

Distribution 5. more complete participation in Distribution 6 (no data for Aldrin, Endrin,

Isodrin, op’DDT and PCB 31). PCB 31 possibly reported with PCB 28.

Laboratory 20

Aqueous Dcicrminands

Rcccived samples for nutrients only. Full participation and excellent comparability (apart from

posidve bias for nitriie in Distribution 5).

Laboratory 21


Received samples for all determinands cxccpt marine nutrients for Distribution 5. Received

all samples exccpt marine nutrients and metals for Distribution 6. Good comparability for

estuarine nutrients for Distribution 5; no daLa for Distribution 6. Good comparability for

Organics (improved for Distribution 6 compared with 5).


Results reported for metals for Distribution 5, apart from Cd (less than) and Al. Reported less

than values for some organochlorines for Distribution 6.

Rinia Determinands

Al! results reported lor Distribution 6 lor Organics in fish oi! were positively hi used.

Otherwise no data.

Laboratory 23


Rcccivcd samples for nutrients, mcrcury and all organic determinands for Distribution 5.

Rcccivcd samples for nutrients and metals in Distribution 6. Full participation for nutrients;

comparability relatively poor for distribution 6. No data for metals or mcrcury. Organics data

for Distribution 5 of good comparability, apan from less ihan values (< 5ng/l) for low

concentration samples for the determination of organochlorine compounds.


Good comparability for metals in the single exercise reported here. No data for Al. No

results for Organics.

Biota Dcicrminands

One biased value (As out of the five reported for meials. Fair comparability for Organics

(Distribution 5 only).

-21-

4.3 Special Exercises

The purpose of ihc spccial cxcrciscs is lo assisi laboratories in improving ihcir standards of

accuracy. The regular proficicncy lesis provide an assessment of die standard of accuracy

achieved, but they arc usually insufficiently detailed lo allow the sources of any analytical

problems to be identified. Dcicrminands for which several laboratories do nol achieve the

required standard of accuracy arc considered as candidates for more imensive inlcrlaboralory

tcsis - ihc so-called spccial cxcrciscs. Such tests involve analyses of a range of different

standard materials and sample types. The results of the test can point 10 ihc source of

analytical error (e.g. calibration error, contamination or matrix interferences) and thereby

suggest an appropriate remedy.

Three types of special exercise were carried out in year 2 of the Schcme: ammonia and TON

(August 1993); trace metals (November 1993 and February 1994); and organochlorine

compounds (November 1993 and May 1994) - all for determinations in water. The tests on

metals and organochlorine compounds were repeated after an interval of several months to

allow participants to demonstrate the effectiveness of any remedial actions they had carried

out after the initial test. Progress in achieving the target accuracy for ammonia and TON was

monitored via the routine tests.

4.3.1 Ammonia and TON

Participants were asked to provide information concerning iheir methodology. A summary of

the principal sources of error for both determinands was circulated before ihe exercise. For

ammonia, blank correction, calibration and interferences caused by salinity were noted as

potential sources of problems. In the case of TON, the reduction of nitrate before its

determination as nitrite is seen as a likely cause of error.

The test was designed to cover the concentration ranges 0-30 pM for ammonia and 0-50 jiM

for TON. These ranges correspond to relatively uncontaminated samples. The nine solutions

distributed were chosen to help in identifying different sources of error, including those noted

above. Eleven laboratories reported results out of fourteen which received samples.

-22-

A number of laboratories demonstrated a high standard of accuracy for all the samples

distributed. All participants received a summary ol' their data and recommendations

concerning remedial measures, where necessary. The main problems encountered lor ammonia

were related to blank correction and matrix effects. In particular, ihcrc was a tendency for a

blank bias which increased wiih increasing salinity. Results from a few laboratories were

subjcci to a fixed blank error. The solulions lo these problems include application of ihc

calibration factor lo ihc blank and a salinity correction for blank determinations. The accuracy

achieved for TON determination was better than for ammonia, though some low recoveries

and biased blank values were noted.

The exercise served to illustrate some sources of error for the dcicrminands conccmed. A

number of modifications were made Lo laboratories’ systems and procedures. Subsequently,

in the latest proficiency lesi, the accuracy for these two determinands has been marginaJly

better, though the changes in participation and the fact that only one test has been undertaken

make it impossible to claim thai a substantial improvement has been achieved. A more

detailed follow-up tesi is planned for year 3 of the Scheme.

4.3.2 Trace Metals in Water

Two special exercises involved analysis of a range of sample types. These were intended to

provide an insight into the causes of analytical error and to suggest corrective measures.

Test Design

Eight filtered (0.2pM) samples (see below) were provided for the determination of trace

metals.

Samples A and B - standards in deionised water low and high, respectively.

Sample C - an unspiked seawater

Sample D - Sample C spiked high in the range of interest

Sample E - a spiked seawater (low to mid-range)

Sample F - Sample E spiked (medium to high)

Sample G - spiked estuarine sample (low to mid-range)

Sample H - Sample G spiked (high)

-23-

All unspikcd samples were analysed he fore ad di lions were made. The rcfcrcncc concern rations

are based on this low background level plus the spiked additions. Laboratories’ results were

compared with nominal concentrations obtained in this wav. The exception was the unspikcd

sample C, lor which a consensus mean (after rejection of outliers) was used.

Results

The level of participation and die performance of individual laboratories is summarised in

Appendix 4.3.2.1. The comments and recommendations made to participating laboratories in

both cxcrciscs arc given in Appendix 4.3.2.2 (1) - (4).

No determinand was subjccl to serious analytical errors in all laboratories, though there was

a tendency for the mean of laboratories’ results lo be lower than the nominal spiked

concentration for cadmium and for lead. Only two laboratories reported results for chromium.

These laboratories’ results were in good agreement with the nominal values.

The standard of accuracy achieved in the second exercise was better than in the first. This

is due to small improvements achieved by some participants, but also because the two

laboratories having the poorest performance in the first exercise did not take part in the second

(see Appendix 4.3.2.1). Of these two laboratories, one reported calibration problems and the

other has closed.

Il was evident, from a review of methods used by the more successful participants, that the

choice of method is noi the critical factor in meeting accuracy targets and that a wide range

of trace analytical techniques arc capable of adequat c performance.

There was no evidence in cither of the two tests for differences in the accuracy of results for

the estuarine and the seawaicr samples.

Conclusions

The two spccial exercises for the determination of trace metals in saline samples indicated that

at least four laboratories participating in the National Marine AQC Scheme are capable of

meeting the defined accuracy targets.

-24-

Only six laboralorics took part in both spccial cxcrciscs. A comparison between the level of

pa il ici pa l ion in the routine proficiency tests and that in the special exercises (Appendix 4.2.4

and 4.3.2.1) indicates that around half the laboratories providing data for the National

Monitoring Plan have demonstrated adequate accuracy or the capability to achicvc it. Data

from the five remaining laboralorics are nol supported by satisfactory performance in

intcrlaboratory icsls.

Recommendations

Lower reporting limits for several metals arc required, in particular for the determination of

cadmium and lead. Control of contamination and a small number of calibration biases also

require attention. Evidence from Distribution 6 suggests that several laboralorics have made

progress in this area.

Improved participation in AQC tests is required to support NMP data for the determination

of trace metals in water. The absence of satisfactory AQC data should raise questions

concerning the validity of data for any determinand. This is particularly true in the case of

the trace metals, where interlaboraiory tests have demonstrated that it is difficult (though not

impossible) to comply with the defined accuracy requirements.

4.3.3 Organochlorine Compounds

Two spccial exercises in November 1993 and May 1994 have involved checks on calibration

and recovery' tests for seawater samples.

Test Design

The following samples were provided:

(i) first test only - two standard solution (A and B) in methanol. These were to be

diluted with solvent and analysed directly (i.e. omitting any extraction step) as a check

on the accuracy of the instrumental calibration. Laboratories were informed that a

dilution of the stock standards by a factor of lOOx would produce samples of

concentration covering the range 0.5 to 15pg/l for the range of parameters of interest.

(ii) ihrc.c spiking solutions which were to be diluted with filtered seawater (also supplied)

lo provide three water samples which slum Id he analysed as if they were routine

samples (Samples (\ I.) and L).

(iii) 2L oT seawaicr spiked at WRc with a range of organochlorine compounds. This was

also lo be analysed as a routine sample (Sample F). This sample was identical to

Sample D.

Laboralorics were asked to carry out two full replicate determinations using ihcir routine

analytical methods (those used for production of NMP data).

Results

The level of participation and the performance of individual laboratories is summarised in

Appendix 4.3.3.1. The comments and recommendations made to participating laboratories in

both exercises are given in Appendix 4.3.3.2 (1) - (6).

The overall results of spccial exercises and the routine distributions for Year 2 are discussed

in more detail in section 6 of this report.

Conclusions and Recommendations for Routine Distributions and Special Exercises

In the first test six laboralorics reported results for this test, out of fourteen which received

samples (and eleven which might have been expected to take part). In the second test, eight

out of eleven relumed results, though only four laboratories took part in both exercises.

It was recommended at the end of the first exercise that participants should endeavour to

report results for all determinand/sample combinations and that the numbers of less than values

were too high (given that the determinand concentrations were within the defined range of

interest). In the second exercise, participants responded to this recommendation by providing

a more complete set of results.

-26-

In the second exercisc ihc standard of accuracy achieved by participants was high. The

incidence of llaggcd results was in the range 10-15%. No laboratory failed to mccl llie target

for a wide range of parameters. Large errors were more common for determinands for which

laboratories were less experienced, e.g. p HCH and Isodrin. Lowest numbers of results were

reported for the TCBs.

As laboratories’ control over their analytical systems is improved, it becomes possible to dctccl

smaller biases. The fact that a laboratory’s results for all five samples used in this test were

biased by the same amount, might be taken as an indication of systematic error in calibration.

On this basis, calibration bias appears to be an important source of error. The use of biased

standards might explain a small proportion of these problems. Other reasons, involving the

way in which the calibration is applied, arc more likely; for example, reliance on inappropriate

internal standard measurements or failure to control sensitivity changes.

The use of pre-spiked water samples for the determination of organochlorine compounds has

proved successful. Several laboratories obtained excellent agreement between the sample

spiked immediately before analysis and the sample spiked at WRc more than one day before.

This is a valuable indication that absorbed and dissolved determinand can be recovered from

’’real" samples. Further tests involving checks on recover}' from samples containing particulate

matter are recommended.

4.4 The Standard of Accuracy Achieved in Year 2 of the External Distributions

After six routine proficiency tests, the standard of analytical accuracy achieved by participants

is becoming clear. Improvements in accuracy in many laboratories have been achieved and

arc reflected in performances in both routine and special exercises. Conclusions regarding

performance in cach area arc outlined below.

4.4.1 Nutrients

For nutrient determinands, accuracy targets are met regularly by the majority of laboratories.

The series of interlaboratory tests fulfils the function of confirming adequate performance and

identifying any occasional lapses of control. Early difficulties with the two more problematic

nutrients, ammonia and TON, have been explored and, to a large degree, controlled.

-27-

Rccommendation - Nutrients

Maintain proficiency lesis and pay spccial ailcniion lo low level ammonia detenuination.

4.4.2 Metals in Water

The determination of trace metals in water has been shown to be the area where failure lo

meet the defined accuracy targets is most widespread. The spccial cxerciscs have confirmed

that different analytical techniques arc capable of being used with adequate performance. In

many cases, laboratories which experience problems are those for which there has not been

an established requirement for analysis al the low concentrations found in uncontaminated

marine samples. Improved limits of detection appear to be required for several metals. The

determination of mcrcury and chromium pose particular problems.

Recommendations - Metals in Water

(a) Measures already implemented in some laboratories to improve limits of detection

should be applied more widely.

(b) The techniques used for the determination of chromium and mercury should be

reviewed lo determine whether or not they arc likely to be capable of meeting the

defined accuracy targets. If not, then alternative approaches should be tried. Mercury

is to be the subject of special exercises in Year 3; a metals workshop is also

planned.

(c) Within-laboratory control chans should be established at concentrations relevant to

marine samples. (A regular programme of batches of analysis will help to promote

expenisc and good control over analytical systems).

-28-

4.43 Organics in Water

Initially, many laboratories experienced problems in the determination of trace organic

substances in waicr. There is a clear indication ihal accuracy has improved in individual

laboratories and generally, for the group of determinands as a whole. In the latest tests for

Organics, compliance with targets has been high. Three factors qualify lliis encouraging

picture. Firstly a number of "new" organic determinands have been introduced for which there

arc fewer analytical problems. This automatically makes the overall picture better. Secondly,

the type of samples used in the tests (spiked filtered waters) do not present all the potential

difficulties which may affect real samples, where the influence of particulate matter may be

important. Finally, the error threshold of 50% is less stringent than might be desired for many

data uses.

Recommendations - Organics in Water

(a) Laboratories should continue to improve Limits of Detection for trace organochlorine

compounds.

(b) Interlaboratory tests for other organic determinands need to be designed to use

samples which are as realistic as possible (consistent with adequate control over

sample homogeneity and stability).

(c) The list of determinands of interest should be reviewed in the light of monitoring data.

4.4.4 Sediments

The determination of metals in sediments has shown a small improvement in comparability

of results in Year 2 compared with Year 1, though fewer laboratories now take part in the

Schcme. A small number of laboratories have good control over the accuracy of results;

others show evidence of problems. The issue of defining the determinand of interest has still

not been translated into the required changes of sample preparation and digestion. However,

it is now appreciated that a total metal determination in a <2000 pm sample has been selected

for NMP purposes.

-29-

Thc determination of Organics in sediments has been addressed though ihc circul at ion of iwo

spiked sedimeni samples in Year two. A direci comparison \s.'i 111 Year 1 is complicated hy Ihc

changes in participation. In Year iwo, the incidence of flagged results was reduced. Only

four oul of eight laboratories reporting data for organic substances relumed results for more

than half of the required parameters.

Recommendations - Sediments

(a) Comparability of sample digestion for metals should be examined (spccial cxcrciscs

are planned).

(b) The effectiveness of extraction of Organics from sediments requires investigation.

Intcrlaboratory tests at relatively elevated concentrations should be maintained until

satisfactory accuracy is achieved by a larger number of participants. In the meantime

effort should be devoted to the characterisation and introduction of more realistic test

samples.

(c) Laboratories should ensure that adequate resolution is achieved in separating PCB

congeners. The reporting of PCBs 28 and 31 is a test of this resolution. Participation

for all determinands should be sought, especially for arsenic and aluminium.

Biota

Relatively little information has been obtained concerning the accuracy of the determination

of metals and Organics in biota samples. The available evidence indicates an improvement in

accuracy since Year 1 for both sets of determinands, with a greater number of participants for

Organics. Further assessments of capability arc to be made via the QUASIMEME programme.

Recommendation - Biota

Maintain assessments via QUASIMEME and devise test and control materials suited to

laboratories’ needs and capabilities. Extend participation to include all parameters - notably

PCBs 28 and 31, op’DDT and HCBD.

-30-

4.4.6 l.cvcls of Participation

Many of the laboralorics which took pun in ihc scheme lor the first year have changed or have

been replaced in ihc coursc of ihc sccond year. Againsl such a changing background, an

inicrlaboraiory AQC program provides a valuable indication of overall data quality. However,

ihe lack of a stable group of participants makes it difficult lo establish a co-ordinaicd approach

and to bring about demonstrable improvements in ihe accuracy achieved in individual

laboratories.

However, this AQC programme has served to indicate the areas and laboratories where

improvements arc necessary and Lhc type of action required. Some analytical problems such

as calibration bias arc corrccted relatively easily and quickly. Other sources of analytical error

cannot be remedied in a few weeks or months. For example, method development or the

purchase of new' equipment may not be possible in less than a year. This prompts two

conclusions. Firstly, a long-term commitment to a monitoring programme may be required,

if progress is 10 be made in achieving accuracy requirements and raising the level of analytical

competence. Secondly, effective co-ordination between laboratories and a common

programme of AQC. when combined with an emphasis on problem solving and exchange of

information, can make it possible to accommodate the changes which occur in the laboratories

taking part in a monitoring programme.

-31-

NATTONAL MONITORING PLAN RETURNS AND PARTICIPATION IN THF]

NM AQCSCHKM K

1 Introduction

Ai ihc 4th Ociobcr, 1993 meeting of ihc Marine Pollution Monitoring Management Group

participation in the National Monitoring Plan (NMP) and National Marine AQC Schcmc

(NMAQC) were discussed. MPMMC have agreed that all organisations providing NMP data

not subjcct to consistent monitoring wilhin the NMAQC scheme would be "flagged". In due

coursc ii may be necessary to provide a second "flag" to indicate where ihc data has been

subjcct to Lhc AQC schcmc but has failed to meet the performance standards required.

It was decided that a questionnaire should be circulated to all organisations contributing to the

NMP to ascertain their intended level of participation and to ensure that all those data

submitted to the NMP would be quality assured within the NMAQC scheme. Currently this

is only possible for the chemical determinands in the scheme. An equivalent biological

scheme has recently commenced.

This section describes the results from these two questionnaires. It assesses the consistency

of participation of organisations/laboratories in the NMAQC against their intended (required)

participation levels in the NMP. Any gaps between these two programmes are identified and

commented on. No comments are made regarding the performance levels of individual

laboratories against the accuracy targets for determinands as required by the NMAQC scheme.

These are detailed and discussed in section 4 of this report.

In section 5.2, each organisation, which may have more than one laboratory contributing

analytical results to the NMP, has been reported on. At the time of preparation for this report

only data for distribution 3, 4 and 5 were available. The level of performance of laboratories

wilhin the NMP and NMAQC scheme arc assessed for these distributions ONLY. The March

1994 version of the NMP has been used as the text for NMP information.

-32-

Appendix 5.1.1. (H - (?_) lisl the levels til' participation in the NMAOC scheme lor exercises

3, 4 and 5. ll has been assumed that a reluni (positive result or less ilian value) counis as

participation. Where repeated less than returns are made by laboratories, these arc referred

to in the following text. If laboratories have indicated that they arc contracting out analyses,

this is also referred to.

5.2 NM P returns and N M A Q C Participation

5.2.1 North West Region. NRA

NRA, North West Region are responsible for returns from 5 estuarine sites and, jointly, 2

intermediate sites within the National Monitoring Plan (NMP). No questionnaire return was

received to confirm that the region would be meeting this requirement. However, from other

sources it is clear that North West Region cxpect to achieve 80% of the NMP protocol for

year 1993 rising to 100% for 1994.

The Warrington and Carlisle laboratories had been participating in the NMAQC scheme up

until the autumn of 1993. The laboratories were closed at that time and all analyses

transferred to the Nottingham Laboratory of the NRA. For participation levels of this

laboratory in NM AQC see section 5.2.6.

5.2.2 MAFF

MAFF indicated that for NMP they would be reporting nutrients, and all other required

determinands (in the required matrices).

MAFF laboratories have participated in nutrients, metals (including mercury) and volatiles in

aqueous samples; sediment Organics and trace metals; biota Organics and trace metals

exercises. No chromium in seawater returns have been made. Recent returns for

organochlorines in seawater have only included y and a-HCH. No return for PCP or OPs

have been made. No arsenic returns for sediments have been made. Coverage of biota

Organics in returns has been good but excludes op-DDT, Aldrin, Endrin, HCBD and PCP.

None of these Organics are required by NMP.

-33-

Aqueous - chromium

HCB.

PCP

Tria/.incs - dependent on detection at estuarine sites

Organophosphorus compounds - dependent on

dclcclion at estuarine sites.

More frequent reporting for Hg and volatilcs.

Sediment - Arscnic

Biota - Arscnic

The Burnham laboratory reported that in distribution 6 they would participate for Cr in

seawater, HCB in seawater, iriazines in seawater and As in sediment/biota. Participation for

other determinands such as OPs in seawater and PCP in seawater would await results from

estuaries. The only outstanding determinands are therefore PCP in biota and Hg in seawater.

Analysis for PCP in biota should require the inclusion of at least two metabolites.

Forth RPB

FRPB indicated that for NMP they would be reporting all nutrients, metals and Organics in the

required matrices, but contracting the total sediment digests, together with arsenic analyses for

sediments and biota to SOAFD.

FRPB has consistently participated in the nutrients, metals (including mercury), OCs, PCP and

OPs exercises aqueous samples. Only one volatiles return has been made. Some OCs in

aqueous samples have not been reported, namely, HCBD, a-HCH, and the TCBs. Three of

the volatilcs have not been reported, dichioroethane, trichloroethane and tetrachlorethane. No

arsenic analyses for sediments or biota have been reported. Coverage of biota Organics in

returns is generally good but excludes a-HCH, PCB(28, 31), HCBD and PCP.

Thc following! list of deicrminnnds/mniriccs gives details of the currcni gaps in NMAQC

scheme participation. where p:uiicipmion is required bccause of ihc NMP reported

contribution.

-34-

Aqueous - HCBD, y-HCH, TCBs.

more consistent reporting of volatilcs.

DCB, trichlorocihanc and tctrachloroclhcnc.

Biota - oc-HCH, PCB(28, 31),HCBD, PCP.

5.2.4 DAN1

DANI indicaicd in their NMP Questionnaire return that all Nonhem Ireland estuarine and

intermediate sites would be compiled by the IRTU laboratory (DOENI); all offshore sites

would be samples, analysed and reponcd by DANI (NCI, NC2 and IS2).

DANI have participated in distributions for nutrients only in aqueous samples, sediment trace

metals, biota trace metals and biota Organics. For both sediments and biota matrices there

have been a number of missing returns. For sediments, no arsenic returns have been made;

PCBs 28, 31 and 52 have not been reponcd; PCP and op-DDT have not been reported. This

will mean that DANI will be required to add trace metals and OCs in seawater to their

analytical returns.

The following list of determinands/matrices gives details of the current gaps in NMAQC

schcmc participation, where participation is required because of the NMP reported

contribution.

Aqueous

Sediments

Thc fo llow ing lisl o f dcicrminands/mmriccs gives dcn ils of !hc currcnt g:ips in N M A Q C

schcnic participation. whciv participation is required ba';uisc o!' the NMP reported

contribution.

Biota

trace metals (inc Hg), OCs (inc PCP).

Arsenic

PCBs 28, 31 and more consistent reporting of 5 2 ,

101, 105, 118, 156, 180.

More consistent reporting of Aldrin, Endrin,

Dieldrin, pp-DDE and pp-DDD.

Arsenic

PCBs 28, 31 and 52; PCP and op-DDT.

-35-

CIvdc RPB

CRPB indicated that for NMP they would he reporting all nuirients, tracc metals and Organics

in the required mairiccs. a number of these requirements are lo be contracted out to other

laboratories, namely, volaiilcs and chromium aqueous samples lo FRPB and As in sediment

and biota samples to SOAFD. CRPB arc to analyses SOAFD’s trace metal aqueous samples.

CRPB have consistently participated in the nutrients, metals (including mercury), OCs, PCP

and OPs exercises for aqueous samples. No volatile returns have been made. No Chromium

returns have been made. Some OCs in aqueous samples have not been reported, namely

Trifluralin, HCBD and the TCBs. For sediments no arsenic or Organics resulted have been

reported. For biota Organics, no PCP, HCBD or PCB 31 resulis have been reported.

The following list of determinands/m alrices gives details of the current gaps in NMAQC

scheme participation, where participation is required because of the NMP reported

contribution.

CRPB reported that HCBD will be reported for waters and biota in future exercises.

Severn Trent Region. NRA.

Severn Trent Region NRA make no direct contribution to the NMP and participation was

limited accordingly, the returns in the NMAQC scheme from the Nottingham laboratory being

restricted to sediment and biota matrices. In the reported data for distributions 3, 4 and 5, the

reporting of OCs and PCBs for sediments has been erratic - no PCBs or OCs were reported

for distributions 3 and 5, similarly for biota. Full returns were made for sediment and biota

trace metals.

Aqueous

Bioia

Isodrin, HCBD, TCBs and Trifluralin.

more consistent reporting of all Organics required, in

particular Isodrin, op-DDT, PCB 31, PCP.

All Organics

-36-

\

5.2.7

The reorganisation of ihc laboratory scrvice within the NRA has transferred all North West

Region, NRA samples collected for NMI’ to the Nottingham Laboratory. The Nottingham

Laboratory will therefore be required lo participate fully in the NMAQC scheme.

The following list of dcicrminands/mairiccs gives details of the current gaps in NMAQC

schcmc participation, where participation is required because of ihc NMP reported

contribution.

Aqueous - nutrients, tracc metals, Hg, OCs, volatilcs, OPs.

Sediments - PCBs, OCs

Biota - PCBs, OCs

These gaps are now filled by full participation.

Northumbria and Yorkshire NRA

Returns for the NMP questionnaire indicated that the Northumbria and Yorkshire region would

be reporting all nutrients, metals and Organics in the required matrices, analyses being carried

out at the Washington laboratory for Northumbrian samples. The Yorkshire Region, NRA

elements of the NMP were analysed by Anglian Region NRA laboratory until it closed in

1993.

The re-organisaLion of laboratory services within the NRA resulted in the closure of the

Northumbria NRA Laboratory at Washington during 1993. Analyses previously carried out

at Washington have been transferred to the Leeds Laboratory.

Participation in ihe NMAQC schcmc by the Leeds laboratory has been as follows. For

aqueous nutrients, returns have been erratic; silicate has not been reported, ToN and nitrite

were not reported in distribution 4 and no nutrients were reported in distribution 5. Data for

nutrients returns has been produced using inappropriate methodology. In future, nutrients will

be contracted to another NLS laboratory’. For aqueous trace metals no return have been made;

these analyses will be performed at another NLS laboratory participating in NMAQC.

-37-

For the aqueous OCs. ihcsc have all been reported but in distribution 5. limits of dctcction

returns were made for most OC detenu inane Is. In distributions 3 and A. no OC’s or I’C'Hs weir

reported lor sediment or biota. This improved in distribution 5 with only PCP and PCB 52

not reported for the biota matrix and a full report for sediments.

The Leeds laboratory intend to continue participation for Organics in all matrices and trace

metals in sediment and biota.

The following list of determinands/matrices gives details of the currcnt gaps in NMAQC


contribution.

.2.8 Welsh Region. NRA

Welsh Region NRA indicated that they would participate fully in the NMP making returns for

all the required matrices.

Llanelli laboratory have participated in aqueous nutrients, trace metals, OCs, volatiles, PCP,

OPs and mercury distributions; sediment/biota, trace metals and Organics distributions. There

have been omissions for some of the suites of determinands within the scheme. For

distribution 3; no sediment PCBs. 28, 31, Endrin or pp-DDT and biota Cd, y-HCH, PCBs, 28,

31. In the sediment distribution 3, no PCBs, 28, 31, 105, 156, Aldrin, Endrin, pp-DDT and

pp-DDD were reported. In distribution 5, no returns were made for OCs or PCBs in

sediments; a-HCH, y-HCH, (3-HCH, HCBD and PCP were not reported for biota; Isodrin,

Azinphos-ethyl, Azinphos-methyl, 1, 3, 5-TCB and low level mercury were not reported.

This laboratory currently provides some support to other NRA laboratories for some NMP

analyses.

Aqueous

Sediments

Possible improvements in dctcction limits for OCs.

more consistent reporting of OCs and PCBs.

-38-

Aqueous - consistent reporting of OCs and OPs

Sediment - PCB 28, 31; Endrin, pp-DDT

more consistent reporting of OCs and PCBs

Biota - y-HCH

more consistent reporting of some OCs and PCBs

PCP

5.2.9 SOAFD

SOAFD has reported through the questionnaire that all NMP requirements will be met, with

the trace metal analyses in seawater being contracted to CRPB.

SOAFD have provided returns within the NMAQC scheme for low level seawater nutrients;

aqueous OCs; for distribution 3 sediment/bioia trace metals and Organics. No returns have

been made for tracc metals in seawater (inc Hg); No HCB on HCBD returns in seawater have

been made. For sediments and biota, no trace metal or Organics returns were made in

distributions 4 or 5, and in distribution 3, no As, pp-DDT, Aldrin, HCBD and PCBs were

reported.



contribution.

Aqueous - consistent reporting of OCs, PCP

Sediments - PCBs and OCs

Ni, Cr, As

more consistent reporting of trace metals

Biota - PCBs

more consistent reporting of OCs

As

Thc fo llow ing lis! o f determinands/m at rices t:ivcs details of ihe currcnt gaps in N M A Q C

scheme partic ipation . whcrr participation is ivquirvd Ivcausc ol' ihe N M P reported

contribution.

During distributions 4 and 5 the SOAFD laboratory was closcd down due to safety problems.

Il has now re-opened. The conclusions described above have ihe re lb re mostly been drawn

from distribution 3 reporting.

5.2.10 South Western Rctiion. NRA

Soutii Western NRA have indicated through the NMP Questionnaire return that they will

provide all data for their sites. There may be problems with collecting samples of flounder

or dabs as well as mussel samples at some sites in the Tamar for bioaccumulation studies.

The Exeter laboratory has participated fully in the aqueous distributions 3, 4 and 5. Only the

low level mcrcury reports, which arc all less than values and some missing reports for Zn, Cr

(distribution 3) and op-DDT, trifluralin, total endosulphan, TCBs and dichloroethanc arc not

meeting requirements.

For distribution of sediment and biota, no reports of trace metals or Organics in biota have

been made and no sediment trace metals reports. The sediment Organics reports in distribution

3 were all less than values; distributions 4 and 5 comprised a full set of results for Organics,

cxcept for one less than PCB 52 value.

The Exeter laboratory contracts its sediments and biota to another NLS laboratory providing

NMAQC cover.



contribution.

Biota

Sediments

Aqueous low level mercury

consistent reporting for trace metals

consistent reporting for op-DDT, TCBs, Trifluralin,

Total endosulphan, dischloroethane at actual levels

rather than less than values.

all samples are contracted out, therefore no gap

trace metals and Organics

-40-

5.2.11 Tav RPR

The NMP questionnaire reium from ihe 'l ay KPB indicated that ihey would be providing daia

on all aqueous samples, including saline chromiums which would be done by Forth RPB; all

sediment, analyses were to be contracted to SOAFD; all biota analyses would be carricd out

by Tay RPB.

The Tay RPB laboratory have provided returns wilhin the NMAQC scheme for estuarine

nutricnis, aqueous tracc mclals and OCs. aqueous PCP and scdimeni/bioia trace metals. Only

sediment iracc mclals (Cu, Pb, Cd, Zn. Ni and Cr) have been consistently reported for all three

distributions.

The aqueous returns have been inconsistent, for example, no returns were made for distribution

5; no volaiiles returns were made for distributions 3 and 4; reporting of nutrients was erratic.

For sedimenis only the tracc mclals Cu, Pb, Cd, Zn, Ni and Cr were reported. Only one biota

return for trace metals was made in distribution 5.

The following list o f dctcrminands/matrices gives details of the current gaps in NMAQC


contribution.

Aqueous low level nutrients

more consistent reporting of estuarine nutrients

volatiles, PCP

Cr, Hg

Sediments none

Hg, As, more consistent reporting of other trace

metals

OCs, PCBs, PCP

Biota

-41 -

5.2.12 Anglian Region NRA

The NMP questionnaire return indicated lhai Anglian region would be providing data on all

aqueous, sediment and biota matrices as required in the plan. These analyses were previously

provided by the Anglian laboratory and arc now provided within the NRA’s National

Laboratory Scrvice. The saline nutrients arc currently being analysed by Llanelli laboratory

and all the remaining analyses arc to be done by Fobncy Mead (Reading) laboratory NRA.

The Anglian NRA laboratory' in the return to date has provided returns for a very wide range

of the determinands in the NMAQC scheme. However, the laboratory has recently closed and

it is now therefore not appropriate lo use their data for quality assurance purposes other than

for historic reasons i.e. assessment of 1992, 1993 performance.

Llanelli laboratory currently participate fully in nutrient distributions. However, there are a

number of significant gaps for the Fobncy Mead laboratory. These are described in section

5.2.14.

5.2.13 Industrial Research and Technology Unit fDoENI)

Returns for Lhe NMP questionnaire indicated that IRTU would be responsible for returns for

aiJ estuarine and intermediate sites. All biological analyses for Organics and trace metals

would be carried out by DANI laboratories.

The returns in the NMAQC scheme for the IRTU laboratory' have included aqueous nutrients,

trace metals, organochlorines, volatiles and PCP, only OPs have not been analysed for.

Sediment Organics and trace metal returns have also been made, but no biota returns. Over

the three distributions there have been the following omissions; for aqueous matrices, the

occasional ammonia or silicate result, no Cr results, all Hg results have been "less than"

reports, occasional "less-than" reports for Cd, Cu and Pb, HCBD, CHC13, PCP results have

occasionally been missing, all OPs were not reported in distribution 5, finally a number of the

OC results in distribution 5 were reported as "less than" values. For sediments no As results

have been reported, PCBs 31, 105 and 52 were either not reported or reponed as "less-thans",

Drins and DDT isomers were not reported in distribution 5.

-42-

The fo llow ing 1 isi o f determinands/m nlrices gives dcinils of ihc currcnt gaps in N M A Q C

scheme pariieipniion. where p;inicipalion is fctjiiirccl hee;mse of ihe NMP reported

coniribuiion.

.14 Thames Region. NRA

In the NMP questionnaire return, Thames NRA indicated that they would only be supplying

data for water and sediment matrices.

Fobney Mead (Reading) laboratory NRA have provided returns for all determinands in the

NMAQC schcmc except low level seawater nutrients. For the three distributions there have

been however, many inconsistencies in returns for a significant number of the determinands.

For aqueous determinands, no nitrite returns have been made, "less than” returns have been

made for PO/\ Hg, Pb, Ni, no chromium or zinc returns have been made, for Organics "less

than" values for CHC13, CC14, PCP, HCBD, some of the isomers of TCB have not been

reported. For biota no metals or Organics were reported for distribution 5; for distribution 3

no Zn, As or PCB 180 results were reported and ’’less than" returns were made for PCBs 28,

31, 52. For sediments, no returns were made for distribution 4; for distribution 5 no OCs or

As returns were made; for distribution 3, no As and "less than" values were reponed for Cd,

Drins, PCBs 31, 138, 153, 180, pp-DDD.

Aqueous

Sediments

fuller reporting of ammonia, silicate analyses

Cr, Hg (belicr dciection limits)

Cd, Cu, Pb * more consisleni reporting

HCBD, CHCI? and PCP - more consisicnt reporting

OPs

Dicldrin, DDT isomers, 1, 2, 3 -TCB

1, 2 Dichlorocthanc,

Total cndosulphan, trifluralin - more consistent

reporting.

As better detection limits for Cd

PCBs 31, 105, 52

More consistent reporting of Drins, DDT isomers

The reorganisation of laboratory services in ihc NRA and ihc formaiion of ihc National

Laboratory Service lias resulted in a rationalisation of the sample analysis programme. All

sediment, bioia and aqueous iracc mclal analyses for Thames NRA arc now to be done at the

Waterlooville laboratory; Organics will continue to be carried out at Thames except for the

sediment matrix data, which will be provided by the Exeter Laboratory NRA.

The following list of determinands/matrices gives details of the eurreni gaps in NMAQC

schcmc participation, where participation is required bccausc of the NMP reported

contribution.

Aqueous - low level nutrients, Nitrite.

better detection limits forCHCl3, CC14, PCP, HCBD,

TCB isomers.

Sediments - all samples are contracted out, therefore no gap.

Biota more consistent reporting of OCs.

better detection limits for PCBs, 28, 31, 52, 180.

.15 Southern Reeion NRA

No questionnaire return was received from Southern Region. It is therefore assumed that the

NMP returns for the three estuarine and one intermediate will be made by the Region.

Waterlooville laboratory is also contracted to carry out Thames and Anglian Region NRA,

sediment biota and trace metal analyses.

Watcrlooville laboratory,. NRA have participated in only one of the three distributions for

aqueous, biota and sediments. In distribution 5 all determinands with the exception of

sediment Organics and seawater tracc metals were analysed for and returns made. There were

also a significant number of "less than" values reported for the low level OCs in aqueous

samples and some in the high level OC returns. For biota PCBs 31, 105, 156 and PCP were

not reported.



contribution.

Aqueous seawater trace metals Tine Hc>

better detection limits tor OCs.

more consistent participation for each distribution,

generally.

Sediments OCs

more consistent returns for each distribution

more consistent returns for cach distributionBiota

better detection limits for PCBs, 28, 31, 105,156, PCP

CON CLU SION S

For the NMP and NM AQC questionnaire returns the following observations can be made:

Most laboratories arc consistently providing returns to the NMAQC scheme, as

required by their NMP commitments for nutrients in seawater, trace metals in

sediments and biota.

Generally, there is an inconsistent pattern in the returns of laboratories for other

determinands, especially PCBs and OCs in sediment and biota.

Generally, returns for ihe recently introduced OPs in seawater were comprehensive

and consistent.

Some determinands for example, As in biota and sediments; PCP in biota, PCBs 28,

31 in sediments and biota; low level mercury; are either not reported or reported by

only a few laboratories.

Rationalisation of the laboratories within the NRA to set up the National Laboratory

Service has resulted in the loss of a very high performing laboratory. It has also

resulted in some cases in the redistribution of samples to NRA laboratories, a

coasequent reduction in the number of participating laboratories, and the need for the

NRA to reassess its participation in the scheme.

Temporary' closure of one of the Government laboratories has resulted in an almost

complete absence of data for one laboratory.

CONCLUSIONS AND RECOMMENDATIONS ON FUTURE STRATEGY

The NMAQC schcmc which commenced in 1992 has been successfully mainiaincd through

a sccond year and a contract has been set for year 3.

The sccond year of the contraci included determinands additional to those included in the first

year. The number of determinands now eovcrcd in the NMP has increased from some 80%

lo greater than 90%. The additional determinands were the organophosphorus pesticides,

triazinc herbicides and sclcctcd volatiles for estuarine samples.

A review of overall performance of laboratories over the two distributions in year 2 compared

with the four distributions in year 1 is shown in Appendix 6.1. When these are assessed

against the two criteria established in year one i.e.

60% of NMP determinands analysed for.

80% pass rate on those reported.

it may be seen that overall performance has been maintained and some improvements

recorded. A critical assessment of this information has been made more difficult by the

reorganisation of the NRA laboratory service and the temporary closure of one Government

laboratory. This has led to lower participation in some instances e.g. laboratory 18’s

participation fell from 87.7% to 56% because of the closure part way through the year;

similarly laboratory 14 which was temporarily closed where participation fell from 38.7% to

17%.

However, the pass rate has improved in most laboratories. Specific performance for individual

determinand groups is described below.

-46-

The standard of required accuracy for nutrients has been met by the majority of laboratories.

For trace metals in seawater, failures against the required standards was most widespread. A

small corc of laboratories that routinely analyse samples at low tracc metals concentrations

performed as required, however, particular problems still persist for chromium and mercury.

For these 2 determinands there is an urgent need to improve performance if meaningful data

is to be available within the NMP. Improvements in the determination of trace Organics in

water, both overall and for individual laboratories were recorded; the new organic

determinands introduced in year 2 presented few analytical problems. Similar improvements

for the determination of metals in sediments were observed, though participation numbers are

low. The determination of Organics in sediments has established a baseline for performance

o f laboratories. Finally from the comparatively small amount of data for metals and Organics

determinations in biota, it can be tentatively concluded that accuracy has marginally improved

in Year 2 relative to Year 1.

As NMP progressed and developed, further additions have been agreed for year 3, namely the

inclusion of dichlorovos in water, azinphos-ethyl in water, Chlorophyll-a in water and organic

carbon in sediment.

A small number of determinands are currently not included in the NMAQC but are required

to be analysed for in NMP. These are detailed below;

TBT in water/biota - very few laboratories analyse for this determinand in these

matrices. It may be more appropriate to adopt a one laboratory approach for this.

PAHs - similar conclusions as those for TBT.

PCBs (128, 170) in biota/sediment. These were added to the NMP during the year.

It was deemed preferable to demonstrate control over current determinands rather than

expand list at this stage.

PCP in biota - very few laboratories analysing for this. In addition, it has been shown

that PCP metabolises in biota and it would be necessary to look for the metabolites,

as well as PCP.

During year 2 of ihc schcmc ihc links with ihc international AQC schcmc, QUASIMEME,

were maintained and developed. The principal purposes in such liaison were lo ensure

dissemination of information on common problems wilhin both schcmcs, to rcducc 10 a

practical minimum "dual" analysis for laboratories in both schcmcs and to ideniify common

areas of interest e.g. production of reference materials, where benefits in working together

could accrue. In year 2 ihcsc arrange menus were reviewed and specific problems identified.

Through ad-hoc meetings, a simpler set of arrangements with QUASIMEME have been agreed

for liaison in Year 3, namely;

Reporting deadlines between the two schcmcs will be standardised, as far as

practicable.

Single instruction sheets will be issued to cover both schemes.

Collation of responses, as far as the laboratory is concerned, will be through one

agency.

These arrangements will be kept under continuous review through both NCC and further ad-

hoc meetings. Through these arrangements the long-term relationship between the

QUASIMEME scheme, which is funded up until March 1996, and NMAQC have been

explored. The proposals for QUASIMEME II for 1996-1999 are currently being developed.

Every opportunity will be explored to ensure that the UK national scheme and QUASIMEME

develop and meet the needs of their participants without prejudicing either scheme.

The detailed programme for year 3 therefore consists of two routine proficiency tests, which

have been scheduled to occur over 4 distributions, in order to spread the impact on

laboratories, in particular those with smaller volume turnovers. There will be further

distributions for special exercises on nutrients (ammonia and TON) and organochlorines/metals

in seawater to maintain the year 2 programme. The special exercises will be extended to

include mercury in water and metals in sediments (to include a review of digestion

procedures). In addition there will be workshops on trace metals in seawater (inc Cr) and

sediment/biota trace metals analysis. These will follow up on the special exercises and

information feedback from similar exercises in QUASIMEME. These workshops are seen as

an ideal opportunity for the analysts to present and discuss mutual problems and to agree

possible improvement action plans.

In year 2 a document, endorsed by NCC, outlining the preferred approach to in-house AQC

was issued to all participants. As a follow-up NCC is now collating the returns from

participating laboratories describing Uieir in-house AQC data. This approach is viewed as

providing an essential ’’continuum" of evidence on the quality of marine analysis, to reinforce

performance "snap-shots” from the routine distributions and other exercises. The assessment

of in-house AQC data will be extended in year 3.

In a broad sease, NCC as part o f the overall quality assurance strategy, has encouraged the

participants lo seek NAMAS accreditation or BS 5750 certification. It is encouraging to note

that significant progress has been made during the year on this issue with a greater percentage

of laboratories cither NAMAS accredited or in the final stages of applications. NCC will

coniinue lo encourage adoption of formal quality assurance schemes.

Regarding analytical methods, a number of observations are possible. For nutrients, the

methods in use in laboratories can provide adequate quality data. Similar conclusions can be

drawn for all the other determinand techniques, used for metals and Organics in water.

Exceptions to this general observation might include the methods for mercury and to a lesser

extent chromium which still present significant problems. Urgent action is required in this

area if appropriate quantities of reliable data are to become available for the NMP.

During the year, again as part o f the overall approach to QA, NCC have circulated information

on sampling and sample preparation, chemical methods and various NMP related publications.

The planned workshop of trace metals in seawater will cover sample preparation and sampling.

The preparation of bulk-reference materials for routine use in laboratory AQC has also been

progressed. It is planned that a bulk sediment will be available to participants in year 3 for

trace metal and organic determinands.

A contract has been set with WRc for the operation of the scheme in year 3. The funding

arrangements for years 2 through to 4 are discussed below.

-49-

Thc accounts for year 2 of the schemc (July 93 - June 94) have now effectively closed with

a surplus of 114.222.53 being earned forward lo Year 3. Financial projections for year 3

(July 94 - June 95) suggest a surplus of funds in the region of £6,0()0; and for year 4

(July 95 - June 96) a shortfall of around £8 - £10,000.*

The changc around in the financial position of the scheme is due to a combination of factors;

1. The reducing membership of the scheme from 21 laboratories to 17 as a consequence

of reorganisation of the NRA’s laboratory service and withdrawal of two RPB

laboratories.

2. The reducing level of stan-up funding from the DoE.

Year 1 funds from DoE £15,000



The cumulative effect of this, presuming no other change, will be that the scheme will become

non-viable in it present form in year 4. There are a number of options available to the NCC

which, if implemented, would prevent this happening. These options are;

1. Reduce the overall scope of the scheme, hence reduce the cost Projected costs for

year 4 are £58,000.

2. Increase the membership fee from £3,500 to cover the overall cost of the scheme.

The rise in fee would have to be around £750 - £1,000.

3. Recruit more members to the scheme.

4. Continue a contribution from DoE or international sources.

Option 1:

It would seem ill-advised to reduce the overall scope of the scheme at this stage, having just

set up the scheme for >90% of NMP determinands and with tangible benefits starting to be

achieved.

-50-

Options 2 and 3:

Several approaches lo new members for ihc scheme have been made (sec Appendix 3.4.3).

The laboratories approached have been in both the private and public sector, some have shown«

definite interest in joining at a "lower level" than full membership. One laboratory has shown

interest in joining at the full membership fee. Approximately 2 full members would be needed

to ensure continued operation of the schcmc. A steep rise in the fee by up to £1,000 is

unlikely to cncouragc new membership and could result in currcnt members reviewing their

participation.

Option 4:

A continuation of the present level of funding i.e. £5,000 per year would be required to ensure

the viability of the scheme into and beyond year 4.

In conclusion, although the funding of the NMAQC scheme is in place for year 3, year 4

funding is uncertain. A number of options are available to NCC to remedy this situation.

Reviewing all four options, it would seem reasonable to recommend that MPMMG should;

approve the present scope and overall direction o f the overall programme,

encourage additional membership of the scheme through any means at its disposal.

The two remaining options 1 and 4 require further consideration by NCC and DoE. NCC will

review the membership fee during year 3 and set a level, it feels appropriate to ensure

continuity of the scheme. To some extent this will depend on the outcomes from the other

options. Regarding possible funding from DoE (or International sources), these are currently

under investigation.

Finally, returns from Questionnaires concerning the level of participation in the scheme against

that required by the NMP have been collated and the findings summarised (section 5). This

information can be used to ensure that data submitted for NMP purposes is subject to the

rigors of the NMAQC scheme and that required performance standards are being met; all data

provided for NMP purposes not complying with these requirements would be flagged.

-51-

7. DEFINITIONS AND EXPLANATIONS OF TERMINOLOGY

The purpose of Analytical Quality Control (AQC) cxcrciscs is lo ensure lhat analytical

performance is within the statistical variation set. To determine these errors, measurements

of precision and bias arc made.

In the statistical calculations made on the results it has been assumed that the distribution of

random errors follows the normal (Gaussian) distribution. This allows prediction of the

expected magnitude of the analytical errors from the standard deviation of the results.

Terms used in Precision and Bias Calculations

Below are brief explanations of the terms used in the AQC precision and bias calculations.

A fuller discussion can be found in Water Research Centre NS30 ’Manual on Analytical

Quality Control for the Water Industry’.

Batch of Analysis

An operational terni used to refer to a series of determinations which have been made on a

single occasion or under broadly similar experimental conditions. A batch is usually taken to

refer to analysis for which a given calibration applies.

Precision

The degree of agreement existing between repeated measurements on the same sample made

under special conditions. Precision of results (or rather lack of it) is usually expressed in

terms of standard deviation).

Bias

Systematic error - a consistent difference between the mean of many results and the true value.

Total E rror o r ’A ccuracy’

This is a combination of the precision and bias errors and is the total error on an analytical

result. It is not strictly possible to add random and systematic components of error (one

measured in absolute units and the other being standard deviation-based), but an estimate of

the maximum error can be obtained from a linear combination. If the normal precision and

bias targets of 5% relative standard deviation and 10% bias are taken, the total error on any

one result could be 20% (10% from the random errors and 10% bias).

Control Sample

A sample which is analysed for quality control purposes.

Level of Interest

The concentration or value which is used as an assessment of analytical results. The level of

interest usually corresponds to a statutory limit value or 10 times the required Limit of

Detection.

Total Standard Deviation

The standard deviation of individual results selected at random from any batch of analysis.

Total standard deviation comprises components of both within and between batch random

error; it is intended to be a measure of all the elements of random error which might affect

the results.

Within-batch Standard Deviation

The standard deviation of results obtained by replicate determinations in single batch of

analysis. It is a measure of short-term random error.

Bciwecn-haich Standard Deviation

The standard deviation of results obtained by replicate determination in different batches of

analysis. It is a measure of longer-term random error.

Statistical Control

The condition where sources of random error affccting analysis arc consistent. When a state

of statistical control is achieved the measurement process can be thought of as stable,

predictable and free from unexpected sources of error.

Test Control

A sample analysed for purposes other than analytical quality control.

Limit of Detection

Limit of detection should be estimated by following the guidance giving in NS30. In

summary LOD is based on 4.65 aw, where ow is the within batch standard deviation of blank

determinations, an estimate of aw , Sw, is obtained in the precision tests. The factor 4.65

corresponds to 2.2t, where t is the value for the student’s t statistic for the chosen probability

level of 0.05 and an infinite number of degrees of freedom. The value for t used in practice

should be modified accordingly to the number of degrees of freedom associated with Sw. For

example, with 11 degrees of freedom LOD is 5.1 Sw.

R EFER E N C E S

Chccscman, R. E. Wilson revised by Gardner, M J 1989 - A Manual on Analytical Qualily Control

for the Water Industry - WRc Report no. NS30.

ACMP 1989 Report (ICES 1989).

National Marine AQC Scheme - Marine Methods Report in Preparation.

Interim Report on the National Marine Analytical Quality Control Scheme 1992/93. March 1993. Dr.

M. A. Jessep and Dr. A. Griffiths.

Report on the National Marine AQC Scheme 1992/93 (MPMMG 93/12).

APPENDIX 2.1.1

ROLE OF TH E NATIONAL CO-ORDINATING COMM ITTEE (NCC)

The functions and role of the National Co-ordinating Committee for the national marine AQC scheme

are as follows:-

Define what services are required

Interact with FRPB as managers of the contract.

Review other organisations/laboratories that should be approached to join the

scheme.

Agree and set an annual budget and itemise contributions from individual

participants.

Assess the funding requirements of FRPB to service the scheme and the NCC.

Develop all necessary definitions.

Develop and document an overall plan for the scheme.

Receive and review reports from participating laboratories on any problems

arising from internal and external AQC exercises.

Receive and review reports from the FRPB on the management of the scheme.

Establish the frequency and location of committee meetings.

Receive and review reports from the tendering organisation on AQC exercises.

As necessary, establish ad-hoc groups to address problems as they arise and

provide members to chair each sub-group.

Produce an annual report, which will be presented to MPMMG and DoE for

information.

Establish links and stimulate collaboration with international inter-comparison

exercises.

Encourage NAMAS accreditation and co-ordinate in-house AQC policy.

Make recommendations and receive reports from participating laboratories on

in-house AQC.

Establish a timetable and dates for reports.

APPENDIX 2.1.2

RO LE OF THE FORTH RIVER PURIFICATION BOARD

OBJECTIVES

1. To establish a managed national marine analytical quality control scheme.

2. To co-ordinate the in-house AQC policy of participating organisations on a national basis.

3. To recommend and, where necessary, produce appropriate quality materials.

4. To manage the schemes finances.

SCHEDULE OF WORK

1. Provide secretarial and operational support for the National Co-ordinating Committee.

2. Implement the plan for the national AQC Scheme.

3. Audit and report to the Committee on the planned work programme.

4. Receive and manage funds donated by participating members of the AQC consortium.

5. Co-ordinate with the Committee the content of the tender document, put it out to relevant

laboratories, evaluate tenders, provide a report with recommendations to the NCC and set the

contract.

REPORTS

Provide progress reports to the NCC for each meeting with a longer and fully documented annual

report. Every publication from the work should acknowledge all consortium contributors.

f APPENDIX 2.2.1

Analytical Requirements

D e t e r m i n a n d

C o d e U W F W

M a t r i x & U n i t s

S S S F F M F L

M e ta lsAi (Aluminium) AL - * mg/kg - - *Hg (Mcrcury) HG - ng/1 PfA g mg/kg mg/kg -Cd (Cadmium) CD - ng/l MfAg mg/kg - mg/kgCu (Copper) CU * Me/* mg/kg - - -Pb (Lead) PB - M&/1 mg/kg mg/kg - mg/kg

Ni (Nickel) NI - Pg/1 mg/kg - - -Zn (Zinc) ZN - Pfi/1 mg/kg mg/kg - -As (Arsenic) AS * - mg/kg * mg/kg -Cr (Chromium) CR - Me/1 mg/kg - - -

TBT (Tributyl tin) TBTIN ng/1 - fJg/kg mg/kg - -[in conjunction with Dogwhelk survey - See paragraph 8]

Organic CompoundsPCB (Polychlorinated biphenyls) CB28,CB52^ic - - Pfi/kg Pg/kg - Pg/kg

[congeners: 28,52,101,105,1 J8.128.138,]53.156.170,180} 'cx-HCH (A Ipha-hexachJorocyclohcxane) HCHA ng/1 - - Pg/kg - -fl-HCH (Beia-hcxachlorocyclohexane) HCHB ng/1 * - - - -

[estuarine sites only]y-h c h (Gamma-hexachlorocyclohexane: Lindane) HCHG ng/1 • - P£/kg - -

Dieldrin [Unfiliered Water: estuarine sites only] DIELD ng/1 - Me/kg Pg/kg - Mf^kgAldrin [estuarine sites only] ALD ng/1 - HE/kg Pg/kg * pg/kgEndrin [estuarine sites only] END ng/1 - ME/kg Pg/kfi - Pg/kgLsodrin [estuarine sites only] ISOD ng/1 * - - * -

HCB (Hexachlorobenzene) HCB ng/1 - M£/kfi Mg/kg - *PCP (PentachJorophcnol) PCP ng/1. - • pg/kg * -DDT (D ichlorod ipheny ltrichlorocthane ) TDEPPJDDEPP - - ME/kfi pg/kg - PC/kg

[pp TDE, pp DDE, pp DDT] DDTPPop DDT [estuarine sites only] DDTOP ng/1 - - - - -

HCBD (Hexachlorobutadiene) [estuarine sites only] HCBD ng/1 - - M&/kg * -

I Priority Hazardous Substances to be analysed on UnfiUered Watersamples at estuarine sites only * See Table la] Me/1 * - - - -

PAH’S (Polycyclic aromatic hydrocarbons) [See Table lb] - - Pg/kg Pg/kg Pg/kfi -/ Part o f Special Survey o f Additional Determinands * See paragraph 8]

Nutrients ctcNH4 - N (Ammonium) AMON * mg/r - -N 0 3 - N (Nitrate) NTRA - mg/1* - -N 0 2 * N (N itrite) NTRI - mg/1* - -p o 4 - P (Orthophosphat e) PHOS - mg/1* - -S i04 - Si (Silicate) SLCA - mg/1* - -

Dissolved Oxygen DOXY mg/IT - - -Suspended solids SUSP mg/1 * - -Chlorophyll a CPHL Pg/1 “ ■ -

Physical M easurem entsSecchi depth ox other appropriate measurement SECCI m - - - - -Salinity [See Table lc ] * - * - -Temperature TEMP •c * *

Oyster Embryo BioassayPercent net response 2 PNR % “ %

1 Also Congeners 77, 126 and 169 if possible.2 PNR “ ft tret abnormality ■ % control abnormality x 100

100 * % control abnormality

Alternative units: Chemical measurements can alternatively be given as required by ICES,ie as g/1 (* ■ moles/1; t *• 1/1) or g/g in scientific notation expressed in the form: x.xxxxExxx. (See Appendix 3, p i6)

Code: ICES Parameter/Contaminant Code, to be used as determinand identifier when recording data.

UW: U nfiltercd w aterFW : Filtered water • pore size 0.45 micronsSS: Total Surficial Sedim ent - Total analysis of <2 mm fraction of sediment; dry weightSF: Shellfish - wet weight (plus % solid and % lipid)FM: Fish M uscle - wet weight (plus % solid and % lipid)FL: Fish L iver - wet weight (plus % solid and % lipid)

8

AQC DESIGN MANUAL

liXll-RNAL CYCLL

INTUR-LABMANUAL

I

INDIVIDUALLABORATORY

REPORTS

SUITINGSTANDARDS

TARGETS

CORRECTIONIMPROVEMENTDEVELOPMENT

ANALYSISCONTROL

STANDARDSREPLICATES

LAB APPRAISAL BY AD HOC

EXPERTS

•'

CONTROLCHARTS

ASSESMENT LABORATORY AQC

COMMITSTATISTICAL

ANALYSIS

ACCREDITATION e.g. NAMAS

Overview o f the National Marine AQC Scheme

Appendix 2.2.3

* W ater matrix only

APPENDIX 2.3. i m

NATIONAL MARINE AQC SCHEM E JULY 1993/JUNE 1994

DETERMINAND GROUPS

TABLE 1

Aqueous D eterm inands (Samples at both low and high concentrations will be provided)

Two D istributions per year

GROUP 1 Determinand Units

> Ammonia pM’ TON pM

. 1 Nitrite pMOrthophosphate pMSilicate pM

Sample size - 2 litres of filtered, stabilised, unpreserved seawater for low concentration Sample A and 2 litres for high concentration Sample B. Spiking solutions (30 ml) will also be provided for ammonia, TON, nitrite and orthophosphate.

G R O U P 2 ** AmmoniaTONNitriteOrthophosphateSilicate

pMpMpMpMpM

Sample size - 2 litres of filtered, stabilised, unpreserved estuarine water (salinity approx. 5 %<>) for low concentration Sample A and 2 litres for high concentration Sample B. Spiking solutions (30 mi) will also be provided for ammonia, TON, nitrite and orthophosphate.

GROUP 3 Dissolved Cadmium Dissolved Copper Dissolved Lead Dissolved Nickel Dissolved Zinc Dissolved Chromium

pg/1pg/iMg/1Mg/1Mg/1Mg/1

Sample size - 1 litre of filtered seawater for low concentration Sample A and 1 litre for high concentration Sample B (each preserved with 0.2% nitric acid).

fjRO U P 4 Dissolved Mercury ng/1

Sample size - 1 litre of filtered seawater for low concentration Sample A and 1 litre for high concentration Sample B (each preserved with 0.6% nitric acid).

IAPPENDIX 2.3.1(2)

TABLE 1 - CONTINUED

G R O U P 5 D eterm inand Units

a-H CH ng/IY -HCH ng/1HCB ng/1HCBD ng/1p-HCH ng/1Dieldrin ng/1Aldrin ng/1Endrin ng/1Isodrin ng/1p , p —DDT ng/Ip , p —DDE ng/1p f p-DDD ng/1o , p —DDT ng/ITrifluralin ng/1Total Endosulphan ng/11.2.4 trichiorobenzene ng/I1.3.5 trichlorobenzene ng/1 1,2,3 trichlorobenzene ng/1

Sam ple size - 2 litres of filtered, unpreserved seawater for low concentration Sample A and 2 litres for high concentration Sample B. Two spiking solutions in methanol (7 ml) will also be provided.

G R O U P 6 Chloroform pg/1Carbon Tetrachloride pg/1Trichloroethane pg/1

') 1,2 Dichloroethane pg/1Trichloroethene pg/1

Tetrachloroethene pg/1


G R O U P 7 Pentachlorophenol ng/1


APPENDIX 2 .3 .in ')

TABLE I - CONTINUED

GROUP 8 (New Group)

Determinands Units

Simazine ng/1Atrazine ng/1

Sample size - 2 litres of filtered, unpreserved seawater for low concentration Sample A and 2 litres for high concentration Sample B. Two spiking solutions in methanol (7 ml) will also be provided.

GROUP 9 (New Group)

Azinphos-methyl ng/1Fenthion ng/1Malathion ng/1Parathion ng/1Parathion-methyl ng/1Fenitrothion ng/1

Sample size - 2 litres of filtered, unpreserved seawater for low concentration Sample A and 2 litres for high concentration Sample B. Two spiking solutions in methanol (7 ml) will also be provided.

All groups except group 2 = Full seawater salinity

** Group 2 = Salinity = 5%°

Performance Targets;

(1) For Groups 1,2,3 and 4: 20% Total Error @ 10% Bias, 10% Precision

(2) For Groups 5,6,7,8 and 9: 50% Total ErTor @ 25% Bias, 25% Precision

APPENDIX 2.3.1(4)

N A TIO N A L MARINE AQC SCH EM E - SEDIM ENT DETERMINANDS

TA BLE 2

Two distributions per year

G R O U P 1 D eterm inand Units

Copper mg/kgLead mg/kgCadmium mg/kgZinc mg/kgNickel mg/kgChromium mg/kgMercury - mg/kgArsenic mg/kgAluminium %

G R O U P 2 HCB P g/kg

PCB 28 p g /k gPCB 31 Pg /kgPCB 52 Mg/kgPCB 101 Pg /kgPCB 105 P g/kgPCB 118 p g /k gPCB 138 p g /k gPCB 153 p g /k gPCB 156 P g /k gPCB 180 P g /kg

Aldrin P g /k gEndrin p g /k gDieldrin P g/kgIsodrin P g /k gP t p —DDT p g /k gp , p - d d e p g /k gp ,p -D D D p g /k go , p-DDT p g /k g

Sam ple size - 25 g of a dried, sieved (63 pm) marine sediment will be provided for Group 1. Two portions of a dried sieved (63 pm) sediment as specified by the laboratory will be provided for Group 2.

Performance Targets

(1) For Group 1: 20% Total Error (a) 10% Bias, 10% Precision

(2) For Group 2: 50% Total Error (2) 25% Bias, 25% Precision

APPENDIX 2.3.1(5)

NATIONAL MARINE AQC SCHEM E - BIOTA

TABLE 3

Two distribution per year (three samples of fish tissue will provided for Distribution 6 and three of oil for Distribution 5, otherwise one sample of each type for each distribution).

GROUP 1 Determ inand Units

Lead mg/kgCadmium mg/kgZinc mg/kgMercury mg/kgArsenic rng/kg

GROUP 2 Dleldrin Mg/kgIsodrin Mg/kga-HCH P g/kgy -HCH P g/kgp-HCH Pg /kgP > p—DDT p g /k gp , p—DDE P g /kgp * p—DDD P g/kgo , p—DDT P g/kgaldrin p g /kgendrin P g/kgHCB p g /k gHCBD p g /k g

PCB 28 p g /k gPCB 31 p g /kgPCB 52 p g /k gPCB 101 P g/kgPCB 105 p g /k gPCB 118 p g /k gPCB 138 p g /k gPCB 153 pg /kgPCB 156 p g /k gPCB 180 p g /k g

GROUP 3 PCP Pg/kg

Sample size - 5g of each freeze-dried fish tissue for Group 1 and 5g of each fish oil for Groups 2 and 3.

Perform ance Targets

(1) For Group 1: 20% Total Error <H) 10% Bias, 10% Precision

(2) For Groups 2 and 3: 50% Total Error @ 25% Bias, 25% Precision

APPENDIX 2.3.1 rtft

SUM M ARY PRO G RA M M E FOR TH E NATIONAL MARINE AQC SCHEME 1993/1994

1. In troduction

It is intended that the scheme should satisfy two aims:

a) to provide a continuing check on comparability for the full suite of determinands and matrices required for marine analysis;

b) to assist participating laboratories in achieving the improvements in performance where accuracy falls short of that required.

The proposed approach is outlined below.

2. R outine d istributions

The continuing check on comparability would comprise two distributions (Nos 5 and 6, inSeptember 1993 and February 1994, respectively) of the kind carried out in year I. Additionalfeatures of these exercises would be:

(a) inclusion of more biota samples to provide a more detailed summary of performance in this matrix - to form the basis of a future programme of work);

(b) addition of further organic determinands to all three matrices - to cover Annex 1 of the Dangerous Substances Directive, e.g. ’drins, volatiles, DDTs, trichlorobenzenes, triazines and organophosphorus compounds for water analyses and less extensive additions for sediments and biota;

(c) determination of aluminium in sediment.

3. Intensive Exercises

T he programme of improvement will be directed towards determinands which have been shown to be subject to inadequate accuracy and poor comparability. The following determinands are suggested for year 2. A schedule of actions is given below.

(a) Ammonia and TON in sea and estuarine waters. ~

(b) Cadmium, chromium, lead, and zinc in seawater (any interlaboratory tests would include copper and nickel). Mercury would be approached separately.

(c) Organochlorine determinands in seawater

T he basic approach is one of reviewing the likely sources of poor comparability and examining existing performance data. This is followed by an interlaboratory test involving a range of test samples, chosen with the aim of identifying different types of analytical error, and on the basis of the results making recommendations to participants.

APPENDIX 2.3.1(7)

The emphasis would be modified according to the likely sources of error and the best way in which these might be controlled. For example, in the case of nutrients in seawater, the key areas of blank correction and the effect of salinity would need to be examined; in the case of metals in seawater a more general appraisal of performance would be required.

TIM ETABLE

Ammonia and TON

July 1993 digest of recommendations on methodology

August 1993

October 1993

distribution of ten test samples to examine effectiveness of calibration and blank correction for samples of different salinity.

summary of performance and recommendations

M etals in Seawater

October 1993

November 1993

January 1994

Review of methods and performance (precision and recovery) information available from participating laboratories

Distribution of eight test samples to examine effectiveness of calibration and blank correction for samples of different salinity.

Distribution of further test samples to confirm improved accuracy.

O rganochlorine Compounds in Seawater

October 1993 Review of methods and performance (precision and recovery) information available from participating laboratories

November 1993 Distribution of six ’standards’ as a check on calibration and recover)'.

March 1994 Distribution involving real samples.

NATIONAL MARINE AQC SCHEME (July 1993 - June 1994)

A) Routine Distributions

DISTRIBUTION DISTRIBUTION DATES NUMBER

5. 29 September 1993

6. 2 February 1994

B) Special Exercises

DISTRIBUTION DISTRIBUTION DATES

Ammonia and 11 August 1993 TON in Water

Trace metals 9 November 1993 in water (not Hg)

O/Cl Compounds 9 November 1993 in water

Trace metals 19 January 1994 in water (not Hg)

O/Cl Compounds 30 March 1994 in water

REPORTING DATE

29 October 1993

4 March 1994

REPORTING DATE

10 September 1993

13 December 1993

13 December 1993

25 February 1994

6 May 1994

MATRIX

AQUEOUS SEDIMENTS SAMPLES

AQUEOUS SEDIMENTS SAMPLES

10 Saline water samples / standards

8 test samples

6 test samples

Follow-up to previous exercise

BIOTA

BIOTA

Follow-up to previous exercise

N A TIO N A L M ARIN E AQC SC H EM EAPPENDIX 2.3.2m

JULY 1993/JUNE 1994

DETERMINAND GROUPS

TABLE 1

Aqueous Determinands (Samples ai both low and high concentrations will be provided)

Two distributions per year

GROUP 1Determ inand Units Sample Spike

Ammonia jiM 5 20TON |iM 5 25Nitrite ]iM 0.5 5Orthophosphate jiM 0.5 3Silicate pM 5 15

Sample Size - 2 litres of filtered, stabilised, unpreserved seawater for low concentrationSample A and 2 litres for high concentration Sample B. Spiking solutions (30ml) will also be provided for ammonia, TON, nitrite and orthophosphaie.

GROUP 2 *»

Ammonia pM 20 100TON pM 15 100Nitrite pM 2 10Orthophosphaie jiM 5 10Silicate pM 20 100

Sample Size - 2 litres of filtered, stabilised, unpreserved estuarine water (salinity approx.5%) for low concentration Sample A and 2 litres for high concentration Sample B. Spiking solutions (30 ml) will also be provided for ammonia, TON, nitrite and orthophosphate.

GROUP 3

Dissolved Cadmium Pg/1 0.1 0.2Dissolved Copper pg/1 0.5 2Dissolved Lead Pg/1 0.2 2Dissolved Nickel Pg/1 0.5 2Dissolved Zinc Pg/1 2 10Dissolved Chromium pg/1 2 5

Sample Size - 1 litre of filtered seawater for low concentration Sample A and 1 litre for highconcentration Sample B (each preserved with 0.2% nitric acid).

TA BLE 1 (continued)APPENDIX 2.3.2(2)

Sample Spike

G R O U P 4

Dissolved Mercury ng/1 5 20

Sam ple Size - 1 litre of filtered seawater for low concentration Sample A and 1 litre for highconcentration Sample B (cach preserved with 0.6% nitric acid).

G R O U P 5

a-HCH ng/1 2 5y-h c h ng/1 2 5

HCB ng/1 2.5 10HCBD ng/1 2.5 10

p-HCH ng/1 2 5Dicldrin ng/1 5 15Aldrin ng/1 5 15Endrin ng/1 5 15Isodrin ng/1 5 15pp’DDT ng/1 3 10pp’DDE ng/1 3 10PP’DDD ng/1 3 10op’DDT ng/1 3 10Trifluralin ng/1 5 15Total Endosulphan ng/1 0.5 21,2,4 tri chlorobenzene ng/1 6 151,3*5 trichlorobenzene ng/1 6 151,2,3 trichlorobenzene ng/1 6 15

Sam ple Sire - 2 litres of filtered, unpreserved seawater for low concentration Sample A and2 litres for high concentration Sample B. Two spiking solutions in methanol (7ml) will also be provided.

G R O U P 6

Chloroform pg/1C arton Tetrachloride pg/1

Additional Determinands

Trichlo roe thane pg/11,2 Dichloroethane pg/1Trichlo roe thene pg/1Tetrachloroethene pg/1

0.1 20.1 2

0.1 11 10

0.1 10.1 1

TABLE 1 (continued)

APPENDIX 2.3.2(3)

Sample Siz£ - 2 litres of filiered, unpreserved seawater for low concentration sample A and2 lilrcs for high concentration Sample B. Two spiking solutions in methanol (7ml) will also be provided.

Sample SpikeGROUP 7

Pcntachlorophenol ng/1 25 125

Sample Size - 2 litres of filtered, unpreserved seawater for low concentration Sample A and2 litres for high concentration Sample B. Two spiking solutions in methanol (7mJ) will also be provided.

GROUP 8 (New Group)

Simazine ng/1 50 250Atrazine ng/l 50 250

Sample Sire - 2 litres of filtered, unpreserved seawater for low concentration Sample A and2 litres for high concentration Sample B. Two spiking solutions in methanol (7ml) will also be provided

GROUP 9 (New Group)

Azinphos-m ethyl ng/lFemhion ng/lMalathion ng/lParathion ng/lParathion-m ethyl ng/lFenitrothion ng/l

10 4010 4010 4010 4010 4010 40

Sample Size - 2 litres of filtered, unpreserved seawater for low concentration Sample A and2 litres for high concentration Sample B. Two spiking solutions in methanol (7ml) will also be provided.

All groups except group 2 = Full seawater salinity

** Group 2 = Salinity = 5%

Performance Targets;

(1) For Groups 1,2,3 and 4; 20% Total Error (3> 10% Bias, 10% Precision(2) For Groups 5,6,7,8 and 9; 50% Total Error @ 25% Bias, 25% Precision

APPENDIX 2.3.2(4)

N A T IO N A L M ARIN E AQC SCHEM E - SEDIM ENT DETERMINANDS

TABLE 2

T w o d is trib u tio n s per year.

GROUP 1 Determinand

CopperLeadCadmiumZ incNickelChromiumMercuryArsenicAluminium

Units

rag/kgm g/kgm g/kgm g/kgm g/kgm g/kgrag/kgm g/kg%

Range

10-10020-1000.5-225-10010-5010-1000.05-210-508-10

GROUP 2

HCB

PCB 28 PCB 31 PCB 52 PCB 101 PCB 105 PCB 118 PCB 138 PCB 153 PCB 156 PCB 180

AldrinEndrinDieldrinIsodrinpp’DDTpp’DDEpp’DDDop'DD T

Pg/kg

Pg/kgPg/kgPg/kgPg/kgPg/kgPg/kgPg/kgPg/kgPg/kgPg/kg

Pg/kgPg/kgPg/kgPg/kgPg/kgPg/kgPg/kgPg/kg

0.1-2

0.2-5

Sample Size 25g of a dried, sieved (63 pm) marine sediment will be provided for each group.

Perform ance Targets

(1) For Group 1; 20% Total Error @ 10% Bias, 10% Precision(2) For Group 2; 50% Total Error @ 25% Bias, 25% Precision

APPENDIX 2.3.2(5)

NATIONAL MARINE AQC SCHEME - BIOTA

TABLE 3

Two distribution per year (three samples of fish tissue and three of fish oil will be provided for Distribution 5 and one sample for Distribution 6).

GROUP 1

GROUP 2

GROUP 3

Determ inand Units Range

Lead mg/kg 2-50Cadmium mg/kg 0.5-5Zinc mg/kg 10-300Mcrcury mg/kg 0.1-3Arsenic mg/kg 3-20

Dicldrin 5*50Isodrin Pg/kg n

a-HCH Pg/kg k

y-h c h Pg/kgn

P-HCH Pg/kg w

pp’DDT Pg/kg n

pp’DDE Pg/kgn

p p ’DDD Pg/kg ft

op’DDT pg/kg ft

Aldrin Pg/kg *

Endrin Pg/kgft

HCB Pg/kg n

HCBD Pg/kgft

PCB 28 Pg/kg 5-25PCB 31 Pg/kg

pi

PCB 52 Pg/kg*

PCB 101 pg/kg ft

PCB 105 P&/kgR

PCB 118 Pg/kgit

PCB 138 Pg/kgM

PCB 153 Pg/kgX

PCB 156 Pg/kgft

PCB 180 Pg/kgn

PCP Pg/kg 5-50

Sample Size 5g of each freeze-dried fish tissue for Group 1 arid 5g of each fish oil for Group 2.

Performance Targets

(1) For Group 1; 20% Total Error (2> 10% Bias, 10% Precision(2) For Group 2; 50% Total Error @ 25% Bias, 25% Precision

- APPENDIX 2 .3 .3 0 )

ANNEX 2 NATIONAL MARINE AQC SCHEM E - ERROR THRESHOLDS

The Lowest level of interest is ihc lowcsi concentration ai which relatively precise measurement and interpretation are required. High standards of accuracy may be needed ncario this concentration, for example for the determination of trends or calculation of loads. It follows that the required Limit of Detection should be set at one tenth of this value.

The lowcsi level of interest may correspond to the relevant Environmental Quality Standard or it may represent the concentration level likely to be found in uncontaminated samples. If it is the latter, it is likely to be lower than the EQS.

AQUEOUS SAMPLES

Group 1 - Seawater Nutrients

Lowest level of interest

Thresholds

Absolute %

AmmoniaTONNitriteOrthophosphateSilicate

5 pM 5 pM 0.5 pM 0.5 pM 5 pM

0.50 pM 200.50 pM 200.05 pM 200.05 pM 200.50 pM 20

Group 2 - Estuarine Nutrients

AmmoniaTONNitriteOrtho phosphate Silicate

20 pM 15 pM 2 pM 5 pM 20 pM

2.00 pM 20 1.50 pM 200.20 pM 200.50 pM 202.00 pM 20

G roup 3 - Trace Metals (A and B)

CadmiumCopper

0.1 pg/1 0.5 pg/1 0.2 pg/1 0.5 pg/1 2 pg/1 2 pg/1

0.01 pg/1 200.05 pg/1 200.02 pg/1 200.05 pg/1 200.20 pg/1 200.20 pg/1 20

LeadNickelZincChromium

Group 4 - M ercury (A and B)

Total Mercury 5 ng/l 0.50 ng/l 20

APPENDIX 2 3 .3( 2)

Lowest level of interest

G ro u p 5 - O rganochlorines (A and B)

cx-HCH 2 ng/lr -HCH 2 ng/1HCB 2.5 ng/1HCBD 2.5 ng/1p -HCH 2 ng/1Dicldrin 5 ng/1Aldrin 5 ng/1Endrin 5 ng/1Isodrin 5 ng/1p p ’DDT 3 ng/1pp'D D E 3 ng/1p p ’DDD 3 ng/1o p ’DDT 3 ng/1Trifluralin 5 ng/1Total Endosulphan 10 ng/11.2.4 TCB 6 ng/11.3.5 TCB 6 ng/1 1,2,3 TCB 6 ng/1

Thresholds

Absolute %

0.2 ng/1 0.2 ng/1 0.25 ng/1 0.25 ng/1 0.2 ng/1 0.5 ng/1 0.5 ng/1 0.5 ng/1 0.5 ng/1 0.3 ng/1 0.3 ng/1 0.3 ng/1 0.3 ng/I 0.5 ng/1 1 ng/1 0.6 ng/1 0.6 ng/1 0.6 ng/1

50

5050

505050505050505050505050505050

G roup 6 - C hloroform and C ar bon tetrachloride (A and B)

Chloroform 1 pg/1 0.1 pg/1 50Carbon tel. 1 pg/1 0.1 pg/1 50Trichlorocthanc 1 pg/1 0.1 pg/1 501,2 Dichlorocthanc 10 pg/1 1 pg/1 50Trichlorocthcne 1 pg/1 0.1 pg/1 50Tctrachlorocthenc - 1 pg/1 0.1 pg/1 50

G roup 7 - Pentachlorophenol (A and B)

PCP 1000 ng/1 100 ng/1 50

G roup 8 - Triazines

Simazinc 100 ng/1 10 ng/1 50Atrazinc 100ng/I 10 ng/1 50

APPENDIX 2.3.3(3)

(Jroup 9 - Organophosphorus Compounds

Azinphos-mclhyl 200 ng/1 20 ng/1 50A/.inphos-clhyl 200 ng/1 20 ng/1 50Fcnihion 100 ng/1 10 ng/1 50Malathion 150 ng/1 15 ng/1 50Paraihion 100 ng/1 10 ng/1 50Paralhion-mcthyl 150 ng/1 15 ng/1 50Fcnitrothion 100 ng/1 10 ng/1 50

APPENDIX 2.3.3(4)

SKDIMKNTSThresholds

Absolute %

G roup I

Copper 1.00 mg/kg 20Lead 2.00 mg/kg 20Cadmium 0.05 mg/kg 20Zinc 2.50 mg/kg 20Nickcl LOO mg/kg 20Chromium LOO mg/kg 20Mcrcury 0.005 mg/kg 20Arscnic 1.00 mg/kg 20Aluminium % 20

G roup 2

HCB 0.01 pg/kg 50PCBs 0.01 pg/kg 50Aldrin 0.01 pg/kg 50Endrin 0.01 pg/kg 50Dicldrin 0.01 pg/kg 50Isodrin 0.01 pg/kg 50p p ’DDT 0.02 pg/kg 50pp’DDE 0.02 pg/kg 50p p ’DDD 0.02 pg/kg 50op’DDT 0.02 pg/kg 50

APPENDIX 2.3.3(5)

IlIOTAThresholds

Absolute %

G roup I

Lead 0.20 mg/kg 20Cadmium 0.05 mg/kg 20Zinc LOO mg/kg 20Mercury 0.01 mg/kg 20Arsenic 0.30 mg/kg 20

Group 2

Organochlorine cpds 0.50 pg/kg 50PCBs 0.50 pg/kg 50

G roup 3

PCP 0.5 pg/kg 50

APPENDIX 2 .4 .1 0 )

N M A Q C W o rk sh o p ' S am pling , F iltra tio n and D e te rm in a tio n of M e rc u ry in Sea a n d E s tu a rin e W a te r ’ B u rn h am -o n -C ro u ch , 24-25 N ovem ber 1993

List of p a rtic ip a n ts

Michael Coffey Alison Fry Alastair Gunn Alan Lawlor David McMullan Peter Small Una Thom Richard Yates

Rebekah Laslett Moira Salmons Mike Waldock

A pologies from

Dave Allen

In troduction

Mike Waldock began by summarising the NMAQC intercom parison experience to date. This is arguably one of the m ost problem atic determ inands in the scheme. The problem s are reflected by the small num ber of laboratories who have reported results, and the poor agreement between the results of these laboratories*

Sam pling and S am p le T re a tm e n t

Rebekah Laslett gave the first presentation which lasted about 40 minutes. Topics included the concentrations of trace elements in the oceans, reasons for the low concentrations, and the introduction of the concept of partition coefficients and mean oceanic residence tim es of metals in the oceans. D ecreasing accepted values for dissolved mercury in the oceans from 30 ng/l (Brewer, 1975) to 0.3-2 ng/l (Bruland 1983) was attributed to increasing aw areness of sample contam ination and the lowering of detection limits during this period. Typical present day accepted values (<5 ng/l for reactive mercury) w ere given for oceanic w aters and British coastal waters. The requirem ents for trace metal sam plers were identified, and examples of 'clean' sam plers were given. Methods of mercury sample storage w ere then discussed. Some m echanisms of mercury loss from samples were given as well as those for contamination of samples. Typical contributions of reagents to the overall blank values w ere given and a slide dem onstrating the im portance of atm ospheric contamination was shown.The presentation ended with some results from the Burnham laboratory on the stability of reactive mercury samples. They appear to indicate that concentrations of reactive m ercury decreased with time over a 30 hour period.

Forth RPB. EdinburghClyde RPB. East KilbrideWRc. Medmenham (Day 2 only)NRA (Northumbria/Yorkshire), LeedsIRTU, LisburnNRA (Wales). LlanelliTay RPB, PerthNRA (Severn-Trent), Nottingham

M AFF Burnham -on-CrouchM AFF Bum ham -on-Crouch (Day 2 only)MAFF Burnham -on-Crouch (Day 1 only)

NRA (SW), Exeter

APPENDIX 2.4.1(2)

The discussion that followed (about 20 minutes) highlighted the fact that not all analysts present were responsible for collecting their own samples, but had to rely upon the expertise ' of others. There was some discussion of the methods that had been used successfully for sam pling inshore w aters by the group members. It was also noted that intcrcom parison exercises cannot test for contamination at the sampling stages. Even if the m ercury concentration in a sea water sample can be precisely and accurately determined, greater errors may arise from the sam pling and sample treatment. "Hiis is a critical point when the data from the NMP are assessed.

Analytical Methods

After tea, Rebekah Laslett gave a second presentation lasting about 25 minutes. This included a discussion of the speciation of mercury in sea water, and the approxim ate separation of these species into operationally defined fractions. She then w ent on to describe the methods of mercury analysis used at the Burnham laboratory. This included the precleaning of sam pling bottles, filters, the other equipm ent and reagents. A schem atic o f the analytical procedures for dissolved reactive, total dissolved and total mercury w as then shown, as well as a schematic of the instrumentation.

During the discussion that followed, (about 15 minutes) m any participants were able to identify areas in their procedures which could be changed to lower their blank values or reduce mercury loss or contam ination. These included the use of clean air cabinets, using gold traps to clean the argon entering the system, cleaning the hydroxylam m onium chloride by adding SnCl2 and purging with argon. There was some discussion about the various grades of acids available, their prices and the relative merits of buying in acids or purifying them in-house. Other people suggested using com m ercially available drying traps and KBr/Br0 3 solutions instead of m aking them up on site.

Demonstration o f Mercury in Seawater Analysis

This began by fully describing the m ercury instrum entation currently in use in the laboratory. Some reagents were then prepared, and this led to some discussion about the practicalities of working at sea. A sample was then analysed for reactive dissolved mercury', and a second sample was prepared for the determ ination of dissolved mercury. Subsequently the analysis of the total dissolved sample was dem onstrated. There was considerable discussion throughouU he dem onstration sessions. This included the need for m atrix matching of the calibration standards, the effects of using different volumes in the reaction vessel, the pros and cons of measuring sample masses instead of volumes, the hazards associated with the analysis, the sporadic contam ination of mercury from coloured pipette tips, and w hether the method would lend itself to the use of an autosampler.

Concluding session

The workshop concluded with some slides of seawater sam pling from RV Cirolana and the analysis of mercury' at sea. There was a further opportunity for questions, and the key things which people had learned from the workshop were drawn together.

APPENDIX 2.4.1(3)

Conclusions

One of the most useful aspects of ihc workshop was the opportunity for informal discussions with others directly involved in seawater mercury analysis, the presentations and dem onstrations merely acted as the springboard for this interaction. 'Hie discussions were of good quality and were very relevant to im mediate problems. Everyone contributed lo the discussions, and their approach was generally very positive.

Q uestio n n a ire

A questionnaire was circulated to all participants after the workshop, and the results are summarised on the attached sheet.

Rebekah Laslctt Robin Law9 December 1993

APPENDIX 2.4 .K4)

MERCURY IN SEAWATER WORKSHOP PARTICIPANT REACTION QUESTIONAIRE

SUMMARY OF RESULTS

Six quesiionaires w eie teturned. Results ate sum m onsed in holies

Pre-workshop contact with organisers Hospitality during workshop

PRESENTATIONS AND DISCUSSIONSPresentation, contents Presentation, relevance Presentation, delivery Visual aids, clarity Visual oids. relevance Votue of discussions

TOO DETAILED ABOUT RIGHT 6 POOR DETAILRELEVANT 6 OK tRRELEVANT

G O O D 5 OK 7 POORG O O D 5 OK 1 POOR

RELEVANT 5 OK 1 IRRELEVANTVERY USEFUL 6 OK NOT USEFUL

G O O D 3 OK 3 POORG O O D 6 OK POOR

DEMONSTRATIONDemonstration, contents Demonstration, relevance Demonstration, delivery Were your questions onswered

HANDOUTSHandout, contents Handout, relevonce

TOO DETAILED ABOUT RIGHT 6 POOR DETAILRELEVANT 6 OK IRRELEVANT

TOO DETAILED ABOUT RIGHT 6 POOR DETAILRELEVANT 5 OK 1 IRRELEVANT

G O O D 3 OK 3 POORYES 5 SOME 1 NO

OVERALLTwo things you liked best

Two things you disliked most

Exchange of information from participants (2)Informal atmosphere (2)About the right number of people (1)O pen discussion (1)Useful demonstration of analysis (1)Lack of name bodges (VDiscussion occasionally too unstructured (1)

What, if anything, will you take awoy from the workshop which may help improve your analyticalprecision, accuracy or detection limits ?

Addition of tin chloride to hydroxylammonium chloride to reduce mercury blank (2)Using o gold trap in the argon line to absorb mercury from argon supply (2)Using a clean air cabinet (2)Installing a few clean up procedures/equipment changes to reduce blanks (1)

Things I am going to test and consider chonging at Burnham after workshop:- Using Convol KBr.KBr03 solution to minimise preparation steps Using the Perma-pure drying system from PS Analytical instead of CaCI2 drying traps Purer acids from TS BakerCRM for Hg (but I think the one suggested has too high an H g concentration for SW work)

APPENDIX 2.4.2 m

NATIONAL MARINE AOC SCHEME

REPORT ON ORGANICS WORKSHOP

The Workshop was held al ihc Clyde RPB Headquarters in Easl Kilbride, on 6-7 June, 1994. There

were 17 panicipants from 11 organisations:

from 3 Government labs: SOAFD - Dave Wells, John Pirie, Lesley Campbell and Douglas

Campbell; MAFF - Colin Allchin and Steven Morris; Department of Agriculture Northern

Ireland - Stephen Wilson;

\

from 3 RPBs: Forth RPB * Michacl Coyle; Tay RPB - Peter Semple; Clyde RPB

David Pirie, Alison Fry and Agnes Wright;

from 3 NRA labs: Thames - John Quick; Northumbria/Yorkshire - M Daniel; South-west -

David Samuels;

from 2 others: IRTU - David Edwards; WRc - Mike Gardner.

Agenda

Dave Wells was in the chair, and each session being introduced by the speaker. Discussion followed

on various points, with "round table" input of current practices.

The Workshop was relatively informal, and was a general learning experience for many participants,

so that awareness of alternative strategies was heightened, some of which may be put into practice in

participants labs.

Main Points of Discussion

It was apparent that different methods were used by the participating laboratories, with the split often

being into two distinct groups, with the "open ocean" labs in one group and the "estuaries" labs in the

other.

Introduction

APPENDIX 2.4.2C2)

REPORT ON ORGANICS W ORKSHOP (CONT.)

Conclusions

* Specific conclusions were nol made; cach participant was left 10 implement whaicvcr changes

he/she fell were necessary and practical.

* The need for training in the use of control charts were highlighted.

* A follow-up workshop on sediment and tissue analysis was requested.

* The suggestion was made (afterwards) that more detailed recommendations arising from the

workshop in terms of practices to be used or avoided would have been helpful.

* It was hoped Lhat the Workshop would lead to an improved response by laboratories to the

NMAQC scheme, in terms of both (a) participation level (only 6 labs relumed results of 16

taking pari in the special exercise) and b) analytical performance.

APPENDIX 2.6.1

NRA

Oruanisaiion

IRTU

DAN I

MAFF

SOAFD

RPB

CURRENT NAMAS/BS5750 STATUS (5.7.94)

Laboratory Slaius

Nottingham Laboratory

Llanelli Laboratory

Leeds Laboratory

Fobncy Mead Laboratory

Exeter Laboratory

Waterloovillc Laboratory

Forth

Clyde

Tay

NAMAS Accrcditcd

NAMAS Accredited

NAMAS Accrcditcd

NAMAS Accrcditcd

NAMAS Accrcditcd

NAMAS Accrcditcd

N A M A S A ccrcd i ted /B S5 750

certificated

Under active consideration



NAMAS application in/BS5750 by

1995


1995


1995

PA R TIC IPA T IO N IN Q U A SIM EM E

1. Dcpanmcni of Economic

Development Industrial Scicncc Centre

(DoENI)

2. Plymouth Marine Laboratory

3. Clyde River Purification Board

4. NRA Welsh Region, Llanelli Laboratory

5. SOAFD

6. MAFF, Bumham-on-Crouch

7. MAFF, Lowestoft

8. Forth River Purification Board

Participating Organisation

APPENDIX 2.7.1

Determinands

Organics, Metals, Nutrients





Metals, Organics

Nutrients


APPENDIX 2.10.1

DOCUMENTATION CIRCULATED TO PARTICIPANTS IN THE NMAQC

SCHEME IN YEAR 2.

Reports

1. Distribution 5 report

2. Distribution 6 report

3. Approach lo Analytical Quality Control (NMAQC Schcmc)

4. Report lo NCC on NMP and NMAQC Schcmc.

5. 2nd Year report on the NMAQC Schcmc.

6. NMAQC Schcmc. Special Exercises for Metals and Organochlorine

Compounds in Water: Nov 1993.

7. NMAQC Schcme, Intcrlaboratory Test for the Determination of Ammonia

and TON in Saline Water: August 1993.

Questionnaires

1. Laboratory AQC Information

2. UK National Monitoring Plan: Levels of Participation

3. UK NMAQC Scheme: Participation

Information Papers

1. Sampling Marine and Other Saline and Deep Water and Related Sediments

(Chapt.6). Standing Committee of Analysts. Draft report.

2. Measurement of Volatile Organic Compounds at UK NMP Stations. Marine

Pollution Bulletin 1993. Dawes and Waldock.

3. Contaminants in Seawater around England and Wales: Results from

Monitoring Surveys, 1990-92. Law, Waldock, Allchin, Laslett and Bailey.

4. NMAQC Workshop. ’Sampling, Filtration and Determination of Mercury in

Sea and estuarine waters. November 1993.

5. Directory of Marine and Freshwater Institutions, Scientists and Research

Engineers in the UK and Republic of Ireland. FBA, 1992.

APPENDIX 3.2.1

NATIONAL MARINE ANALYTICAL QUALITY CONTROL SCHEM E

NATIONAL CO-ORDINATING COM M ITTEE (NCC)

Dr. M. Jessep

Dr. A. Griffiths

Mr. E. Donaldson

Mr. R. Law

Dr. D. Miles

Mr. B. Miller

Dr. S. Milchcll

Dr. M. Roberts

Dr. D. Toft

Dr. D. Wells

(NRA, National Laboratory

Service, Nottingham)

(Forth RPB)

(DoENI/IRTU)

(MAFF)

(BGS)

(Clyde RPB)

(DANI)

(DoE)

(NRA, National Laboratory

Service, Leeds)

(SOAFD)

Chairman

Schcmc Manager

RPB Representative

Secretary

NRA Representative

Project Manager QUASIMEME

Committee Changes:

Dr. D. Toft (NRA Yorkshire/Northumbria) replace Mr. G. Firth and is the NRA Representative.

Dr. A. Kelly (SOAFD) retired due to ill health.

Mr. T. Long (NRA H.Q. Bristol)

APPENDIX 3.2.2

ANNEX 1. LABORATORIES PARTICIPATING IN THE SCHEME (YEAR 1 AND 2)

BGS KEYWOKTH’

CLYDE RPB’

DANI AQUATIC SCI.*

DANI FOOD & AGR.*

FORTH RPB*

HIGHLAND RPB

IRTU IND. SCIENCE*

MAFF BURNHAM*

MAFF LOWESTOFT’

NRA ANGLIAN

NRA NORTHUMBRIA

NRA NW CARLISLE

NRA NW WARRINGTON

NRA NOTTINGHAM’

NRA EXETER*

NRA READING'

NRA LLANELLI’

NRA LEEDS’

NRA WATERLOOVILLE*

SOAFD’

SOLWAY RPB

TAY RPB’

UNIVERSITY OF EAST ANGLIA*

’ - Currently taking part in National Marine AQC Scheme (Year 2)

NRA Northumbria, Carlisle, Warrington and Anglian closed during Year 2.

APPENDIX 3.3.1

TIM KTAKLK - N ational M arine AQC Schem e l< m - IW 5 +

Distribution Reporting by*

Ju ly 94 M etals and Organics in sedim ent and b io ta 12 Nov 94

10 Aug 94 Hg in seawater - distribution of six test 9 Sep 94sample special exercise

21 Sep 94 D istribution 7 (n u trien ts and m etals 24 O ct 94plus norm al OCIs and triazines in seaw ater)- including "specia l" am m onia and TO N

Sept 94 Metals in seawater workshop

Oct 94 Hg in seawater - summary of performance and recommendations

Oct 94 Sediment metals - Review of methods for aqua regia and total digestion.

16 Nov 94 D istribu tion 8 (Organics - Volatiles, O Ps 19 Dec 94an d PCP)

16 Nov 94 Sediment metals - Distribution of two sediments for laboratories to digest.Digests to be returned for analysis 9 Dec 94

*Dec 94 Metals and Organics in sediment and biota 26 May 95

8 Feb 95 Distribution 9 (nutrients and metals 13 M ar 95plus normal OCIs and triazines) - including

special" metals including Hg

1 Mar 95 Sediment metals - Distribution of , 8 May 95standards, digests, and sediment samples

5 A pr 95 ' D istribu tion 10 (Organics - Volatiles, 8 M ay 95O Ps and PCP) - including special OCIs

May 95 Sediment workshop

+ "Proficiency tests" ie routine interlaboratory checks are indicated in bold type. Theseare interspersed with special exercises and workshops.

* Routine interlaboratory tests on solid samples (metals and Organics in sediments and biota) are to be integrated with the QUASIM EM E programme. This will involve distribution of QUASIM EM E materials in July ana December.

Results for all solids samples will be reported to SOAFD.

National M arine AQC Scheme

Financial Report Year 2

The finances of Ihc NMAQC Schcmc for year 2 arc as follows;

YEAR 2 (July 93 - June 94)

Balancc Brought Forward £ 3,918.34

Coniribuiions Received

DoE £10,000.00

NRA Regions £28,000.00

RPBs £10,500.00

Government Laboratories £14,500.00

Total Contributions £66,918.34

iPlus Interest £ 2,523.41

Total Income £69,441.75

Expenses/Workshop fees/Contractors’ fees £55,219.22

Funds carried forward to Year 3 £14,222.53

APPENDIX 3.4.1

Financial Projections for Year 3 (July 94 - June 95)

APPENDIX 3.4.2

Funds transferred for Year 2 £14,222.53

Contributions (projccicd)

DoE £ 5,000.00

NRA £17,500.00

RPBs £10,500.00

Government Laboratories £14,500.00

Interest (estimate) £ 1,500.00

Total Available Funds £63,222.53

Management Expenses/Workshops (est)/Contractors’ fees

Estimates of funds available for Year 4

£57,320.00

£ 5902.53

The projected surplus for year 3 will be in the region of £5,900. No allowance has been set

aside for any purchases of "materials" that may be required from QUASIMEME.

a 't*A

APPENDIX 3.4.2 (Cont.)

Financial projections for Year 4 (July 95 - June 96)

Funds transferred from Year 3 (est) £ 5,900.00

Membership contributions £42,500.00

Interest (csl) £ 1.000.00

Total funds available £49,400.00

The projected funds available for year 4 are estimated to be £49,400. The costs for running

the schcmc for years 1, 2 and 3 have been as follows;

Year 1 £54,613.00

Year 2 £55,219.00

Year 3 £57,320.00 (est)

Year 4 £59,000.00 (est)

APPENDIX 3.4.3

ORGANISATION APPROACHED TO BECOME

NMAQC MEMBERS.

Fisheries Research Centre, Dublin.

IC1 Brixham Laboratory, Devon.

lnsmuic of Terrestrial Ecology, Monks Wood, Cambridgeshire.

M. Scan Ltd., Sunninghill, Ascot.

Strathclyde Regional Chemists Department, Glasgow.

Lothian Regional Council, Dept, of Water and Drainage, Edinburgh.

Wessex Scientific Services, Bristol.

University of Wales, Bangour, Gwynedd.

Southampton University, Southampton.

PML, Plymouth, Devon.

Polytechnic South West, Plymouth.

Thames Water Utilities Ltd., London.

North West Water Ltd., Warrington.

Yorkshire Water Enterprises Ltd., Sheffield.

Southern Science Ltd., Hampshire.

Analytical and Environmental Services, Wallsend.

University of Liverpool, Liverpool.

Wallace Evans Laboratories, Bridgend.

Anglian Water Services Ltd., Cambridge.

University of Cambridge, Cambridge.

Bristol University, Bristol.

University College Wales, Swansea.

IOS, Godalming, Surrey.

APPENDIX 4.2.1(1)

1.1 Practical Approach

Samples for the fifth routine inteilaboratory test were distributed on 29 September1993. The test comprised:

A Q U EO U S SA M PLES

G R O U P 1) (Ammonia, TON, Nitrite, Orthophosphate and Silicate in Seawater)

Sample A Two litres o f filtered, unpreserved, sterilised seawater

Sample B Two litres of filtered, unpreserved, sterilised seawater one mixed spiking solution for ammonia, nitrite and onhophosphate and a spiking solution for TON.

G R O U P 2) (Ammonia, TON, Nitrite, Onhophosphate and Silicate in Estuarine Water)

Sample A Two litres of filtered, unpreserved, sterilised estuarine sample (of salinity approximately 5%°) and a mixed spiking solution for ammonia, nitrite and orthophosphate.

Sample B Two litres of filtered, unpreserved, sterilised estuarinesample (of salinity approximately 5%°), one m ixed spiking solution for ammonia, nitrite and orthophosphate and a spiking solution for TON.

G R O U P 3) (Cadmium, copper, lead, nickel, zinc and chromium)

One litre of filtered seawater sample for Sample A and one litre for Sample B (each preserved with 0.2% nitric acid)

G R O U P 4) (Total Mercury)

One litre of filtered seawater sample for S any le A and one litre for Sample B (each preserved with 0.6% nitric acid)

G R O U P 5) (Organochlorine compounds) Two litres o f filtered,unpreserved seawater and a spiking solution for Sample A ana two litres of filtered, unpreserved seaw'ater and a spiking solution for Sample B.

- 2 -

i APPENDIX 4.2.1(2)

G R O U P 6) (Volatile, chlorinated solvents) Two litres of filtered,u n p r e s e r v e d seawater and a spiking solution for Sample A and two litres of filtered, unpreserved seawater and a spiking solution for Sample B.

G R O U P 7) (PentachJorophenol) Two litres of filtered, unpreserved seawater ana a spiking solution for Sample A and two litres of filtered, preserved seawater and a spiking solution for Sample B.

G R O U P 8) (Triazines) Two litres of filtered, unpreserved seawater and a spiking solution for Sample A and two litres of filtered, unpreserved seawater and a spiking solution for Sample B.

G R O U P 9) (Organophosphorus compounds) Two litres of filtered,unpreserved seaw aterand a spiking solution for Sample A and two litres of filtered, unpreserved seawater and a spiking solution for Sample B.

M A RIN E SED IM EN TS

G R O U P 1) (Copper, Lead, Cadmium, Zinc, Nickel, Chromium, M ercury, Arsenic and Aluminium)

25 g o f a dried, sieved (63 jim) marine sediment.

G R O U P 2) (HCB, PCBs, Aldrin, Endrin, Isodrin, Dieldrin, p p ’DDT, p p ’D D E o p ’ DDT and p p ’DDD)

Two portions of a dried, sieved (63 Jim) marine sediment. W eight - specified by the laboratory for a single determination.

M A R IN E BJQXA

G R O U P 1) (Lead, Cadmium, Zinc, Mercury and Arsenic)

5 g of freeze-dried, sieved (250 pm) mussel tissue.

G R O U PS 2A, B and C

(Dieldrin, isodrin, a-H CH , y -HCH, f>-HCH, p p ’DDT, p p ’DDE, p p ’DDD, o p ’DDT, Aldrin, Endrin, HCB, HCBD and PCBs)

Three 5g portions of fish oil.

- 3 -

APPENDIX 4.2.1(3)

G R O U P S 3A , B an d C

(PCP)

Three portions of fish oil.

Participants w ere provided with the general guidance given in Appendix A and were asked to report their results by 29 October 1993.

APPENDIX 4 .2 .2 0 )

1.1 Practical A pproach

Samples for the sixth routine interlaboratory test were distributed on 30 March 1994. The test comprised:

AQUEOUS SA M PLES

G roup 1) (Ammonia, TON, Nitrite, Orthophosphate and Silicate in Seawater)

Sam ple ATwo litres of filtered, unpreserved, sterilised seawater, one mixed spiking solution for ammonia, nitrite and orthophosphate and a spiking solution for TON.

Sam ple BTwo litres of filtered, unpreserved, sterilised seawater, one mixed spiking solution for ammonia, nitrite and orthophosphate and a spiking solution for TON.

G roup 2) (Ammonia, TON, Nitrite, Orthophosphate and Silicate in Estuarine Water)

Sam ple ATwo litres of filtered, unpreserved, sterilised estuarine sample (of salinity approximately 5%°) and a mixed spiking solution for ammonia, nitrite and orthophosphate.

Sam ple BTwo litres of filtered, unpreserved, sterilised estuarine sample (of salinity approximately 5%°), one m ixed spiking solution for ammonia, nitrite and orthophosphate ana a spiking solution for TON.

G roup 3) (Cadmium, copper, lead, nickel, zinc and chromium)\


G roup 4) (Total Mercury)


- 2 -

APPENDIX 4.2.2(2)

(■ ro u p 5) (O rg a n o c h lo r in e c o m p o u n d s ) T w o litre s o f Tillered,unpreserved seawater and a spiking solution lor Sample A and two litres of Tillered, unpreserved seawater and a spiking solution for Sample B.

G ro u p 6) (Volatile, chlorinated solvents) Two litres of filtered,unpreserved seawater and a spiking solution lor Sample A and two litres of filtered, unpreserved seawater and a spiking solution for Sample B.

G ro u p 7) (Fentachlorophenol) Two litres of filtered, unpreserved seawater and a spiking solution for Sample A and two litres of filtered, preserved seawater and a spiking solution for Sample B.

G roup 8) (Triazines) Two litres of filtered, unpreserved seawater and a spiking solution for Sample A and two litres of filtered, unpreserved seawater and a spiking solution for Sample B.

G roup 9) (Organophosphorus compounds) Two litres o f filtered,unpreserved seawater and a spiking solution for Sample A and two litres o f filtered, unpreserved seawater and a spiking solution for Sample B.

M A R IN E SE D IM E N T S

*G roup l)(C opper, Lead, Cadmium, Zinc, Nickel, Chromium, Mercury, Arsenic and Aluminium)

One sample of a dried, sieved marine sediment (Quasimeme - serial num ber 1993-1

G ro u p 2) (HCB, PCBs, Aldrin, Endrin, Isodrin, Dieldrin, pp’DDT, p p ’DDE op* DDT and pp’DDD)

G ro u p 2A)Two portions of a dried, sieved (63 pm) marine sediment as specified by the laboratory.

*G roup 2B)A further sample (Quasimeme - serial number C l 1993-1) was also provided for the determination of Group 2 parameters.

APPENDIX 4.2.2(3)

MAKI NK 1UOTA

* G ro u p 1) (Lead, Cadm ium , Zinc, M ercury and Arsenic)

O ne sam ple of homogenised mussel tissue (Quasim em e - serial num ber QAM4).

G ro u p 2 (D ieldrin, isodrin, a-H C H , y -HCH, p-HCH, p p ’DDT, pp’DDE, p p ’DDD, o p ’DDT, Aldrin, Endrin, HCB, HCBD and PCBs)

G ro u p 2A 5g of fish oil.

* G ro u p 2BO ne sam ple of hom ogenised cod liver (Quasim em e - serial num ber 0 A O ])

Participants w ere provided with the general guidance given in Appendix A and w ere asked to report their results for the National M arine AQC samples by 7 M ay 1994. The results for the QUASIM EM E samples were to be reported separately to D r D W ells at SOAFD by 13 May 1994. These QUASIM EM E sam ples are m arked with * above. Summaries of results for these samples have not been included in this report; the data will be processed at a later date. T he reporting date for organic substances in sediment was deferred until 10 June 1994; summaries of results for this sample are also not included in this report.

SUMMARY OF LABORATORIES' RESULTSP i t r i b u t i on n u m b e r Data setD a t e o f d i s t r i b u t i o n

A q u e o u s d o t e r m i n a n d s SEPTEMDER 1993

05

D e t e r m i n a n d3 4 5

G r o u p 1 - S e a w a t e r s a m p l e A ° Ammonia (A)* TON (A) - 5 3 f

68- 6

8 N i t r i t e (A) - 7 - 1 4* O r t h o p h o s p h a t e {A) 1 6• S i l i c a t e (A) - 3 8

G r o u p 1 - S e a w a t e r s a m p l e B - Anvnonia (B) 12 - 9* TON (B) 21 f -2

N i t r i t e (B) - 5O r t h o p h o s p h a t e (B) - 1 5

* S i l i c a t e (B) - 5 5

G r o u p 2 - E s t u a r i n e s a m p l e AAnroonia (A) - 1 6 -3

° TON (A) - 3 0N i t r i t e ( A ) 5 6O r t h o p h o s p h a t e (A) 0 4

* S i l i c a t e (A) - 1 0 7

G r o u p 2 - E s t u a r i n e s a m p l e BAnrnonia (B) 13 - 5

• TON (B) - 2 -1N i t r i t e (B) 13 13O r t h o p h o s p h a t e (B) -1 -1

• S i l i c a t e (B) 4 4

G r o u p 3 - T r a c e m e t a l s s a m p l e A D i s s o l v e d Ca dmi um (A) - 1 5 - 3D i s s o l v e d C o p p e r (A) 4 - 3D i s s o l v e d L e a d (A) - 21 f - 1 1

•* D i s s o l v e d N i c k e l (A) 1 -an D i s s o l v e d Z i n c (A) - 7 0

D i s s o l v e d C hr omi um (A)

G r o u p 3 - T r a c e m e t a l s s a m p l e D i s s o l v e d Ca dmium (B)

B- 2 6£

-4

- 4 fifD i s s o l v e d C o p p e r (B) - 1 2 - 5 0 £

~ D i s s o l v e d L e a d (B) - 6 - 5 8 fD i s s o l v e d N i c k e l (B) - 1 5 -7D i s s o l v e d Z i n c (B) - 2 5 £ 2 3 fD i s s o l v e d C hr omi um (B) 7

G r o u p 4 - M e r c u r y s a m p l e AT o t a l M e r c u r y (A) - 7 7 f 3 4 8 £

G r o u p 4 - M e r c u r y s a m p l e BT o t a l M e r c u r y (B) - 0 8 f 1 7 0 f

MEAN DIFFERENCES FROM REFERENCE CONCENTPATION <»)

L a b o r a t o r y n u m b « r7 10 11 12 14 15 1? 10 19 20 21 23

74 54 122 - 8 8 - 9 6 - 7 5 40 - 1 0 01 - 3 - 1 0 0 8 - 3 3 -1 12

17 - 2 2 f 24 1 £ 17 *27 £ 2 3 f 24 £ 89 f - 110 0 64 f 2 -4 1 • 7 -4 -7

-1 - 9 - 1 2 - 1 2 15 6 7 - 5 5 f

2 8 f IB - 2 5 f 17 - 1 2 0 12 9 4- 6 -4 - 1 6 - 7 0 - 3 6 - 5 13

■11 - 1 5 2 3 £ - 1 8 - 1 5 - 21 £ - 1 5 32 f 77 3 4 8 f - 7 - 31 £ 0 0 -1 5

-2 -2 1 - 9 9 -1 -2 6

2 1 1 - 3 0 - 1 3 5 7 - 6 -7 -50 0 4 - 5 2 -1 2 -1 3

-1 - 5 - 2 -4 -4 2 f -1 51 £ 129 16 - 5 2 9 f - 14 4 3 - 1 3 - 9

- 8 4 0 2 1 -2 5 1

3 3 f 2 0 - 3 0 f 4 6 - 0 - 4 4 6 f11 2 0 2 8 5 f 1 -1 2 -1 0

0 -1 - 2 -7 7 13 5 6 £ 83 1 - 4 24 £ - 1 2 3 1 - 8 0

-17 1 - 3 - 3 0 - 2 1 -1

3 - 3 - 5 4 £ - 2 0 £ - 1 08 1 2 2 £ - 1 7 - 1 4 23 f 7 1 14£

4 2 f - 2 8 f0 3 0 -11 15

16 56 £ 13 -7 12 11 9 f 7- 47 f 1 1 3 3 f

11 - 1 14 - 3 7 f - 5 4 f - 2 8 f - 82 54 f - 5 - 4 -2 -4 1 f 3 33 f

I 90 f - 8 - 1 0 2 4 £ - 3 0 £ - 1 3 - 2 2 f- 6 - 22 £ 0 1 - 1 2 - 67 £ -2 - 2 2 £- 8 22 f 7 - 2 - 1 2 - 9 -4

- 5 3 £ 2 3

6 6 f

3 0 f 5 284 £

SUMMARY OF LABORATORIES' RESULTS

Di s t r i b u t i o n n u m b e r : 05D a t a s e t : f t qu e o ua d e t e r m i n a n d sD a t e o f d i s t r i b u t i o n : SEPTEMBER 1993


G r o u p 5 - O r g a n o c h l o r i n e s s a m p l e A- a-HCH (A) - 6 5 f- g-HCH (A) - 3 0 8- HCB (A) - 3- HCBD (A)- b-HCH (A)

D i e l d r i n (A) 9 5 fA l d r i n (A) - 1 6E n d r i n (A) 0 5 f

® I s o d r i n (A) 17- pp ' DDT (A) 93 f- pp ' DDE (A) 1 5 1 f- pp ' DDD (A) 2 2 4 f ~ op ' DDT (A)

T r i f l u r a l i n (A) 62tT o t a l E n d o s u l p h a n (A)

- 1 , 2 , 4 T r i c h l o r o b e n z . ( A )• 1 , 3 , 5 T r i c h l o c o b e m . (A.)~ 1 , 2 , 3 T r i c h l o r o b a n i . ( A )

G r o u p 5 - O r g a n o c h l o r i n e s s a m p l e B- a-HCH (B) - 60 f- g-HCH (B) - 5 5 f - 1 7- HCB (B) - 1 3- HCBD (B)- b-HCH (B)- D i e l d r i n (B) 30~ A l d r i n (B) - 1 1- E n d r i n (B) 119 I s o d r i n <B)- pp ' DDT (B) 3~ p p ' DDE (B) 42- p p ' DDD (B) 72 f- op ' DDT (B)

T r i f l u r a 1 i n (B) 9- T o t a l E n d o s u l p h a n (B)- 1 , 2 , 4 T r i c h l o r o b e n z . fBJ* 1 , 3 , 5 T r i c h l o r o b e n z . (B)

1 , 2 , 3 T r i c h l o r o b e n z . ( B )

APPENDIX 4.23(2)

MF.AN DIFFERENCES FROM REFERENCE CONCENTRATION ( I )

L a b o r a t o r y n u m b e r7 10 11 12 14 15 17 : I S 19 20 21 23

- 3 4 46 - 2 3 - 5 1 f 17 46 - 3 0 37 2 8 5 f 2 3 0 f- 5 9 £ 221 £ - 4 5 - 5 5 9 f - 11 22 9 9 f 13 8 8 f- 1 8 22 - 1 2 48 3 48 12 26 37

- 9 13 - 6 ■ 1 18 2 23 f54 6 f 10 10 0 1 5 2 £ - 2 1

- 2 8 101 f 10 2 25 5 2 f- 4 3 30 - 1 2 41 0 6 6 f - 2 4 45 15- 2 0 - 1 5 222 f 13 8 5 f -1 43 30

- 1 729 2 7 6 f - 1 6 12 22 24

77 £ - 2 5 9£ 67 £ 1 4 4 £lOOf 19 12 9 f 4330 5 £ - 1 8 82 £

31 - 5 120£ 8 3 f 3 - 2 5 3677 £ 27 - 3 1 3 3 f

52 f - 1 2 - 2 2 20 43 67 f- 6 7 67

- 3 - 1 1 13

- 2 9 43 - 6 34 19 - 1 2 - 6 6 f - 8 8 2 f 28- 4 1 l OOf - 2 2 -3 15 - 3 3 - 3 3 24 24 1- 21 5 - 3 16 1 - 2 0 - 6 4 f - 2 10 - 9

- 1 4 14 10 - 1 9 ~ 67 f 13 16 163 66 f 167 f 30 6 - 5 2 £ 52 f 9

- 5 3 - 2 2 44 6 4 - 5 6 f - 1 0 - 2 40- 3 7 31 - 4 16 4 - 1 2 - 7 4 f - 2 17 3- l f l 14 - 2 0 11 8 £ 16 11 - 61 f - 7 15 0

0-1 - 3 6 - 2 4 1 27 £ - 1 21 - 3 6 - 7 9 1- 9 6 - 1 2 36 5 24 -4 6 - 3 - 9 52 £

- 1 2 - 2 6 77 f 18 - 4 5 -1 19 430 - 1 1 123 f 29 - 7 7 f 7 2

30 17 1 58 f 7 14 - 5 5 f 48 - 1 5- 2 7 6 3 f 3 0 - 7 Of 0

42 - 1 0 - 6 4 f 21 5 5- 5 0 50

5 -1 - 1 3 - 6 8 f - 2 4 - 1 0

APPENDIX 4.2.3f3)


D i s t r i b u t i o n n u m b e r 05D a t a s e t : A q u e o u s d e t e r m i n a n d sD a t e o f d i s t r i b u t i o n : SEPTEMBER 1993

MEAN DIFFERENCES FROM 'REFERENCE CONCENTRATION (%>

L a b o r a t o r y n u m b e r3 4 5 7 10


G r o u p 6 - V o l a t i l e s s a m p l e AC h l o r o f o r m (A) - 1 9 - 2 2 27C a r b o n T e t r a c h l o r i d e (A) - 5 1 f - 2 5 - 2 2Tr i c h 1o r o e t h a n e (A) - 5 1 , 2 P i c h l o r o e t h a n e (A) - 2 3 T r i c h i o r o e t h e n e (A) - 34 T e t r a c h l o r o e t h e n e (A) - 3 5 - 3 4

1149

- 1 3- 2 5

G r o u p 6 - V o l a t i l e s s a m p l e B,C h l o r o f o r m (B) 9 - 69 £ 21C a r b o n T e t r a c h l o r i d e (B) - 4 2 9 -1T r i c h l o r o e t h a n e (B) 5 6 f 1 , 2 D i c h l o r o e t h a n e (B) - 5 T r i c h l o r o e t h e n e (B) -21 T e t r a c h l o r o e t h e n e (B) -31 - 3 7

1446-2

- 1 0

G r o u p 7 - P e n t a c h l o r o p h e n o l s a m p l e A- PCP (A) - 2 7 - 2 4

G r o u p 7 - P e n t a c h l o r o p h e n o l s a m p l e B- PCP (B) 17 - 2 5

C r o u p 8 - T r i a z i n e s s a m p l e AS i m a z i n e (A) - 1 7 - 1 0At r a z i ne (A) - 1 6 - 1 1

G r o u p 8 - T r i a z i n e s s a m p l e BS i m a z i n e (B) - 2 0 - 1 0

~ A t r a z i n e (B) - 1 8 - 3

G r o u p 9 - O r g a n o p h o s p h o r u s Compounds A z i n p h o s - m * t h y 1 ( A )

s a m p l e A - 8 - 7 16

A l i n p h o s - e t h y l ( A) - 5 0 23F s n t h i o n (A) 6 - 1 6 -2M a l a t h i o n (A) 17 - 3 0 - 5P a r a t h i o n (A) 12 -4Pa r a t h i o n - m e t h y l (A) 1 - 2 3 1F » i u t r o t h i o n (A) - 6 - 0 1

G r o u p 9 - O r g a n o p h o s p h o r u s Co mp ou n d s A z i n p h o s - m e t h y l (B)

s a m p l e B - 3 3 - 1 7 32

A z i n p h o s - e t h y 1 (B) - 9 . - 6 43F » n t h i o n (B) - 7 - 3 11MaI a t h i o n (B) - 1 0 7 4P a r a t h i o n (B) - 2 8 0P a r a t h i o n - m e t h y 1 ( B) - 2 2 - 1 2 11Fen i t r o t h i o n (B) - 2 3 5 a

11 12 14 15 17 18 19 20 21 23

36 - 8 -1 10 19 1 04 f - 3 647 10 - 2 0 - 2 0 - 9 1 1 6 f - 1 234 16 - 2 5 4 2 1 2 7 f -11

- 1 2 2 94 f -2 1■31 - 1 0 1 -7 13 11 6 f - 1 0■52 f - 1 4 - 1 5 - 2 2 - 8 1 1 0 f - 1 0

- 5 - 3 1 20 29 - 2 - 2 126 22 - 1 0 - 9 14 - 2 6- 2 21 - 2 8 4 17 5 - 615 -2 38 - 3 -2- 3 0 17 0 20 0 3

■33 -1 - 5 - 7 5 -1 5

•16 - 9 - 6 41 0 - 1 5 - 1 3 - 4 7

- 9 - 8 - 7 13 0 - 1 0 - 9 - 4 7

-33 - 1 0 - 1 7 - 1 1 - 3 3 15 - 5 - 2 0 - 8 - 1 5 3

-35 - 9 - 2 9 - 1 8 - 3 5 117 -1 - 2 6 - 1 3 - 1 9 5

10 - 5 - 2 3 16 91 f - 1 4 - 2 0 3

- 7 - 21 - 1 1 2- 7 5 - 2 8 - 2 6 - 2 2 - 2 6

6 12 21 1 9 - 1 2 -75 - 1 2 39 12 - 11 - 57 - 1 9 - 4 - 1 8 - 1 5 - 1 0

10 - 1 9 - 1 1 104 17 - 3 - 2 6 13

23 - 6 6 f - 2 5 80 -14 - 3 8 - 2 5 - 3 3 - 2 00 -2 - 1 0 -24 - 2 4 - 1 0

- 3 - 1 0 8 - 2 0 - 2 6 -111 - 2 4 - 2 8 -14 - 3 0 - 5

N c t e s :f i n d i c a t e s f a i l u r e t o a c h i e v e t h e p r e s e t s t a n d a r d o f a c c u r a c y a H»«n o f a l l l a b o r a t o r i e s u s e d f o r c a l c u l a t i n g mean d i f f e r e n c e

it***'! f n r era 1 m 1 * t: i no m»an rti f f»r^nr»>

APPENDIX 4.2.3(41


D i s t r i b u t i o n n u i nbe r : 05D a t a s e t : S e d i m e n t d e t e r m i n a n d sD a t e o f d i s t r i b u t i o n : SEPTEMBER 1993

MEAN DIFFERENCES FROM REFERENCE CONCENTRATION P )

L a b o r a t o r y n u m b e r3 4 7a 8 9 10 I I 12 15 17 18 19 21 23 7b

D e t e r m i n a n d -

■ C o p p e r *7 3 - 3 5 5 10 5 4 -4 - 3 - 1 0 - 4 - 8 6l - a d - 1 5 8 4 9 1 5 3 - 2 -7 0 - 8 0 - 3 5

r Ca dmium - 1 5 1 8 34 f - 7 7 f 5 11 31 f 13 - 4 5 f 1 3 5 f - 1 6 8 34 fr Z i n c 1 2 9 6 0 - 1 7 - 5 5 1 9 -8 - 7 -4 99 NicV.el - 1 5 4 2 - 7 -5 - 1 7 8 2 9 f -1 15 - 1 5 - 1 2 -2 17, C h r om iu m - 9 37£ - 2 0 f - 1 0 - 2 8 f - 1 7 31 £ 2 3 f 41 f -1 - 1 2 -2 4 f - 1 0 -1’ M e r c u r y 2 7 - 3 9 7 6 0 - 6 - 9 - 1 30 A r s e n i c 3 -4 14 - 1 3* A l u m i n i u m - 2 5 - 3 5 f 60 f

C r o u p 2- HCB 2 16 - 9 - 4 0 - 2 8 1 - 4 5- PCB 2 6 1 2 0 f 127 f - 1 6 - 1 5 5- PCB 3! 87 f 48 - 7 35- TCB 52 3 40 f 76£ SO 6 f- PCB 101 0 6 9 f - 1 4 - 5 3 f - 3 0 21 - 3 8

TCB 105 44 40 - 6 - 2 3 - 3 6 73£ - 1 5PCB 1 1 B 1 05 £ 93 f 32 - 1 4 - 1 3 1 7 5

- PCB 13 0 29 26 - 2 0 - 3 6 - 2 5 - 1 2 - 2 7- PCB 15>3 5 9 f 24 1 - 2 8 - 3 5 - 2 4- t c b 26 - 2 - 1 4 - 3 6 - 2 5 3 - 1 8- PCB 190 7 3 £ - 4 19 - 1 8 - 5 - 2 - 5

A l d r i n - 1 3 - 34 - 83 f - 4 8 - 6 9 fE n d r i n 26 - 1 1 - 5 6 £ 6 24D i e l d r i n l e 61 £ 27 - 47 -7 38I s od r i n 2 - 04 f - 5 3 f - 31

- pp ' DDT - 1 8 14 - 1 3 - 4 2 - 1 8 32- p p ' Dt'E 1 6 32 14 - 3 3 - 3 67 f- p p ' DPD 0 81 f 7 - 3 6 - 1 6 46

op ' DDT - 5 0 - 2 3 51 £

Not e s :f i n d i c a t e s f a i l u r e t o a c h i e v e t h e p r e s e t s t a n d a r d o f a c c u r a c y

M>?an o f a l l l a b o r a t o r i e s u s e d f o r c a l c u l a t i n g moan d i f f e r e n c e N o m i n a l v a l u e u s e d f o r c a l c u l a t i n g mean d i f f e r e n c e

APPENDIX 4.2.3(5)


Di s t r i b u t i o n n u m b e r : 05D a t a s e t : MARINE BIOTAD a t e o f d i s t r i b u t i o n : SEPTEMBER 1993

MEAN DIFFERENCES FROM REFERENCE CONCENTRATION ( t )

L a b o r a t o r y n u m b e r

D e t e r m i n a n d3 4 7 0 9 10 11 12 17 10 23

G r o u p 1 L e a d 12 - 6 -1 5 19 - 24 f 1 - 91 £ 4 - 1 0

* Ca dmium - 1 8 -1 7 4 8 8 13 . 6 -31 f 4* Z i n c - 1 3 0 4 1 4 6 f -2 - 3 1 -1 2 -2* M e r c u r y - 1 2 - 1 1 7 3 7 1 f 17 - 3' A r s e n i c 62 - 3 4 23 - 5 0

G r o u p 2 - SAMPLE AD i e l d r i n 93 f 36 17 - 1 3 - 2 0 24 2 f 7 33I s o d r i n 47 - 2 6 - 2 6 - 4 4 60 f 11 5 f

- a-HCH 30 6 f - 2 6 - 5 0 - 2 3 29 7 5 f- g-HCH 51 7 £ i s -2 11 - 2 9 - 3 9 9 f- b-HCH 2 5 8 f - 5 5 - 1 0 15

p p ' DDT 7 4 f - 5 4 f - 5 0 f 8 - 4 7 - 4 5 23 - 1 0- p p 'DDE - 6 - 1 7 9 0 - 1 9 - 7 3 f 22 6

pp ’ PDD l l O f - 4 0 - 11 - 5 5 f - 4 3 - 5 17op 'DDT - 7 3 f 0 - 4 5A l d r i n 60 f - 5 - 3 4 - 6 - 4 3 1 9 8 fE n d r i n - 3 9 - 7 3 f 47 - 2 6 - 67 f 22 - 2 6

- HCB -2 49 39 - 4 3 5 6 16 7 0 f- HCBD - 8 2 f 72 f -1 1 10- PCB (28) 27 - 5 - 52 f - 5 l f- PCB (31 ) 38 39- PCB (52) 17 8 f 7 5 f 7 3 f 77 f 4- PCB (101) - 2 9 44 11 5 - 1 5 - 5 6 f -2 4- PCB ( 10 5 ) 23 - 3 0 - 3 2 - 1 4 - 3 7 5 1 f 10- PCB (11B) 1 6 15 - 1 7 - 6 2 6 - 1 2 17- PCB ( 13 0 ) 6 - 2 5 2 - 60 f 12 12 13 31- PCB ( 15 3 ) 0 - 2 2 15 -44 8 - 5 9 f 5 7 4 £- PCB ( 15 6 ) 27 - 61 f - 2 2 -31 -1 6 41 23~ PCB ( 10 0 ) 9 - 7 0 f - 2 3 - 2 8 - 3 4 - 1 5 4 - 2 1

G r o u p 3 - SAMPLE A- PCP

Hot e s :f i n d i c a t e s f a i l u r e t o a c h i e v e t h e p r e s e t s t a n d a r d o f a c c u r a c y8 Mean o f a l l l a b o r a t o r i e s u s e d f o r c a l c u l a t i n g mean d i f f e r e n c e

N o m i n a l v a l u e u s e d f o r c a l c u l a t i n g mean d i f f e r e n c e

APPENDIX 4.2.3(6)

P i ? t r i b u t i o n n u m b e r : 05D a t a s ^ t MARINE BIOTAP a t e o f d i s t r i b u t i o n SEPTEMBER 1993


MEAN DIFFERENCES FROM REFERENCE CONCENTRATION (»)

L a b o r a t o r y n u m b e r

D e t e r m i n a n d3 4 7 8 11 12 18 23

G r o u p 2 - SAMPLE BLi 1 e 1d r i n 98 f 48 - 5 8 f - 14 - 2 3 256C 4 38I s o d r i n 41 - 2 3 - 3 2 - 5 0 0 7 2 f

- a - HCH 1 4 1 7 f - 1 9 8 0 f - 4 6 271 f~ g-HCH 17 4 5C 78 f 21 84 £ 7 -21 337 f- b-HCH 3 3 5 f 18 - 3 7 2- p p ’ DDT 70 f 30 - 71 f - 2 2 - 4 9 - 5 2 f 19 -4- p p ' DDE - 1 5 29 5 -7 - 2 2 - 7 9 f 27 5

f-p ’ PDD 1 04 f - 4 1 - 50 f - 1 0 - 60 f - 62 f - 2 19- c p ’ PDT - 93 C 12 31

A l d r i n 3 - 1 5 - 3 3 - 3 3 - 6 - 1 6 67 £Knd r i n - 5 3 f - 02 f 38 - 2 6 -71 f 26 - 2 9

- HCB 20 29 41 4 0 O f 1 0 5 f 20 20 1 33 f- HCBD - 5 6 f 90 f - 53 f 75 f- t c b (28) 39 - 4 4 - 69 f 1 22 £- r c n (31 ) 1 2 8 f 25

PCD (52) 26 1 21 f 1 4 5 f 1 6 6 fPCB < 101 > - 4 3 7 11 - 3 7 - 51 f 13 1

- PCB (105) 26 72 f - 4 4 7 - 4 0 43 26- r c e ( 118) 14 1 3 3 f - 2 6 - 2 - 1 3 - 3 - 1 2 34- PCB (138) 1 10 .7 f - 2 - 59 f 23 - 3 11 43- PCB (153) - 1 2 1 04 f 3 - 5 0 2 - 6 6 f - 3 87 f

t c b ( i *i e > 28 51 £ - 3 0 - 3 1 50 10 15- F’CB ( 180) - 5 15 - 2 8 - 2 6 10 - 3 3 1 - 1 0

G r o u p 3 - SAMPLE B- PCP

Not e s :f i n d i c a t e s f a i l u r e t o a c h i e v e t h e p r e s e t s t a n d a r d o f a c c u r a c y 1 M»an o f a l l l a b o r a t o r i e s u s e d f o r c a l c u l a t i n g mean d i f f e r e n c e


APPENDIX 4.2.3m

D i s t r i b u t i o n n u m b e r : 05D a t a s e t : MARINE BIOTAD a t e o f d i s t r i b u t i o n : SEPTEMBER 1993


MEAN DIFFERENCES FROM REFERENCE CONCENTRATION ( I )

L a b o r a t o r y n u m b e r3 4 7 0 11 12 18 23

Pe t e r mi n a n d

G r o u p 2 - SAMPLE C- D i e l d r i n 40 30 11 - 1 7 - 3 6 178 f 30 6- I s o d r i n 40 - 3 4 - 2 9 - 51 f 6 49- a-HCH 2 31 f - 3 7 - 3 7 - 3 7 17 46- g-HCH 307 f -3 - 6 -4 - 2 3 8 5 2 f- b-HCH 1 97 £ - 1 0 - 2 3 8- P P ' DDT 24 26 - 3 9 -3 - 51 f - 66 f 8 -4- PP ’ DDE - 2 6 18 - 3 - 1 2 - 3 0 - B l f 11~ PP ' DDD 5 9 f - 37 - 3 0 - 1 7 - 60 f - 53 f 0 -1- Op ’ DDT - 2 3 -1 - 4 2

A 1 d r i n 29 -2 - 53 f - 3 5 -31 -3 11- End r i n - 2 2 - 5 6 f 35 - 4 5 -51 f 19~ HCB - 2 4 16 24 - 4 7 5 - 6 24 0 9 f- HCBD - 60 f 124 f - 5 24- PCB (2 B) -1 - 3 3 - 5 6 f - 2 9- FCB (31) 6 - 4 8 36- PCB (52) 92 f 44 27 50 f - 42- PCD (101 ) - 36 77 f 7 - 2 - 70 f - 4 5 -1 2- PCB (1 05 ) 7 50 f - 3 0 - 1 8 - 4 0 11 -3~ PCB (110) 6 l l O f - 1 2 12 34 -21 4 17- PCB (1 39) - 6 95 f - 2 0 - 52 f - 1 0 - 3 3 -7 33- PCB (153) - 1 3 77 f 4 - 5 1 f - 1 3 - 7 3 f - 1 6 62 f- PCB (156) -3 41 - 2 5 - 3 9 -1 - 34 7- PCB (1 00) - 1 4 18 - 1 0 -26 - 6 - 57 f - 1 5 - 3

G r o u p 3 - SAMPLE C- FCP

Nc>t e a :f i n d i c a t e s f a i l u r e t o a c h i e v e t h e p r e s e t s t a n d a r d o f a c c u r a c y* Mean o f a l l l a b o r a t o r i e s u s e d f o r c a l c u l a t i n g mean d i f f e r e n c e


<• ,T * '

V'1

u

f

Stf-MARY ZF LA BO RAT CRIES ' RESULTS

" i s ; : : b ’j : i s n nu: r .ber : 06D a t a s e t : A q u e o u s d e t e r m i n a n d s C a t o o : d i s t r i b u t i o n : MARCH 199*1 ;

■

*; • 4 5 7i*

*’►> ,C e t e r nv . na r . c

■

* ' c r r - j p 1 - S e a w a t e r s a m p l e A•’ A - T . T . s r . i a (A) - 1 7 10 - 1 6

' i r ' » TCN (A) 12 - 7 2 9 6 2 f• 5r - N i t r i t e (A) e 58 f - 3

‘ - O r t h c p h c s p h a t e (A) 16 1 - 5V » S i l i c a t e (A) - 6 16 - 5t•p’ • I c r c u p - S e a w a t e r s a m p l e 5

A - T . T . o m a ( 2 ) - 2 -S 3\ 6

‘TCN (5) 5 - 3 4 9 0 fN i t r i t e (3) 7 9 - 3

¥ C r t h c o r . o s p h a t e (3) 6 20 - 1*> fc S i l i c a t e (3) -4 13 - 2

j? Gr o u p 2 - E s t u a r i n e s a m p l e A.* ► ’ - A-t.t.c r. i a ( A) -1 - 2 8■1 t o :: (A) 9 - 1 1 - 1 3;* i ' . K it. r i t e (A) 2 IS - 3

( C r t r . c p h o s p h a t e (A) 1 _ -5 - 50 S i l i c a t e (A) 0 -2 - 2

*,r Gr c u p 2 - E s t u a r i n e s a m p l e B- -A - 2 4

**; c TON < = > 17 _ T - 2 6 f■\ * N i t r i t e (3) l l O f 12 - 1 6r ‘ * C r t r . c p h c s p h a t e (3) - 6 _ 2 - 1 8»

• S i l i c a t e ‘(B) 1 - 4 - 2r

c r o u p 2 - T r a c e m e t a l s s a . - p l e A/ , D i s s o l v e d Cadmium (A) - 32 f - 2 4 f

- D i s s o l v e d C c p p e r (A) 3 4 f 9 3 fV - D i s s o l v e d Load (A) 3 4 fI* D i s s o l v e d N i c h e 1 (A) 9 - 5* • t • > « D i s s o l v e d Z i n c (A) - 2 2

j • , ~ D i s s o l v e d C hr omi um (A) - 1 6

■.1 c r c u p 2 - T r a c e m e t a l s ss .T.ple 3• I i s s e l v e d Cadmium (E) - 3 2 f - 1 2

* D i s s o l v e d C o p p e r (B) 1 1 21 f/ D i s s o l v e d L e a d (3) 4 18

’ D i s s o l v e d N i c k e l !2> - 5 - 4* ~ D i s s o l v e d Z i n c (E) - 1 6 10

* D i s s o l v e d C h ro m iu m <B) - 2 3 f

; ■ G r c u p 4 - X e r c u r y s a m p l e A- T o t a l X e r c u r y (A) 62 f 112 f

C r s u p 4 - Xo r c u r y s a r . n l e 2' T c t d 1 X - i r c v r y (B > 1 - f 8 9 f

APPENDIX 4.2.3(8)

NATIONAL MARINE AQC SCHEME

MEAN DIFFERENCES FROM REFERENCE CONCENTRATION (%)

L a b o r a t o r y n u m b e r9 11 12 13 14 15 17 19 20 21 23

■92f 11 - 31 f - 2 6 f - 1 3 - 2 6 f - 7 - 1 97 4 - 1 7 - 1 4 - 1 8 7 5 2 0 f

-2 16 16 - 2 1 f 13 - 3 8 4 - 3 6 f6 9 15 1 2 3 f - 1 5 - 7 O'

13 3 3 - 1 7 - 8 8 13 - 1 8

-2 4 - 1 7 -221 2 - 1 5 1 - 110 1 - 3 -2 1 0 1 - 1 10 2 4 - 7 1 0 0 8 - 8 9 f2 4 3 - 2 7 f 4 1 1 4 - 6 4 f6 - 5 - 2 5 0 f -7 1 4 - 3

9 - 6 3 - e - 7 4 - 1 5 - 2 1 f5 - 3 2 2 5 4

- 2 12 17 i - 2 4 9 27 f1 - 5 - 3 2 3 - 3 - 2 9 f0 -1 1 1 2 0

■49f 5 0 5 3 - 1 1 - 2 4 f0 4 e 7 6 - 2 1 f

0 1 3 - l - 6 3 f 1 12 82 - 6 - 3 - 2 - 1 - 4 - 1 51 -1 1 -1 4 1

- 1 0 - 2 56 f - 1 844 f - 1 4 3 1 3

7 5 - 50 9 f 5 3 -4 - 7

1 - 2 9 f 3 2 5 f- 2

5 3 f 6 - 2 18 - 1 030 f - 5 - 4 0 832 f 0 -2 - 710 5 - 3 1 - 9

- 1 - 5 3 71

6 9 f - 1 0

SUXT-'-ARY or LABORATORIES' r e s u l t s

D i s t r i b u t i o n n u m be r : 06D a t a s e t : A q u e o u s d e t e r m i n a n d sD a t e o f d i s t r i b u t i o n : MARCH 1994


C r o u p 5 - O r g a n o c h l o r i n e s s a m p l e A- a-HCH (A) - 2 1• g-HCH (A)

HCB (A) - 5 10HCED (A) - 3 0

- b-HCH (A) 4 1- D i e i d n n (A) - 1 6 16

A i d r i n (A) 2 2 4

E n d r i n (A) - 1 3 - 3 I s o d r i n (A)

- pp 'DDT (A) 30 - 2 2 p p ’ DDE (A) - 6 76C

- pp ' DDD (A) 31 0 op ' DDT (A) - 3 0 T r i f l u r a l i n (A) 16T o t a l E n d o s u l p h a n (A)1 , 2 , 4 T r i c h l o r o b e n z . (A)

‘ 1 , 3 , 5 T r i c h l o r o b e n z . (A)1 . 2 . 3 T r i c h l o r o b e n z . (A)

G r o u p 5 - O r g a n o c h l o r i n e s s a m p l e B~ a-HCH (3) 5- g-HCH (3) - 2 7 1- HCB (3) - 1 3 - 4- HC2D (2) - 1 4- b-HCH (21 21 - D i e l c r i n (9) - 1 0 17- A l d r i n < 3) - 6 7- E n d r i n (3) - 5 2

I s o d r i n (B)

- p p 'D D T (3) 30 - 4 0- p p ' S D E (2) - 1 4 4 6- p p ' D 0 D ( B > 17 7

o p ' D37 (3) - 1 7 T r i f l u r a l i n ( B > 32T c t a i E n d o s u l p h a n (B)1 . 2 . 4 T r i c h l o r o b e n z . < Q>: , 2 , 5 T r i c h l o r c b o n z . (3)1 , 2 , 3 T r i c h l o r o b e n z . ( 3 )

APPENDIX 4.2 3 (9)


KEAN DIFFERENCES FROM REFERENCE CONCENTRATION (*>

9 11L a b o r a t o r y n u m b e r 12 13 14 15 17 19 20 21

- 2 5 - 2 5 - 2 5 58 f 26 - 3 6 - 9 - 2 55 6 f - 6 5 f 64 f - 6 - 2 6 - 1 0 - 1 2

3 - 1 5 - 2 1 18 - 2 6 3 - 4- 3 5 - 5 40 16 21

- 2 2 2 7 6 f 27 - 3 8 - 4 75 - 3 3 - 1 2 121 f 5 - 4 7 - 1 4 - 4

5 5 f - 1 4 - 1 7 5 - 3 1 9 24- 2 3 - 3 3 - 7 2 f 164 f - 3 - 7 9 f - 1 5 - 8

4 S 0 f- 5 3 f - 3 2 - 2 1 130 f - 2 4 - 1 9 - 3 6- 3 9 - 3 9 9 6 - 2 4

- 5 - 2 4 5 14 3 f 24 7- 9 - 9 - I B 32 - 2 - 2 3- 7 14 - 1 6 - 5 7 69 f

- 5 0 7 0 - 3 51 - 2 2 - 8 11

13 16

- 3 - 1 0 - 2 1 34 15 - 4 6 - 1 1 - 2 213 - 1 8 - 2 6 6 0 f - 2 - 3 8 - 7 - 2 127 - 1 9 - 8 27 18 - 3 9 - 1 -4

- 2 2 - 2 15 - 1 6 33- 1 1 - 1 4 19 6 f - 3 - 4 2 - 1 1 - 4 2

48 - 2 8 0 60 f 7 - 1 1 - 0 408 9 f - 1 3 11 1 - 2 0 7 - 4

5 - 2 4 9 120 f 5 - 3 6 * 13 53 0 0 f 1 2 9 0 f- 3 9 - 2 3 - 2 3 6 8 f 12 - 30 - 2 5 - 3 4- 1 4 - 2 2 40 67 f 5 - 2 7 - 2 0 - 3 0

- 8 - 21 21 9 5 f 30 - 1 3 1736 - 1 0 1 24 22 - 5 - 030 3 - 2 11 1 6 81 f

- 2 2 - 5 5 f 18 - 3 4 24 - 517 - 2 3 4 - 8 33

8 0 0 f S67£

t

s o ? l a s c r a t o p .i e s ' r e s u l t s

I r :cm; ten r.uT.ber 06a ca set A q u e o u s d e t e r m i n a n d s

I a c & c : d :sinbi:tier. MARCH 1994

• G:■cm?. i - '.’c l a t ' - i e s sa.T.pie A' ~ C 1 c r c f c rrr. (AI - 5

~ T a r b c r. T e t r a c h l o r i d e (A)- Tr : c h i c r c e c ha r . e (A) - 1 4

, - 1 , 2 3 i cr. 1 c r o e t ha ne (A) 5* T r : c h l c r c e c h e r . e (A)*•

' Cr c-jp i - V c l a c i l e s s a - . o l e 5, ~ C h i s r e : c r ~ (2) - 4 2

* - Ca rbc r . T e t r a c h l o r i d e O ) -*15- T r : c h l c r o e t h a r . e (2) - 2 3

, ~ 1 , 2 D i c h l o r c e t h a r . e (2) - 2 5- T r : c h l c r c e c r.or.e (B) - 2 4~ To", e a c h 1 c r o o t h e r . e (3) - 3 5

k Cr c.'-p “ - ? c-.-.c a c h l o r s p h e r . o l s a m p l e A‘ ?C? i A) - a 4

Cr cmc 7 - P e r . t a c h i o r c o h e r . e l s a m p l e B' ? : ? (5) 21 _ 2

Gr cmc i - T n a c i r . e s s a r . ' l e A- Si.T&zir.ft (A) - 2 9 - 2 0- - 3 2 10

t ’* . G: c m c 5 - T r 1 a 2 1 r . es s a - p l e 2

* \ ~ £ i r . i c i r.e f 3 > a - 2 0’*’f ' A c r a z i r . * (B) -2 - 1<?*

G r c m c ; - C r c a r . c p h c s p h o r u s C o mpounds s a m p l e A*' ' Ac: r . p h c s - n e c h y L (A) - 3 5 1/ - A z : r. c h c s - e c h y 1 < A) - 2 5 1Y , ~ - 2 0 - 8

- X a l s t h i c r . (A) ? 13>; ~ r a r a " r . : c r. ! A i 645 30

- F a r a c h : c r . - m e t h y l (A) - 1 5 21“ " o ; . : c r c c r . : c r . < A) -3C 6

VGr c u p y - O r g a r . c p h o s p h o r - j s Cc r .pour .ds s a m p l e B

$ - Ac i r . ph cs -.T.et h y 1 (£) 11 2 2

A - Ai i r . p h c s - o t hy 1 (5) 5 - a- F e r . t h i c r . (3) _ c

- nv

] - . X a l a c h i c r . <B) 1 3/> ' P a r a t h i c r . (2) - 1 0 0

• , ~ ? a r * c h : c r . -.-no c h y 1 < 2 ) - 1 2 - 4•• i.' > ~ ~ e r . i c r c t r . i o r . (3) - 2 1 - 5f

He: . s :i : r. - -. w .i •„ •; s f a i l u r e t o a c h i e •.•o t h e o r e s o t n.

APPENDIX 4,2.3(10^


MEAN DIFFERENCES FROM REFERENCE CONCENTRATION <%)

L a b o r a t o r y n u m b e r9 11 12 13 14

0 - 3 4 10flOf - 9 1 f 12

- 2 0 - 4 3 47- 3 3 6 - 1

- 5 - 3 23- 2 1 - 2 4 12

13 - 8 0- 8 - 8 3 f - 322 3 1349 - 1 4 8- 2 - 3 4

- 1 9 2 - 1

- 6 5 f - 5 5

- 5 6 f 20 6

- 2 5 - 1 3 - 1 3- 2 0 6 - 1

- 1 2 - 4 2 A-7 - 3 6 5

15 - 1 512 - 1 5

5 5 -120 - 5 - 1 131 14 - 1 1

9 - 3 - 320 - 2 - 8

13 - 1 115 - 9 '

3 8 - 021 - 8 - 2 033 17 - 1 020 - 2 - 230 - 2 - 9

15 17 19 20 21 23

3 35 10- 1 2 12 5

- 5 - 3 3 64 f- 7

12 6 3 f 2 5- 1 15 . 15

- 3 36 A- 2 4 17 0- 2 0 3 22

- 1 3- 1 2 36 13- 2 0 15 5

19 - 6 - 3 - 2

3 - 2 6 10 a

12 - 6 2 £ 7 - 3 2

5 - 6 6 f- 7 - 4 8

-34-3T

- 7 720 - 2 8 6 9 f - 4 2 43 - 3 2 39 - 3 4

- 2 4-27

- 9 - 1 319 - 2 35 6 f - 2 829 - 3 131 - 2 4

APPENDIX 42.3(H)

5 wC-lAP.Y or LAHOPJVTGR IES ' RESULTS NATIONAL MARINE AQC SCHEMED i s t r i b u t i o n r. urr.ber I/A - a s e t-■die o f d i s t r i b u t i o n

06

MARINE BIOTA {FISH OIL) MARCH 1994

MEAN DIFFERENCES FROM REFERENCE CONCENTRATION ( I )

^oter-ir.dr.aL a b o r a t o r y n u mb e r

7 11 12 14 15 21

C r o u p 2 - SA.XPLE D i e i d r : r.I s c - d n r. a - H C H c-r

no

PCB PCs PC ■> PC2

(2 5 )(21)(10*)

PCS (105) PC3 11i 2)PCs (: 2 s >

C 5 3 i <:5S)c s :)

3 1 16 - 3 - 6 -7 7 2 6 f- 9 1 7 8 f 1 2

25 19 3 - 1 8 - 1 3: a o f -4 324 f 48 - 3 9 - 3 741 f

78 f 1 5 3 f 424 12 - 9 - 1 1 - 1 7 117 f- 3 5 16 13 15 - 4 9 965

- 3 8 21 - 1 3 - 34 - 2 4 - 2 2 68 f44 - 4 4

-1 50 32 - 2 5- 53 f 0 - 5 4 f -41 35 875

- 1 1 ■il 16 17 14 - 1 5 4 21 f- 3 1 - 5 3 f

5 - 6 4 f 2 3 3 f 5 43 40 - 4 2- 5 5 8 f 47

- 1 4 20 3 f 61 f 63 f 15 8 9 f 42- 2 2 10 0 - 1 0 - 1 6 21 - 1 9 7 1 f- 2 2 -7 - 6 - 3 2 - 4 4 - 2 0 - 5 0 f

- 3 16 - 2 - 4 7 0 14 - 2 4 82 f21 1 0 - 3 5 - 1 15 1 1 3 0 f_ 2 215 1 7 - 2 0 12 2 7 1 1 2 3 ;- 9 0 - 8 S f - 3 3 5 4 ■j- 7 4 11 - 59 f 5 4 - 2 0 2 39£

r . c ^ c a i t s f a i . u r o t o a c r . i e v e t h e p r e s e t s t a n d a r d o f a c c u r a c y ‘Mr. o f a l l l a b o r a t o r i e s u s e d f o r c a l c u l a t i n g mean d i f f e r e n c e C-rrir.al v a l u e u s e d f o r c a l c u l a t i n g rr.ean d i f f e r e n c e

Performance in Proficiency Tests - Years 1 and 2

APPENDIX 4.2.4(11

100

8 0

6 0

4 0

20

01 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 2 0 21 2 2 2 3

Laboratory Number

H i No. Flagged tSSW Nn. Results Reported

Max No results = 80

Aqueous Nutrients Year 1

U | |

1

U IS_EL

11

1 1

Aqueous Nutrients Year 2

Max No results - 40

Laboratory Number

No. Flagged Nn. Results Reported

APPENDIX 4 2 .4(2)

Aqueous MetalsYear 1

M a x N o resu lts = 56

6 0

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 2 0 21 2 2 2 3

Laboratory Number

No. Flagged IS B No. Results Reported

Max No results = 28

Aqueous MetalsYear 2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 2 0 21 22 2 3

Laboratory Number

No. Flagged No. Results Reported

APPENDIX 4.2.4

Aqueous OrganicsYear 1

Max No results = 5660

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 2 l 22 23Laboratory Number

No. Flagged Nn. Results Reported

Aqueous OrganicsYear 2


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23Laboratory Number

No. Flagged . Results Reported

APPENDIX 4.2.4(4)

Max No results = 32

Sediment MetalsYear 1

1 2 3 4 5 6 7 8 9 10 n 12 13 14 15 16 17 18 19 20 21 22 23Laboratory Number

No. Flagged . Resul is Repor ted

Sediment MetalsYear 2

Max No R esu lts = 9

l 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23Laboratory Number


APPENDIX 4.2.4C5)

Sediment OrganicsYear 1

Max No results = 68



Sediment OrganicsYear 2

Max No results = 38

l 2 3 4 * 5 6 7 8 9 10 11 12 13 u 15 16 17 18 19 20 21 22 23Laboratory Number

No. Flagged EHSn o . Results Reported

Max No results = 5

L L

Biota MetalsYear 1

I

I

L

i

APPENDIX 4.2.4(6)

l 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23Laboratory Number


Biota MetalsYear 2



APPENDIX 4.2.4(7)

Mnx No results = 202 5

20

15

10

Biota OrganicsYear 1

II

1

I

I .1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

LaDorator y Number


Biota Organics Year 2


80

60

40

20

01 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

Laboratory Number

I^ H No. Flagged H no . Results Reported

APPENDIX 4.2.5m

Ucferciicc Concentrations «>!' 'IVsc Samples.

AQUEOUS SAMPLES

Group 1 - Seawater NutrientsConcent rations

Distribution Number 5 6

UnitsSample AAmmonia pM 0.32* 5.41°TON pM 14.3* 10.5*Nitriie pM 0.88* 0.57°Orthophosphaic pM 0.80* 0.61°Silicaic pM 4.07* 5.06*Sample BAmmonia pM 16.9° 17.8°TON pM 35.6* 95.7*Nitrite pM 6.07° 5.15°Orthophosphatc pM 3.72° 3.59°Silicaic pM 19.8* 21.6*

Group 2 - Estuarine Nutrients

Sample AAmmonia pM 20.1° 18.9°TON pM 331.5* 347.8=Nitriic pM 2.22° 2.16°Orthophosphaie pM 5.41° 5.92°Silicate pM 175.3* 166.3

Sample BAmmonia pM 81.0° 87.6°TON pM 403.1* 405.5:Nitrite pM 10.2° 1.5°Onhophosphate pM 9.84° 10.10<Silicate pM 245.5* 217.8

APPENDIX 4.2.5(2)

('umuitralions

Distribution Number

G roup 3 - Trace Metals (A and 15)

Sample ACadmium ng/l 94.0°Copper 0.70°Lead PE/» 0.24°Nickel Mg/I 0.60*Zinc PS/1 2.65*Chromium Mg/1 1.92°

Sample BCadmium ng/1 223.0°Copper Pg/* 2.10°Lead Pfi/I 2.03°Nickel Pg/1 2.00°Zinc Pg/1 10.2°Chromium P£/J 4.73°

112.0°0.77°0.22°

1.02°

2.08*1.80°

241,0C 2.27° 2.17° 2.62° 10.1°

4.84°

G roup 4 - M ercury (A and B)

Sample ATotal Mercury ng/1 5.80° 6.85°

Sample BTotal Mercury ng/1 16.4° 17.7°

UnitsGroup 5 - Organochlorines (A and B)

Sample Aa-HCH ng/1 1.82° 2.65°7-HCH ng/1 4.00° 2.56*HCB ng/1 1.82° 3.40°HCBD ng/1 1.86° 9.95°(J-HCH ng/1 1.27° 3.70°Dieldrin ng/1 1.32° 2.85°Aldrin ng/1 2.62° 2.90°Endrin ng/1 2.30° 3.90°Isodrin ng/1 1.12* 0.50°pp’DDT ng/1 1.61° 3.22°pp’DDE ng/1 0.82° 1.65°pp’DDD ng/1 1.05° 2.10°op’DDT ng/1 1.10° 2.20°Trifluralin ng/1 2.95° 5.90°Endosulphan ng/1 1.50° 3.00°1,2,4 TCB ng/1 4.20° 10.9°1,3,5 TCB ng/1 3.11* -1,23 TCB ng/1 1.75° 3.20°

APPENDIX 4.2.5(3)

Omcen(r;itions


Sample Ba-HCH ng/1 4.67° 10.3°y-HCH ng/1 8.90° 22.1°HCB ng/1 5.47° 16.6°HCBD ng/1 5.55° 32.2°p -HCH ng/1 3.22° 10.0°Dicldrin ng/1 3.57° 5.40°Aldrin ng/l 7.27° 14.0°Endrin ng/I 6.50° 8.60°Isodrin ng/l 2.60* 0.50°pp’DDT ng/l 6.45° 21.2°pp’DDE ng/l 3.30° 15.7°pp’DDD ng/l 4.20° 12.0°op’DDT ng/l 4.40° 9.20°Trifluralin ng/l 11.8 18.8°Endosulphan ng/I 6.00 17.4°1,2,4 TCB ng/I 12.4° 26.6°1,3,5 TCB ng/l 2.60* -

1,2,3 TCB ng/l 6.10° 0.30°

Group 6 - Chloroform and Carbontetrachloride (A and B)

Sample AChloroform Mg/1 1.74° 1.14°Carbon ici. Pg/1 1.58° 0.95°Trichloroelhane Pg/1 1.08° 1.10°1,2 Diehl oroethane Pg/1 3.17° 2.3 i cTrichi oroelhene Pg/1 1.27° 0.76°Tetrach loroelhene Pg/I 1.31° 0.78°

Sample AChloroform Pg/1 3.82° 4.27°Carbon let. Pg/1 3.47° 3.79°Trichloroethane Pg/I 2.37° 3.04°1,2 Dichloroethane pg/1 6.98° 8.02°Trichloroeihene Pg/1 2.79° 3.04°Tetrachloroclhene Pg/1 2.87° 3.13°

Group 7 - Pentachlorophenol (A and B)

Sample APCP ng/1 1235° 210.0°Sample BPCP ng/1 2215° 817.0°

APPENDIX 4.2.5(4)

C »rou|> S - I nc.s

Distribution Number

Omcenlralions

Sam ple AS im a /jn eAiraz.ineSam ple BSitna/.ineA lra/.inc

ng/1ng/l

ng/1ng/1

147.7°127.7°

264.4°186.6°

55.2°39.2°

157.0C157.0C

G roup 9 - Organophosphorus Compounds

Sample AAzinphos-mclhylAzinphos-clhylFenihionMalathionParalhionParaihion-meihylFeniirothion

ng/1ng/Ing/1ng/1ng/1ng/1ng/1

219.4°111.2°78.2°120.0°

95.0°96.8°119.4°

54.7°41.0°91.5°52.7°45.7°39.5°75.7°

Sample BAzinphos-meihylAzinphos-eihylFcnihionMalathionParalhionParathion-mcthylFenitrothion

ng/1ng/1ng/1ng/1ng/1ng/1ng/1

482.0°245.0°172.0°264.0°209.0°213.0°263.0°

241.0°138.0°172.0°159.0°131.0°125.0°186.0°

APPENDIX 4.2.5(5)

SKDIMKNTS<'oiK’cntr.'ilioiiN


Group 1

Copper mgAg 43.2*Lead mg/kg 88.1*Cadmium mg/kg 0.52*Zinc mg/kg 280.9*Nickel mg/kg 24.1*Chromium mg/kg 62.9*Mercury mg/kg 1.38*Arsenic mg/kg 17.1*Aluminium % 1.77*

Group 2

HCB Pg/kg

\

3.28° 2.99°PCB 28 Pg/kg 0.75° 0.84°PCB31 Pg/kg 0.50° 0.56°PCB 52 Pg/kg 0.25° 0.13°PCB 101 PgAg 1.10° 0.66°PCB 105 Pg/kg 1.01° 1.12°PCB 118 Pg/kg 1.29° 1.44°PCB 138 Pg/kg 2.68° 1.98°PCB 153 Pg/kg 2.58° 2.10°PCB 156 Pg/kg 2.50° 2.78°PCB 180 Pg/kg 1.68° 1.88°Aldrin Pg/kg 2.26° 1.49*Endrin Pg/kg 2.24° 2.02°Dieldrin Pg/kg 1.02* 1.71°Isodrin Pg/kg 2.00° 0.20°pp’DDT Pg/kg 3.23° 2.92°pp’DDE Pg/kg 2.24° 2.03°pp’DDD Pg/kg 3.00° 2.72°op’DDT Pg/kg 0.62° 0.56°

APPENDIX 4 7

It IOTAConcentrations


(•roup 1

mg/kg 44.5*Cadmium mg/kg 1.9*Zinc mg/kg 232*Mcrcury mg/kg 0.35*Arscnic mg/kg 8.5*

G roup 2

Dieldrin Pg/kg 62.2° 55.6° 88.1° 69.0°Isodrin Mg/kg 20.2° 2.3° 37.9° 26.3°a-HCH Mg/kg 55.6° 17,8° 84.6° 36.7°y -HCH Mg/kg 32.2° 10.3° 9.2° 21.4°3 -HCH Mg/kg 40.0° 12.7° 60.8° 26.4°pp’DDT Pg/kg 103.2° 105.8° 182.6° 106.0°pp’DDE Mg/kg 195.4° 207.7° 297.1° 202.0°pp’DDD Pg/kg 157.3° 158.2° 219.5° 158.0°op’DDT Pg/kg 81.2° 71.5° 9.5° 11.5*Aldrin Pg/kg 31.8° 35.6° 10.7° 34.0°Endrin Pg/kg 105.5° 85.5° 156.6° 95.0°HCB Pg/kg 35.3° 20.0° 60.0° 28.0°HCBD Pg/kg 114.1° 48.0° 164.6° 81.0°PCB 28 Pg/kg 53.2° 42.2° 7!.4° 20.0°PCB 31 Pg/kg 27*1° 1.10° 42.6° 19.0°PCB 52 Pg/kg 32.3° 16.6° 52.0° 24.5°PCB 101 Pg/kg 70.4° 62.3° 90.5° 66.5°PCB 105 Pg/kg 79.8° 71.9° 103.1° 75.5°PCB 1 IS Pg/kg 97.6° 86.7° 122.7° 92.5°PCB 138 ' : pg/kg 103.° 94.6° 138.2° 114.0°PCB 153 Pg/kg 109.6° 103.8° 161.8° 116.5°PCB 156 Pg/kg 60.6° 55.4° 113.6° 58.0°PCB 180 Pg/kg 63.5° 6,7° 119.6° 75.0°

Group 3

PCP Pg/kg no data reponed

* Mean of all laboratories ° Spiked or spiked plus residual value.

Perform ance in Special Exercise - Metals APPENDIX 4.3.2.1

Max No results = 48

Special MetalsNovember 1993

30

20

10

- 0

II1

I

II

1

1I II 1

I

1l 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

Labor ator y Number


Special MetalsFebruary 1994

Laboratory Number


APPENDIX 4 .3 .2 .2 m

Recom m endations In 1 .a h o n itu rirs A ris in g I'n im Special K xem sc fo r Mu* Dcicm m iauon o l Trace Mclals in Waler.

L ab o ra to ry 03

First exercise:

Excellent performance for the determination o f lead. The other metaJs arc subject to large, consistent negative biases: Cd -30%; Cu -50%; Ni -20%; Zn -30%. This consistency indicates excellent control over random error and points to either calculation error o r calibration bias (standards biased as well as real samples).

Recommendation: Check for reporting errors o r calibration bias.

Second Exercise:

No data.

L ab o ra to ry 04

F irst Exercise: Good comparability for the determination o f chromium. Results for the standard solutions are of variable accuracy. For the other metals, large positive and negative biases are evident for both the standards (especially the low standard) and the samples. Larger errors are not necessarily associated with the low concentration samples. In fact, negative biases larger than the 20% target occur more often for the higher concentration samples. One source of error may be that the standards were analysed directly rather than being extracted.

Recommendation: Look for reasons for errors on Standard A and for the negative bias at higher concentrations. The two standard solutions A and B, should be reanalysed if possible.

Second Exercise:Good comparability for chromium, zinc and nickel. Positive bias for copper is evident. Positive and negative bias observed for lead and cadmium suggests that LOD may not be quite low enough.

Recommendation: Investigate bias for copper.

O verall:Improved performance in the second exercise is very encouraging. (11 out o f 48 results flagged, compared with 19 out o f 48 on the first exercise.) This laboratory’s capability to undertake trace metal determinations is supported by full participation in both tests.

APPENDIX 4.3.2.2(2^

I ,al>oi ;tlui y 07

F irs t E xercise:Excellent performance for all metals - only 4 instances o f bias greater than the target maximum of 20% in 40 results. No data for chromium. Some indication of small positive bias for cadmium and lead.

Recom m endation: No further action.S econd Exercise:Excellent performance for all metals, apan from chromium which is not determined routinely - only 5 instances o f bias greater than the target maximum of 20% in 40 results. The reporting limit for lead (0.36 pg/1 is higher than the required LOD of 0 .05 p/1).

Recom m endation: review lead reporting limit (actual LOD achieved looks considerably low er than the reporting limit).

O v era ll:T he results for this exercise confirm the high standard o f accuracy achieved in the first exercise. (5 out o f 40 results flagged in the second exercise, compared with 4 out o f 40 on the first exercise.)

L a b o ra to ry 10

F irs t Exercise:M arkedly different performance for the different metals. Accuracy is good for nickel and cadmium. Results for lead, copper and zinc are subject to serious bias (negative for lead, large and positive in the case o f copper and zinc). For chromium, negative b ias (-15 to -30%) is evident for all higher concentration samples.

Recom m endation: Check for calibration bias for copper and zinc. Review calibration for chrom ium at higher concentrations.

S econd Exercise:N o data - Laboratory no longer participating.

L a b o ra to ry 12

F irs t Exercise:Excellent performance for all metals - only 5 instances of bias greater than the target maximum o f 20% in 48 results. Some indication of small calibration bias for copper (negative) zinc (positive). M ore definite indication o f low recovery (matrix interference) for lead.

Recom mendation: No further action.

Second Exercise:Excellent performance for all m etals - only a single instance of bias greater than the target maximum o f 20% in 48 results. Some indication o f small negative bias bias for

APPENDIX 4.3.2 2(3)

Clipper. In ibi s exer c i se , Ihis bins is nunc cv idcni lo r s . i l inc samples , w h ic h jni ims

10 a mat r i x o f feet.

Recommendation: Maintain performance. Check copper bias.

O verall:Outstandingly good performance. This laboratory provides a demonstration that the NMP accuracy targets can be achieved for trace metals in saline samples. (1 out of 45 results flagged in ihc second exercise, compared with 5 out of 45 on the first cxcrcisc.)

L aborato ry 15

Excellent performance for aJl metals - no instances o f bias greater than the target maximum of.20% in 33 results. No data for chromium.

Less than values suggest that reporting limits for cadmium (200 ng/1) and lead (0.5 jjg/1) may not be adequately low for monitoring baseline concentrations; the Limits o f Detection recommended by Lhe NCC are 10 ng/1 and 0.05 pg/1, respectively. These LODs can be achieved using the laboratory’s analytical technique, so a review o f performance test data and a revision of reporting limits may be all that is needed.

Recommendation: See above.

Second Exercise:Excellent performance for all metals - only a single instance of bias greater than the target maximum. Some indication o f small negative calibration bias for lead. No data for chromium.

Recommendation: Maintain performance. Consider sources of bias for lead.

O verall:Outstandingly good performance. This laboratory provides a demonstration that the NM P accuracy targets can be achieved for trace metals in saline samples. (1 out o f 38 results flagged in the second exercise, compared with 0 out of 35 on the first exercise.) Reporting limits for cadmium and lead have been lowered in response to suggestions made after the first exercise (but they are still higher than the respective required LODs).

L abo ra to ry 17

F irs t Exercise:Good performance for the determination of cadmium and zinc (possibly small negative bias for the latter). Clear evidence of negative calibration bias (of around 20%) for both copper and nickel. Results for lead were unusual in that standards were negatively biased but data for the real samples (apart from one) were satisfactorily accurate. No data for chromium.

APPENDIX 4.3.2 2(4)

Recom mendation: clicck calibration forcop|>cr and nickel.

Second E xercise:

Excellent perform ance for coppcr, lead and zinc (only 3 llagged results. Serious negative calibration bias for cadmium. Some indication of negative calibration bias for nickcl.

Recom m endation: check calibration for cadmium and nickcl.

O vera ll :Improved perform ance for the sccond cxercise, exccpt for cadmium.A ccuracy appears satisfactory for most metals and samples. Where relatively minor problem s are evident, these seem to be caused by calibration bias - and hence should be readily rem edied. (3 out o f 34 results flagged in the second exercise (ignoring Cd data), com pared with 11 out o f 38 on the first exercise.)

L a b o ra to ry 19

F irs t E xercise:Good perform ance for all metals - only 4 instances o f bias greater than the target m aximum o f 20% in 30 results. Three o f these instances were for the standard solutions. No data for chromium. Less than values suggest that Limits o f Detection for several m etals may not be adequate for monitoring baseline concentrations.

Recom m endation: Review LODs and/or reporting limits.

Second E xercise:Excellent perform ance for coppcr and nickel. Negative bias for cadmium and positive bias for lead. Inadequate LOD for zinc.

Recom m endation: Check calibration for cadmium and lead and carry out proposed im provem ents for low er LODs - see below.

O v era ll: The picture o f analytical performance which emerged in the first cxercise is confirm ed in the second. Accuracy tends to be good at higher concentrations in the range o f interest. D ifficulty in achieving the required targets is experienced at low er concentrations. In a written reply, the laboratory indicated that steps were in hand to achieve low er LODs through improved measures to control contamination and m ethod changes to increase sensitivity. (9 out o f 30 results flagged (some only m arginally outside target) in the second exercise, compared with 4 out o f 30 on the first exercise.)

P e r fo rm a n c e in S pec ia l E x erc ise - O rg a n o c h lo rin e compounds

APPENDIX 4.3.3.1

Special OCIsNovember 1993


Special OCIsMay 1994

Laboratory Number

No. Flagged H n o . Results Reported

APPENDIX 4.3.3.2m

tU’Co m m e rK la t io n s to L : i b o r : i t o r i r s Arising f r o m Spw kil K x i T i i s c s lo r l ho ix-icnmnalion of Organochlorine Compounds in Water - Nov. 1993 and May 1994.

L abo ra to ry 04 -

Firs! Excrcisc:Good comparability for the 11 out of 18 determinands for which results were reported (g-HCH, HCB, 'drins, DDTs, Trifiuralin 1,2,4 TCB). No clcar indication of calibration bias, though checks might be made for possible negative bias for HCB, Dicldrin and Aldrin. For many determinands there is a tendency for the pre-spiked sample (Sample F) to be negatively biased - with rcspcct to both the reference value and the laboratory’s own data for Sample D (the same sample spiked at the time of analysis).

Recommendation: Check efficiency of extraction procedure on spiked, stored samples.

Second Exercise:Analysed samples but did not report data bccause of problems with internal standard.

L abora to ry 07 -

First Exercise: Results (other than less than values) reported principally for the high concentration standard (Standard B) and the pre-spiked sample. Less than values for other samples indicate limits o f detection around 4 ng/1. This is approximately ten times higher than the NCC recommend for monitoring of baseline concentrations. Results for the high standard indicate approximately -20 % bias in many instances. (Problems were reported in mixing the standards supplied with the solvent used for calibration standards.) Large positive biases for the pre-spiked sample probably arise from LOD problems.Recommendation: Review limits of detection o r reporting limits

Second Exercise: Results reported for 10 of the 18 determinands. However, this is a marked overall improvement on the first exercise (no less than values on this occasion). W here data were reported a clear indication for the cause o f any bias is evident, even when such bias is small in relation to the accuracy target. This is indicative of good control over the analytical process. In many cases, identical bias for the standard and samples suggests calibration bias - aH C H -30%, pHCH +30%, Aldrin -16 to -20%, Endrin +30%, ppDDT +60 to +80%, DDE +7 to +10%. For y HCH, HCB Dieldrin and HCBD, calibration bias seems to be present in combination with a source of error related to the sample matrix. (NB "calibration" bias may be caused by inaccurate standards or by systematic error in the way the calibration is applied. Errors in the preparation o f the test samples are ruled out by similar performance for the pre-spiked samples.) Overall for this test, excellent compliance with the 50% maximum error target was achieved for the limited number of determinands for which data were reported.

APPENDIX 4.3.3.2(2)

R ecom m endation: Consolidate improvements in reporting limits and extend analysis lo ihc lull set o f determinands. Investigate biases as indicated above.

O vera ll:T h e im provem ents in reporting limits sought after (he first exorcise have been achieved. In the second exercise good comparability (despite some obv ious biases) was dem onstrated , but only for 10 out o f IS determinands.

L a b o ra to ry 09

F irs! Exercise:Did not take pan (no requirem ent for aqueous Organics at ihal time).

Second Exercise:

Reported data for all dcicrm inands apart from HCBD and ihe TCBs. No less thans. No cvidcncc for bias affecting all five samples for a HCH, Endrin, ppDD T, DDE, Trifluralin and Endosulphan. Calibration bias indicated for y HCH +20%, HCB -20%, Dicldrin +25%, Isodrin + about 100%, DDD +40 to 80%. (NB ‘'calibration’’ bias may be causcd by inaccurate standards or by system atic error in ihc way the calibration is applied.) No evidence for matrix effects. Results for Sample C suggest that a mistake was made in analysing/preparing ihis sample.

Overall for this lesi, good compliance with the 50% maximum error target was achieved, apart from for Isodrin, Aldrin and DDD. Results (for the five sam ples for each determ inand) are more variable than those achieved by some laboralorics - though m uch o f this variation is contributed by Sample C (sec above).

Recommendation: Investigate biases as indicaied above.

L a b o ra to ry 11

F irst Exercise:Results reported mainly for the two standard solutions (most determinands) and HCH and Trifluralin (both standards and samples). Less than values for lower concentration sam ples indicate limits o f detection (or reporting limits) o f 1 - 2 ng/l. This is approximately three times higher than the NCC recommend for monitoring o f baseline concentrations.

Results for the standards indicate no serious calibration problems - except for Endosulphan.

Recommendation: Review limits o f detection or reporting limits. Check Endosulphan standards.

APPENDIX 4.3.3.2(3)

Second •ICxeri'isr:Data re purled fur all determinands. No less thans. lixcellem comparability and compiiancc with the 50% maximum error target were achieved. Some ■ cvidcncc for small bias affccling all five samples for p HCH +20 to 60%, Aldrin “20%, Endrin +10% and Endosulphan - 15 10 20%. Sonic isolated instances o f large bias, often for Sample D (usually positive bias lor this sample). Results for the pre-spiked sample (E) tend to be either the same as those lor Sample (C) - the two samples were the same apart from the time of spiking - or, in many cases, positively or more positively biased.

Recommendation: Investigate biases as above. Check data and procedure used for Sample D.

O verall:A marked improvement and completeness o f reporting and the accuracy o f results between the first and second exercises. TTie ability to meet NMP requirements has been demonstrated.

L abo ra to ry 12

First Exercise:Did not report data.

Second Exercise:Reported data for 13 o f 18 determinands (no data for Trifiuralin,Endosulphan and the TCBs). Excellent comparability and compliance with the 50% maximum error target were achieved, apart from for Endrin and Isodrin (negative and positive bias, respectively). Some indication of calibration error, in the form of consistent bias for all five samples for a given determinand, for Endrin -50%, Isodrin +90%, ppDDT -30%, DDD +40%, opDDT +25%. (NB "calibration” bias may be caused by inaccurate standards or by systematic error in the way the calibration is applied. Errors in the preparation of the test samples are ruled out by similar performance for the pre-spiked samples.)

In some cases (HCB, HCBD, ppDDD), evidence of bias (+ve) for the deionised standard, but not the seawater samples, points to calibration differences in different matrices. The fact that results for the real samples, including the pre-spiked sample, arc less biased is reassuring, but attention may need to be paid to samples which are not o f full-strength seawater matrix.

Recommendation: investigate sources of bias (see above). Extend analysis to the full set o f determinands.

APPENDIX 4.3.3.2(4)

L ;tb o ra lo ry J4

F irs t E xercise:Did not take part.

S econd E xercise:Reported daia lor only 10 oul o f 18 determinands. No less Uian values.

W here data were reported a clear indication for the cause of any bias is evident, even when such bias is small in relation to the accuracy target.T his is indicative o f good control over ihc analytical process. In many cases, sim ilar bias for the standard and samples suggests calibration bias - aH C H -20% , p HCH +150% Dicldrin +20%, opDDT -20 to -40%. (NB "calibration" bias may be caused by inaccurate standards or by systematic error in the way the calibration is applied. Errors in the preparation of the test samples arc ruled out by similar performance for the pre-spiked sam ple.)

Overall for this exercise, excellent compliance with the 50% maximum error target was achieved for the limited number of determinands for which data were reported.

Recom m endation: Check standards for p HCH. Consider reasons for small biases indicated above. Extend analysis to the full set of determinands.

L a b o ra to ry 15

F irs t E xercise:Excellent performance for a wide range o f determinands. Results reported for the great m ajority o f samples for all 18 determinands. Relatively few less than values were recorded (see below). In many instances mean bias of less than 20% is achieved. Indication of positive biases for HCB, HCBD and p-H C H .

For som e determinands the reporting o f less than values was justified (eg 1,3,5 TCB and Isodrin which were omitted from some or all solutions). How ever, less than values were also reported for a number of other determ inands which were spiked near to or above the level of monitoring interest. These samples were therefore o f much higher concentration than the LO D defined by the NCC (eg opDDT, Trifluralin and 1,2,4 TCB). Bias for the standard solutions is controlled to within 10%, in many cases.

Recom m endation: Review limits o f detection and/or reporting limits.

Second Exercise:Data reported for all determinands. (Less than values reported for trifluralin and 124TCB). Excellent comparability and compliance with the 50% maximum error target was achieved for all determinands, apart from positive bias for ppDDD (50 to 60%) and 135TCB (100% bias, but apparently near to LOD). Some evidence for a matrix effect for HCBD - bias affecting four samples but not the deionised water standard. No problems of recovery from the pre-spiked sample.

APPENDIX 4.3.3.2(51

Ri’Comnu-mini ion: Investigate biases for ppDDD ;nid J35TCH.

O verall:The high standard o f accuracy achieved in the first exercise was maintained in ihc sccond. In many instances mean bias o fle ss than 20% is achieved. Gaps in rcponing due to high rcporting limiis were almost eliminated. The ability lo meet NMP requirements has been demonstrated.

L aborato ry 17

First Exercise:Good performance for a range o f determinands. Results reported for 12 out o f a total of 18 compounds. (No data for ppDDD, opDDT, TCBs and Isodrin). No less than values reported.

A tendency for positive bias is evident for some parameters, notably HCB, Trifluralin, g-HCH, Dieldrin, Endrin and DDE. This bias applies to the standard solutions (A and B) as well as to the samples and suggests a calibration error. Closer examination o f most o f the above cases indicates a positive "fixed offset". (The bias corresponds to a fixed amount for each determinand, rather than a constant percentage). This is characteristic of an uncorrected instrumental blank.

Recommendation: Check for reasons for positive bias (see above).

Sccond Exercise:Reported results for 12 out o f 18 determinands. No data for Isodrin, ppDDD, opDDT and the TCBs. Excellent comparability and compliance with the accuracy requirement for a maximum error o f 50%. Evidence of calibration bias - similar bias for deionised water and all four seawater samples - for ppDDT - 30 to 40%, Tri Aural in +40% and Endosulphan -30%.

O verall:The ability to meet NM P requirements has been demonstrated in the second exercise. Bias detected in the first exercise was corrected in the second. Some gaps remain in the list of determinands for which data are reported.

L aborato ry 19

F irst Exercise:Excellent performance for a wide range of determinands. Results reported for the great majority o f samples for 13 out o f 18 determinands (no data for Endosulphan, HCBD and the TCBs). Relatively few less than values were recorded (see below). In many instances, mean bias o f 20% is achieved.

The results provide a demonstration that the determinands can be recovered from the pre-spiked sample with near to the same accuracy as from a sample spiked at the time of analysis. There are no important differences between

APPENDIX 4.3-3.2(61

results lor samples I) and l ;, apart Irom those rc|x>iicd Jorg-llCH, Aldiin, ppD D T and opDDT. Results lor these determinands Tor sample F arc 10 - 20% less than those for sample D.

Recom m endation: Review LODs and/or reporting limits with rcspccl to NCC recom m endations.

Second E xercise: No data reported.

Laboratory 21

F irs t E xercise:Did not report data.

Second E xercise:Results reported for all determinands. No less thans. Excellent compliance with the 50% maximum error target was achieved. A clear indication for the cause o f any bias for a given determinand is evident, even when such bias is small in relation to the accuracy target. This is indicative of good control over the analytical process. In many cases, identical bias for the standard and sam ples suggests calibration bias - aH CH -30%, HCB -30 to 40%, p HCH -70%, Dieldrin -20% , Aldrin -30%, Endrin -30%, Isodrin -30%, ppDDT -30% , ppDD E - 30% , opD D T -30%. (NB "calibration" bias may be caused by inaccurate standards o r by systematic error in the way the calibration is applied. Errors in the preparation o f the test samples arc ruled out by sim ilar perform ance for the pre-spiked samples.)

Recom m endation: Cheek sources o f bias indicated above, in particular those for p HCH.

CU R R EN T PA R TIC IPA TIO N IN TH E NM AQC SCHEM E

AQUEOUS

APPENDIX 5.1.10)

Laboratory

No.

S/w

nutrients

Estuarine

Nutrients

S/w

Metals OCs Volatilcs PCP OPs Hg

3, 13. 4, 5 4, 5 3, 5 5 5

4. 3, 4, 5 3, 4, 5 3, 4, 5 3, 4, 5 5 3, 4, 5 5 3, 4, 5

5 & 8. 3, 4, 5 3, 4, 5

7. 3, 4 ,5 3, 4 ,5 3, 4 ,5 3, 4 ,5 3, 4 ,5 5 3, 4, 5

9.

11. 3, 4 3 ,4 3, 4 ,5 3 ,4 , 5 3, 4, 5 5

12. 3, 4, 5 3, 4 ,5 3, 4 ,5 3, 4, 5 3, 4, 5 3, 4, 5 5 3, 4 ,5

14. 3, 4 ,5 3

15. 3, 4, 5 3, 4, 5 3, 4 ,5 3 ,4 , 5 3, 4 ,5 3, 4 ,5 5 3, 4 ,5

17. 4 3 ,4 3 ,4 4

19. 3, 4, 5 3, 4 ,5 3, 4 ,5 3, 4 ,5 3, 4 ,5 4, 5 3 ,4

21. 3, 4 ,5 3, 4 ,5 3, 4, 5 3, 4 ,5 3, 4 ,5 5 3, 4 ,5

23. 5 5 5 5 5 5

Note: - A number against any box indicates returns were made for those exercises.

■ - No OPs in exercises 3 and 4.

APPENDIX 5.1.1(2)

CURRENT PARTICIPATION IN THE NMAQC SCHEME.

Note:

No biota in distribution 4.

a number against any box indicates returns were made for these exercises.

APPENDIX 6.1

Overall Laboratory Performance in Year 1 and 2

for all matrices (aqueous, sediment, biota).

Maximum returns possible in Year 2 = 332

"Change" column - a negative sign indicates a reduction from year 1 to year 2.

a positive sign indicates an increase from year 1 to year 2.