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AMPS 5

Expert Group on

Analysis and Monitoring of Priority Substances

Georg Hanke, Jan Wollgast JRC IES IMW

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AMPS Discussion Document

Chapter 4.

Analytical MethodsQA/QC

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EU Enlargement

AMPS Candidate Country members:

Cyprus

Czech Republic

Slovenia

Slovak Republic

Poland

Estonia

Latvia

Lithuania

Hungary

Malta

Integration of Candidate Countries in European water monitoring schemes

Collaboration with CC in research for policy support,harmonisation, training

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Analytical Methods for

Water Framework Directive

Priority Substances

compliance checking

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Current method situation in water:

Identification of methods Lower Limit Of Application

LLOA

30 % EQS

Calculation of Method Applicability Factor MAF:

LLOA / 30 % EQS = MAF

MAF < 1 Method OK

MAF > 1 Method to be improved

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MAF < 1 Method OK

MAF 1-2 Method to be improved

MAF > 5 Method significantly to be improved

Method not existing

MAF evaluation

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MAF < 1 Method OK

MAF evaluation

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MAF 1-2 Method to be improved

MAF evaluation

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MAF > 5 Method significantly to be improved

MAF evaluation

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Critical substances

MAF

Alachlor 5

Brominated diphenylethers 37

Chlorpyrifos (-ethyl, -methyl) 22

Pentachlorobenzene 10

Polyaromatic Hydrocarbons (PAH´s) 21

Tributyltin compounds 67

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Method applicability Green: MAF < 1

Yellow: MAF < 2

Orange: MAF > 5

Red: no method

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No harmonised method for chloroalkanes available

State of the Art has been identified

Follow-up of Chloroalkanes workshop (CEN/UBA/JRC workshop) needed !

Identification of determinands still to be done !!!

MS activity ?

CEN activity?

DG ENV activity ?

DG ENV/DG RTD activity ?

Chloroalkanes, the way forward

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Identification of harmonised reference methods which are „fit for purpose“ in guidance document

EN methods and other, if appropriate

Guarantees availability of analytical method

Improves initial data quality

Gives basis for improvements

Platform for sharing new developed methods

To be done for Priority Substances, 76/464 substances, river basin specific substances

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All PS need a detailed description of the determinands !

Detailed description of EQS parameters should be included in legislational guidance !

Congeners, isomers

Examples:

PBDE, Chloroalkanes, HCHs, Nonylphenols, DDTs, PAHs, etc.

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Methods for whole water analysis

Checking compatibility of analytical methods with SPM content :

In most standard methods NO information about compatability with SPM present in the samples is given

Need for evaluation of methods by experts group !

Further method development should take SPM into account !

SPM can both interfere with the analysis and/or retain contaminants making them not accessible to extraction procedures !

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Standard methods for organic contaminants in water: « whole water » or fraction analysed ?

No mention of SPM36/50

No mention of SPM36/50

Mention of SPM14/50

Mention of SPM14/50

Defined protocol5/50

Defined protocol5/50

No defined protocol9/50

No defined protocol9/50

FILTRATION4 standard methods

• 6 PAHs (NFT 90-115) • diuron, isoproturon, atrazine, simazine (ISO11369)• nitro-aromatics (EPA8330)• di(2 ethylhexyl) phtalate

CENTRIFUGATION1 standard methodCENTRIFUGATION1 standard method

• COHV (EPA 9020B)

50 standard methods (ISO, EPA, AFNOR)

50 standard methods (ISO, EPA, AFNOR)

Only dissolved fraction !

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Methods for whole water analysis

Grouping of analytical methods:

Filtration/dissolved metal determination methods existing

Liquid/Liquid extraction contaminants embedded in particles might not be extracted

Headspace analysis (static + dynamic) considered uncritical but can be influenced by high SPM (TOC) content

SPE techniques depending on polarity of substances

Use of isotope dilution technique can partially improve applicability of methods for SPM containing samples

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Analytical Methods, the way forward:

Checking of available methods through expert judgement as first step

Identification and promotion of research needs

Continuous monitoring for need of improvement of methods for PS and river basin specific substances

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How to achieve and assure

an equal level of

good data quality for WFD

compliance checking

throughout Europe ?

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Data Quality Requirements

the combined standard uncertainty target value for single measurements of 25% (expressed as relative standard deviation) should be achieved at a concentration of 30 % of the EQS concentration level

A coverage factor of 2 (corresponding to an approximate level of confidence of 95%) is chosen to derive expanded uncertainty, this denotes that the target value for the expanded uncertainty is 50 %

Endorsed

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AMPS discussion document (page 23) :

Adequate QA/QC is fundamental to credibility and scientific value of monitoring under WFD

International criteria should form the basis of a harmonised approach

Need to make appropriate proficiency testing programmes and reference materials available was identified

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QA/QC for WFD PS

3 Pillars

Proof of competence by the MS laboratories

Proof of validation of the methods being used

Quality control on European scale

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Legally binding Data Quality Assurance and Quality Control:

Proposal of mechanism:

Identification of responsible bodies in MS

Accrediation and/or certification by national body

Participation in European proficiency testing scheme

AQC brainstorming Brussels, 29.3.04: Awareness of need for European Proficiency Testing Scheme for water analysis in European Commission and European Research Community !

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Article 3 Implementation and responsibilities For the implementation of this Directive, the Member States shall designate at the appropriate levels the competent authorities and bodies responsible for: - implementation of this Directive,-assessment of ambient air quality,- approval of the measuring devices (methods, equipment, networks, laboratories),- ensuring accuracy of measurement by measuring devices and checking the maintenance of such accuracy by those devices, in particular by internal quality controls carried out in accordance, inter alia, with the requirements of European quality assurance standards,-analysis of assessment methods, - coordination on their territory of Community-wide quality assurance programmes organized by the Commission.When they supply it to the Commission, the Member States shall make the information referred to in the first subparagraph available to the public.

Example: Air Framework Directive 96/62/EC

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Laboratories should work according to internationally accepted QA/QC schemes (e.g. following the accreditation standard EN/ISO/IEC 17025 and international guidelines)

ISO/TR 13530, 1997-09 Water quality – Guide to analytical quality control for water analysis.

Timmerman, J., Gardner, M.J. and Ravenscroft, J.E. (1996). UN/ECE Task Force on Monitoring and Assessment, Volume 4 - Quality Assurance. ISBN 9036945860.

Obligation for QA/QC within Member States laboratories:

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WFD PS AQC, the way forward:

Drafting of a position paper for AQC for WFD PS compliance checking

Distribution to AMPS, commenting with deadline

Presentation to EAF, June

EOS