1. 1 AMPS 5 Expert Group on Analysis and Monitoring of Priority Substances Georg Hanke, Jan Wollgast JRC IES IMW

2. 2 AMPS Discussion Document Chapter 4. Analytical Methods QA/QC

3. 3 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

4. 4 Analytical Methods for Water Framework Directive Priority Substances compliance checking

5. 5 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

6. 6 MAF < 1 Method OK MAF 1-2 Method to be improved MAF > 5 Method significantly to be improved Method not existing MAF evaluation

7. 7 MAF < 1 Method OK MAF evaluation 21

8. 8 MAF 1-2 Method to be improved MAF evaluation 5

9. 9 MAF > 5 Method significantly to be improved MAF evaluation 6

10. 10 Critical substances MAF Alachlor5 Brominated diphenylethers37 Chlorpyrifos (-ethyl, -methyl)22 Pentachlorobenzene10 Polyaromatic Hydrocarbons (PAH´s)21 Tributyltin compounds67

11. 11 Method applicability Green: MAF < 1 Yellow: MAF < 2 Orange: MAF > 5 Red: no method

12. 12 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

13. 13 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

14. 14 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.

15. 15 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 !

16. 16 Standard methods for organic contaminants in water: « whole water » or fraction analysed ? No mention of SPM 36/50 No mention of SPM 36/50 Mention of SPM 14/50 Mention of SPM 14/50 Defined protocol 5/50 Defined protocol 5/50 No defined protocol 9/50 No defined protocol 9/50 FILTRATION 4 standard methods 6 PAHs (NFT 90-115) diuron, isoproturon, atrazine, simazine (ISO11369) nitro-aromatics (EPA8330) di(2 ethylhexyl) phtalate CENTRIFUGATION 1 standard method CENTRIFUGATION 1 standard method COHV (EPA 9020B) 50 standard methods (ISO, EPA, AFNOR) 50 standard methods (ISO, EPA, AFNOR) Only dissolved fraction !

17. 17 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

18. 18 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

19. 19 How to achieve and assure an equal level of good data quality for WFD compliance checking throughout Europe ?

20. 20 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 

21. 21 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

22. 22 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

23. 23 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 !

24. 24 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

25. 25 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:

26. 26 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