Chemical Monitoring Activity Draft Guidance Document on Chemical Monitoring of Surface Water (Version 3.0)

Comments on Version 2.0 Comments to the draft were submitted by Denmark France Germany Norway The Netherlands Sweden UK HELCOM Eurometeaux ESPO Case studies were submitted by Spain, Sweden and Germany

What’s new? New version V3.0! 3. TERMS AND DEFINITIONS 4. MONITORING DESIGN 4.1 General – Monitoring Design 4.2 Sampling Strategy (Matrix selection is now included in this chapter) 5. TECHNIQUES FOR SAMPLING (according to the discussion we had at the Rome meeting the chapter was shortened substantially) 6. TECHNIQUES FOR ANALYSIS 6.1.2 Limit of detection/Limit of quantification 7. Complementary Methods New version V3.0! The Term determinant was substituted by measurand. Measurand is the technical term specified in the VIM The Chapter Monitoring design was re-arranged, matrix selection was included in the new section „Sampling strategy According to our discussion in Rome the Chapter sampling was revised and adjusted in size and level of detail to the other chapters By DK and France A new section LOD/LOQ has been added, drafted by UK The term alternative methods was substituted by complementary methods taking into account discussions at the last SWIFT meeting which was held in September in Porthmouth. It was noticed that the term alternative might indicate that methods dealt with in this chapter could acutally be used as substitute for laboratory methods. But the intention of SWIFT was to develop method, which can complemet existing method and not substitue them.

Comments not (yet) considered General Comments The time period after which the document is to be reviewed and updated has to be specified (NL) Is there need for a specific marine guidance chapter or annex? (JRC) Issues of compliance, statistical treatment and reporting of monitoring data are not within the mandate of this guidance document A political decision is required because the consequences can be enormous (NL) The time period after which the document is to be updated has to be specified (NL) Is there need for a specific marine guidance chapter or annex? (JRC) Issues of compliance, statistical treatment and reporting of monitoring data are not within the mandate of this guidance document A political decision is required because the consequences can be enormous (NL)

Comments not (yet) considered Definition of Total Measurand Concentration Total concentration of the measurand shall mean the total concentration of the measurand in the whole water sample, reflecting both dissolved and particle bound concentrations of the measurand. Comment (NL) This definition must be changed otherwise one should always determine the sum of the determinant in water PLUS the determinant in suspended solid Proposal (NL) ….......the extractable fraction of the whole water sample by liquid-liquid extraction, solid phase extraction, passive sampling extraction or other extraction techniques Comment (NL) This definition must be changed otherwise one should always determine the sum of the determinant in water PLUS the determinant in suspended solid Proposal (NL) ….......the extractable fraction of the whole water sample by liquid-liquid extraction, solid phase extraction, passive sampling extraction or other extraction techniques Definition of „discharged“ Proposal (Eurometeaux) A substance is considered as being discharged into a river basin when it leaves an engineered system of structures or use/end of use product or article either directly, in a diffuse manner or accidentally

Comments not (yet) considered Filtration of Water Samples Draft Guidance ……… for metals, the liquid fraction obtained by filtration or any equivalent pre-treatment of the whole water sample, ………… Comment (JRC) Equivalent pre-treatment procedures should be specified and/or examples should be given examples Collection of SPM Commonly, filtration through glass-fibre depth filters with a nominal retention rate of 99% at 0.7 µm is used Commment (NL, France, Germany) 0.45 µm filtration should be recommended

Comments not (yet) considered How to demonstrate compliance if methods are not sufficiently sensitive or accurate? Comment (NL) Decision to be taken by the commission Proposal (NL) In those cases where compliance checking (analysis in whole water with cost effective analytical methods) is not possible, it is sufficient for a Member State only to check on the no-deterioration principle. This can be done for instance by determining concentrations in sediment. Draft Guidance Document However, demonstrating compliance with EQS in water may be problematic in some cases. Examples include: Available analytical methods are not sufficiently sensitive or accurate for quantification of substances at the required concentration level. Comment (NL) Decision to be taken by the commission, only proposal Proposal (NL) In those cases where compliance checking (analysis in whole water with cost effective analytical methods) is not possible, it is sufficient for a Member State only to check on the no-deterioration principle. This can be done for instance by determining concentrations in sediment One should remind that it takes at least 5 years for concentrations in the top sediment layer to change as a consequence of changing water quality. Using a higher frequency than once per RBMP will not give a better insight

Comments not (yet) considered Use of Models Comment (NL, JRC) Information given in chapter 4.3 should be moved as possible approach or best practice to Annex III “Case Studies” Comment (Norway) CMA must discuss if relationship curves models (BAF/Kow) could be used in compliance checking of water bodies at least in surveillance monitoring where the water bodies classiefied in this way are clearly not at risk Chapter 4.3 Use of Models Comment (NL, JRC) Information given in chapter 4.3 should be moved as possible approach or best practice to Annex III “Case Studies” More specific information should be included in chapter 4.3 on how models might be used to design a monitoring network Proposal (Norway) Since no EQS values are decided for biota CMA must discuss if relationship curves models (BAF/Kow) could be used in compliance checking of water bodies, for instance to propose reasonable border values to be used in monitoring. If necessary a safety factor could be added to ensure that the uncertainty of the relationship curve does not lead to misclassification. At least this approach should be considered in surveillance monitoring where the water bodies classified in this way are clearly not at risk

Comments not (yet) considered Monitoring Frequency Comment (NL) According to the WFD, the frequency is set and compliance checking should be done on the mean of these values. The accompanying level of confidence and precision should be taken accepted There should be no mandatory frequency for seasonal substances in the case of surveillance monitoring It should be acknowledged that surface water in general is a dynamic system and variability in nature is large, especially for micro-pollutants. Achieving “adequate confidence” is only possible with very high frequencies and corresponding costs. Recommendation in the draft To estimate the pollutant load biweekly sampling, 26 samples a year, is recommended

Comments not (yet) considered Group Parameters Comment: Germany, NL Endosulfan only the alpha-isomer should be monitored Hexachlorocyclohexane only the gamma-isomer should be monitored Comment, NL The number of isomers which have to be summed up for calculating concentrations of group parameters should be as small as possible Comment: Italy Octylphenol The CAS No 1806-26-4 as specified in the list of priority substances as well as in the Directive on EQS corresponds to the linear isomer The toxic isomer released to the environment is 4-tert-octylphenol (CAS No. 140-66-9)  Endosulfan only the alpha iomer should be monitored, the beta is hard to analyse, it will cost a lot to comply with the LOQ and U, and is of much less importance Hexachlorocyclohexane only the gamma isomer should be monitored, the other isomers are of much less important, it will cost a lot to comply with the LOQ and U Comment: Italy Octylphenol The CAS No 1806-26-4 of Octylphenol as specified in the list of priority substances as well as in the Directive on EQS corresponds to the liniear isomer The toxic isomer released to the environment is 4-tert-octylphenol (CAS No. 140-66-9)  Required LOQ for the individual isomers of a group of substances With 6 components, each should have a factor 6 lower LOQ!!!. Because the results are summed before compliance checking. This means that these group compounds analyses are much harder to comply with the required LOQs Example: PBDE PBDEs: 6 congeners: the required LOQ is already very low: If each congener reports a “<LOQ” value. The addition of 6 times 50% of the LOQ gives already a high result which may be well above the EQS

Open Questions Treatment of “less than” values as well as specification of indicator substances How to assess results if method performance criteria cannot be met? Proposal was made Group parameters – Indicator compounds Polybrominated diphenyl ethers, HCH, Endosulfan What congeners/isomers should be analysed for? How to report results for substance groups or mixtures of isomers? How to set performance criteria? How to handle “less than” results for individual isomers/congeners? CAS No Octylphenol Use of relationship curves models in compliance checking Support is required from DG/ENV and Drafting Group on Common Issues!!!

Future Work Taking into account comments on version 3.0 received from CMA members Completion of Substance Guidance Sheets Analysis of HCB, hexachlorobutadiene and methy-mercury in biota to be included? Groundwater relevant parameters? A list of complementary methods relevant to WFD chemical monitoring to be added to chapter 7 including method performance criteria CASE Studies Further examples to be submitted Please be brief and use the template provided

Suggested Time Schedule Filling the existing gaps in the current document Substance Guidance Sheets Annex III: CASE STUDIES List of complementary methods December 15 Written comments on V3 of the draft guidance document Revised draft V4 January 15, 2007 Final Drafting Group Meeting January 22/23, 2007 at JRC Ispra Completion of the Guidance Document February 28, 2007

Thank you to all who have participated actively in the drafting process