2nd CHEMICAL MONITORING AND EMERGING POLLUTANTS (CMEP) PLENARY MEETING Task 3.1E (co-chaired by JRC and IT) Survey on available PTs, RMs and other QC tools

Task 3.1e Survey on available PTs, RMs and other QC tools Task with contribution from: EC-JRC-IRMM, Italy, FI, FR, SE, LU, BG, LT The objective of Task 3.1E is to inform WG E about the status of presently available QC tools for laboratories dealing with the implementation of the WFD with regard to monitoring requirements (QA/QC-Directive 2009). - Proficiency Testing schemes - Certified Reference Materials - Standard methods of analysis

QA/QC tools Proficiency testing schemes “external assessment” (Certified) Reference Materials Traceability Measurement uncertainty Tools for QA/QC of analytical data Compliance with the monitoring duties will imply the delivery of reliable measurements which accuracy poses a considerable challenge, considering the generally very low EQSs. The tools needed for such purpose include appropriate CRMs, use of internationally recognised and validated methods and also participation in proficiency testing schemes, for an external assessment of performance. Unfortunately, not all these tools are available for all priority substances “Standardised methods” prescribed methods/procedures (sampling, method-defined parameters)

Mandate of 3.1e in short First focus on the existing Priority substances Future (soon) extension to “new” PSs (the list should be finalised and approved later this year) Revision of EQS for some “old” PS foreseen + extension to other matrices (biota, sediment). Always keeping in mind the requirements of the QA/QC Directive 2009…

New survey on available CRMs Previous lists of this kind date back to 2003 (JEM article) and 2006 (D15 EU FP6 EAQC-WISE project). All WFD relevant matrices included: not only water, but also sediment and biota CRMs. We targeted an exclusive inclusion of CRMs* with some compromise (certificate had to be available, but uncertainty and metrological traceability were not always provided). Marine water, sediment and biota CRMs have also been included for a more general overview and to account for the limited number of matrix-matched CRMs. * definition given in ISO Guide 30/Amd 1 (2008)

New survey on available CRMs Inclusion of the 8 other pollutants not categorised as PS but having nevertheless an EQS Table with matrix CRMs Table with discontinued matrix CRMs No (!) Table for pure compounds or solutions CRMs List of CRMs producers and/or distributors

Some highlights (1) ? No water CRMs for organics common approach used is the “reconstitution” mimicking the real matrix To start soon: EMRP ENV08, Traceable measurements for monitoring critical pollutants under the WFD Biota CRMs for organics Available from different producers, based on aquatic plants or animals So far, only for two PS, HCB and HCBD, EQS are established in prey tissue (10 µg/kg, EQS directive 2008). Two frozen fish tissues (SRM 1946 and 1947) available from NIST are certified around the EQS value. Primary issue for biota RMs is the "commutability“ = close mimic to the routine sample. ? NIST was the first producer introducing fresh-frozen CRMs (early 1990s) QUASIMEME program is providing wet PT samples IRMM is also working in producing fresh texture-improved CRMs. CRM 123

Some highlights (2) Sediment CRMs for organics Available from different producers Absolute number of CRMs is higher than for the biota, but number of PS covered about the same NRC-CNRC and NWRI, producers from Canada, discontinued the largest number of sediment matrix CRMs (over the past five years). This gap was only recently covered by materials from WEPAL, but with informative values and almost always no uncertainty.

Some highlights (3) water CRMs for priority metals EQSs refer to the dissolved concentration General situation much more comfortable than for organic PS. For Hg at or below the level of the EQSs (0.05 µg/L as AA and 0.07 µg/L as MAC), only 3 CRMs are available ERM-CA615 (JRC-IRMM) BCR-579 (JRC-IRMM) ORMS-4 (NRC-CNRS) ERM-CA615, groundwater with a certified value of 0.037 ± 0.004 µg/L BCR-579, coastal seawater with a certified value of 1.9 ± 0.5 ng/kg, NRC-CNRC, ORMS-4, river water with a certified value of 22 ± 1.6 pg/g CRM

Some highlights (4) biota CRMs for priority metals Large number of CRMs EQS is established in prey tissue for Hg as 20 µg/kg (EQS directive 2008). at least a couple of CRMs are available from NIST around this content level, both freeze-dried SRM 1974b (mussel tissue) SRM 1566b (oyster tissue) sediment CRMs for priority metals Sufficient number of representative sediment CRMs

WATER CRMs

BIOTA CRMs

SEDIMENT CRMs

Pure compound/solution CRMs The compilation of a similar list to the matrix CRMs turned out to be a “mission impossible” Compared to the previous survey, a number of pure PS finally appeared on the market PBDEs by NIST in 2006 SCCPs by Chiron in 2007-2008 Several standard CRMs are provided by the CERI. Among others, calibrants for benzene, 1,2-dichloroethane, dichloromethane, DEHP, nonyl and octylphenols. Purity issue

Isotope Pure compound/solution CRMs All organic PSs (except chlorfenvinfos and SCCPs) are now available also as labelled compounds (from Aldrich, Fluka, LGC, C/D/N Isotopes, CIL…). “Inorganic spikes” used in inorganic isotope dilutions applications, are also widely available.

Next CMEP meeting November 2011 JRC-IRMM, Geel, Belgium JRC-IRMM location Next CMEP meeting November 2011 JRC-IRMM, Geel, Belgium

Looking forward to welcome you all!