P B T EUROMET- Project * Traceability for developing Traceability for EU-wide comparable Measurement Results in Water Monitoring Organized by Physikalisch-Technische Bundesanstalt (PTB), Germany Bundesanstalt für Materialforschung- und prüfung (BAM), Germany Laboratoire National de Metrologie et d‘Essais (LNE), France Institute for Reference Materials and Measurements (IRMM), EU *) EUROMET is a cooperative voluntary organisation between national metrology institutes in the EU and EFTA, including the European Commission. Detlef Schiel, PTB, Germany

P B TComparability Motivation:Metrological demand due to the requirement of comparable measurement results for monitoring and assessments of the water quality (Annex V, 1.3.6) Measurement results of the monitoring laboratories Reference point Calibration material Certified Reference material Comparison measurement

P B TComparability Motivation:- Requirement of comparable measurement results for monitoring and assessment of the water quality (Annex V, 1.3.6) Consensus value Confined comparability Motivation:Metrological demand due to the requirement of comparable measurement results for monitoring and assessments of the water quality (Annex V, 1.3.6)

P B TComparability Measurement results of the monitoring laboratories SI (Mol) Internationally accepted traceability basis Traceability and Dissemination chains Motivation:Metrological demand due to the requirement of comparable measurement results for monitoring and assessments of the water quality (Annex V, 1.3.6)

P B T Euromet-Project 924 Objective:- Development of a traceability and dissemination system Subject:- Inorganic elements of the list of priority substances Ni, Cd, Pb, Hg Deliverables:- Sustainability - Link with all monitoring laboratories - Europe-wide comparable measurement results - global acceptance (key comparison of CCQM)

P B T Intended Dissemination Structure Step 2: Validation of the measurement procedure of the PRLs supported by NMIs Step 3: Link of field laboratories and PRLs in the framework of a PT scheme NMIs Monitoring Laboratories Potential Reference Laboratories Step 1: Link of NMIs and PRLs by means of a comparison measurement PRL: Potential Reference Laboratories

P B T Time schedule 2007 MayStep 1: Comparison of NMIs and PRLs 2007 Nov. Meeting of the participants in the PTB 2008 Step 2: Validation of procedures of the PRLs and Step 3: Comparison measurement organised by the PRLs for the monitoring laboratories 2009 Feb.Report for Euromet

P B TParticipants NMIs: PTB (Ge), BAM (Ge), LNE (Fr), IRMM (EU), SP (Se), INM (Ro), NCM (Bg), LGC (UK) PRLs:Ge 8 Fr 4 Se 2 Il 2 Pt 2 Hu 1 It 1 At 1 Registered so far: 8 NMIs and 21 PRLs from 13 EU countries

P B TThanks for your attention

P B T List of participants (preliminary) - Rheinisch-Westfälisches Institut für Wasserwirtschaft - Bayerisches Landesamt für Umwelt - Institut für Hygiene und Umwelt, Hamburg - Landeslabor Schleswig-Holstein - Hessisches Landesamt für Umwelt und Geologie - Thüringer Landesanstalt für Umwelt und Geologie - Inst. f. Siedlungswasserbau, Wassergüte- und Abfallwirtschaft, Stuttgart - Landesumweltamt NRW PTB + BAM LNE - Cemagref - INERIS - BRGM - IFREMER IRMM NPL (Israel) - National Public Health Laboratory - National Water Monitoring Laboratory LGC - ? SP - NIVA - Analytica - ITM (Uni Stockholm) Σ 7 NMIs and 17 PCLs NMIsPCLs National authorities + PT scheme providers National authorities Analytical service provider

P B T CCQM pilot studies CCQM-P100.1CCQM-P100.2  Samples provided in glass bottles 500ml and stabilized in BrCl  Methods of measurement: e.g. ICP MS, AFS combined with cold with cold vapor technique and Au-preconcentration EPA method description 1631: EN  CRMs e.g. BCR-579 or NRC  Pure water  Prepared by BAM  Gravimetrically spiked  Gravimetrical reference value  Concentration 0,02 - 0,1 μg/l  Natural water  Prepared by LNE  Water will be filtered  Spiked, but no gravimetrical reference value  Concentration 0,2 - 1,0 μg/l

P B T Setup of the comparison (step1) Separation in two parts In order to come to unambiguous results Part 1: Synthetic water (BAM) Distribution in April/Mai Sample a: Cd0,1- 0,3μg/l, Pb5-10μg/l Ni 10-30μg/l Sample b: Hg0,04- 0,06μg/l Part 2: Natural water (LNE) Distribution in July Sample a+c: Cd, Pb, Niin PFA- bottles 100ml, acidified with HNO 3 Sample b+d: Hg in glass bottles 500ml, stabilized in BrCl - Gravimetrically spiked - Gravimetrical reference value - Concentrations on the EQS level - Water will be filtered - Spiked, but no gravimetrical reference values - Slightly higher concentrations than in part 1 Sample c: Cd0,3- 0,5μg/l, Pb15-25μg/l Ni 30-50μg/l Sample d: Hg0,3- 0,5μg/l

P B T Additional remarks Methods of e.g. ICPMS, AAS, AFS probably combined measurement:with cold vapour technique or Au-preconcentration for Hg. Traceability:e.g. NIST, PTB/BAM/Merck CRM:e.g. Pb, Cd: BCR- 609; Hg: BCR-579, NRC Costs:about Euro for the comparison step1 Status:Supplementary comparison of EUROMET Planned CCQM Key at least for Hg in the next year avtivities:EMRP Participation:First step towards the proposed dissemination structure Therefore: Also open to countries without any QC system so far

P B T List of priority substances Good water quality is defined by „Environmental quality standards“ (EQS) 33 Substances has been identified to be in particular critical 29 organic compounds and 4 inorganic elements and their compounds Main selection criteria: Persistence, Bioaccumulation, Toxicity substancec in μg/lpriority Pb 7,2ps Cd 0,08-0,2phs Hg 0,05phs Ni20ps (tributyltin0,0002phs) pspriority substance phs:priority hazardous substance

P B T Precision method (PTB) Traceability and dissemination chain Method of the routine laboratory Certification method (Merck) Purity determination (BAM) Gravimetrical preparation (PTB) Sample X Sample solution w X (E) Secondary standard Y Commercial sol., U rel = 0,3% w Y (E) Transfer standard T Transfer sol., U rel = 0,1% w T (E) SI kg and mol NANA Primary standard Primary sol. S, U rel = 0,05% w S (E) Pure material, U rel = 0,01% w pur Dissemination Values of materials assigned by methods of measurement Traceability

P B T SU M 16 0 SU M 16 0