P BP BTT

EUROMET- Project *for developing TraceabilityTraceability for EU-wide comparable

Measurement Results in Water Monitoring

Organized by

Physikalisch-Technische Bundesanstalt (PTB), GermanyBundesanstalt für Materialforschung- und prüfung (BAM), Germany

Laboratoire National de Metrologie et d‘Essais (LNE), FranceInstitute 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 BP BTT

ComparabilityComparability

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 materialCertified Reference materialComparison measurement

P BP BTT

ComparabilityComparability

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 BP BTT

ComparabilityComparability

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 BP BTT

Euromet-Project 924Euromet-Project 924

Objective: - Development of a traceability and dissemination system

Subject: - Inorganic elements of the list of priority substancesNi, Cd, Pb, Hg

Deliverables: - Sustainability- Link with all monitoring laboratories- Europe-wide comparable measurement results - global acceptance (key comparison of CCQM)

P BP BTT

Intended Dissemination StructureIntended 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 BP BTT

Time scheduleTime schedule

2007 May Step 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 BP BTT

ParticipantsParticipants

NMIs: PTB (Ge), BAM (Ge), LNE (Fr), IRMM (EU), SP (Se), INM (Ro), NCM (Bg), LGC (UK)

PRLs: Ge 8Fr 4Se 2Il 2Pt 2Hu 1It 1At 1

Registered so far:Registered so far: 8 NMIs and 21 PRLs from 13 EU countries 8 NMIs and 21 PRLs from 13 EU countries

P BP BTT

Thanks Thanks

for your attentionfor your attention

P BP BTT

List of participants (preliminary)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

NMIs PCLs

National authorities +PT scheme providers

National authorities

National authorities

Analytical service provider

P BP BTT

CCQM pilot studiesCCQM pilot studies

CCQM-P100.1 CCQM-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: http://www.epa.gov/waterscience/methods/1631method.html

EN 13506

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 BP BTT

Setup of the comparison (step1)Setup of the comparison (step1)

Separation in two partsIn order to come to unambiguous results

Part 1: Synthetic water (BAM)Distribution in April/Mai

Sample a: Cd 0,1 - 0,3 μg/l, Pb 5 - 10 μg/lNi 10 - 30 μg/l

Sample b: Hg 0,04 - 0,06 μg/l

Part 2: Natural water (LNE)Distribution in July

Sample a+c: Cd, Pb, Ni in PFA- bottles 100ml, acidified with HNO3

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: Cd 0,3 - 0,5 μg/l, Pb 15 - 25 μg/lNi 30 - 50 μg/l

Sample d: Hg 0,3 - 0,5 μg/l

P BP BTT

Additional remarksAdditional 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 150-200 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 BP BTT

List of pList of priority substancesriority 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

substance c in μg/l priority

Pb 7,2 psCd 0,08-0,2 phs Hg

0,05 phs Ni20 ps

(tributyltin 0,0002 phs)

ps priority substancephs: priority hazardous substance

P BP BTT

Precision method (PTB)

Traceability and dissemination chainTraceability and dissemination chain

Method of the routine laboratory

Certification method (Merck)

Purity determination (BAM)

Gravimetrical preparation (PTB)

Sample X

Sample solution wX(E)

Secondary standard Y

Commercial sol., Urel= 0,3% wY(E)

Transfer standard T

Transfer sol., Urel= 0,1% wT(E)

SI

kg and mol NA

Primary standard

Primary sol. S, Urel= 0,05% wS(E)

Pure material, Urel= 0,01% wpur

Dis

sem

inat

ion

Values of materials assigned bymethods of measurement

Traceability

P BP BTT

registered participated

METABOLITES & SUBSTRATES Total Cholesterol 9 9Total Glycerol 2 2Creatinine 5 3Uric Acid 6 5Urea 3 3Glucose 4 3Total Bilirubine 2 2

ELECTROLYTES Sodium 8 6Potassium 7 4Chloride 4 3Calcium 4 1Lithium 5 2Magnesium 4 1

ENZYMES ALT 12 10AST 8 4CK 9 4LDH 9 4GGT 9 5Amylase 6 2

PROTEINS Total Protein 3 2Albumin 4 3

HORMONES Aldosterone 1 1Cortisol 3 3Progesterone 3 3Testosterone 1 1Estradiol-17ß 1 1Estriol (non-conjugates) 1 1Total Thyroxine (TT4) 1 1Total Tri-iodothyronine (TT3)17-Hydroxyprogesterone 1 1

THERAP.DRUGS Digoxin 1 1Digitoxin 3 3Theophyllin

Glyc. Proteins HbA1c 4 3

SUM 143 97

LaboratoriesMeasurand

Reference Laboratories in Laboratory Medicine

RELA 2003

registered participated

METABOLITES & SUBSTRATES Total Cholesterol 9 8Total Glycerol 2 2Creatinine 12 10Uric Acid 6 6Urea 3 2Glucose 5 4Total Bilirubine 2 2

ELECTROLYTES Sodium 5 5Potassium 12 11Chloride 3 3Calcium 3 3Lithium 4 4Magnesium 3 3

ENZYMES ALT 7 5AST 7 5CK 5 4LDH 18 16GGT 9 7Amylase 7 4

PROTEINS Total Protein 7 7Albumin

HORMONES Aldosterone 1 1Cortisol 8 7Progesterone 2 2Testosterone 1 1Estradiol-17ß 1 1Estriol (non-conjugates) 1 1Total Thyroxine (TT4) 1 1Total Tri-iodothyronine (TT3) 1 117-Hydroxyprogesterone 1 1

THERAP.DRUGS Digoxin 5 5Digitoxin 2 2Theophyllin

SUM 153 134

LaboratoriesMeasurand

Reference Laboratories in Laboratory Medicine

RELA 2004