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(1) Braunschweig, 23.05.13 © PTB2010
…from physics…
…to chemistry!
Metrology in chemistry concepts, structure,strategies, priorities
Metrology...
(2) Braunschweig, 23.05.13 © PTB2010
Aus deutschen Landen frisch auf den Tisch
...
...
...
Quality assurance for chemical measurements
(3) Braunschweig, 23.05.13 © PTB2010
...
...
...
Quality assurance for chemical measurements
Motivation:
• Life and well-being as well as international trade require inter-
tionally comparable measurements in chemistry on a high level
• Analytical measurements cannot be carried out by normal people (the
taxpayer) – a globally accepted infrastructure is required that provides
globally accepted comparability of analytical measurement results
• Similar quality standards must apply für chemical measurements on a
global scale with respect to traceability, measurement uncertainty and
detection/quantification limits
Motivation:
• Life and well-being as well as international trade require inter-
tionally comparable measurements in chemistry on a high level
• Analytical measurements cannot be carried out by normal people (the
taxpayer) – a globally accepted infrastructure is required that provides
globally accepted comparability of analytical measurement results
• Similar quality standards must apply für chemical measurements on a
global scale with respect to traceability, measurement uncertainty and
detection/quantification limits
(4) Braunschweig, 23.05.13 © PTB2010
I. Metrology in Chemistry - what it means & why we need it?
II. How is chemistry integrated into the SI
- Chemistry and Meter Convention
III. How does it work ? - global traceability structures in chemistry an application case IV. Traceable …to what ?
- Reference methods in chemistry….and there future!
V. How to build up international metrological infrastructures?
...in chemistry
Overview
(5) Braunschweig, 23.05.13 © PTB2010
metrological traceability
property of a measurement result whereby it can be related
to a reference through a documented unbroken chain of
calibrations each contributing to the measurement uncertainty
International Vocabulary of Basic and General Terms in Metrology (VIM):JCGM 2008
what is traceability?
NOTE 2 The expression “traceability to the SI“ means
metrological traceability to a measurement unit of the
International System of Units
NOTE 1 For this definiton a “reference” can be a
definition of a measurement unit through its
practical realization, or a measurement procedure,..
to a measurement unit
to the SI ?
(6) Braunschweig, 23.05.13 © PTB2010
SI base unit "mole" (the "chemical" base unit)
• Definition:
1. The unit mole is the amount of substance
which contains as many elementary entities
as there are atoms in 0.012 kilogram of
carbon 12; its symbol is “mol”.
2. When the mole is used, the elementary
entities must be specified and may be
atoms, molecules, ions, electrons, other
particles, or specified groups of such
particles.
• Year of Definition: 1967
• Problem: in practise, a realization for all
measurands (analytes in a matrix) is required (amount-of-substance concentration)
• Solution: primary standards for substances of priority
Si-sphere for the re-determination
of the Avogadro number NA
(7) Braunschweig, 23.05.13 © PTB2010
• 1967 Introduction of the mole as the 7th "chemical" SI-base unit • 1993 Foundation of the "Consultative Committee for the Amount of Substance" – CCQM as part of the Meter Convention • 1999 Signing of the CIPM-MRA (mutual recognition of National Standards)
• since 2003 Cooperation of CCQM with several international organisations
Metrology in Cemistry: Historical overview
(8) Braunschweig, 23.05.13 © PTB2010
Consultative Committee for Amount of Substance –
CCQM - Metrology in Chemistry (est. 1993)
aim
to establish
• - worldwide comparability of measurement results in chemistry
• - traceability to the SI, whenever possible, or other internationally accepted reference points
• development of primary standards (methods & reference materials) and data bases
• validation of the traceability of measurement methods
the route
• cooperation with all important stakeholders worldwide
• national and international comparisons
Consultative Committees: CCQM
(9) Braunschweig, 23.05.13 © PTB2010
Metrology in chemistry - international
Consultative Committee for Amount of Substance –
CCQM - Metrology in Chemistry
• Designation of national/regional testing reference laboratories,
acting as an NMI in their field of expertise - no duplication
• Having MoU’s with WMO, WHO, IFCC, ILAC
• Close cooperation with
– ILAC/IAF
– ISO
– Codex Alimentarius Commission
– Inter-Agency meeting
– Global Food Safety Initiative
– World Anti Doping Agency (WADA)
(10) Braunschweig, 23.05.13 © PTB2010
I. Metrology in Chemistry - what it means & why we need it?
II. How is chemistry integrated into the SI?
- Chemistry and Meter Convention
III. How does it work ? - global traceability structures in chemistry an application case IV. Traceable …to what ?
- Reference methods in chemistry….and there future!
V. How to build up international metrological infrastructures?
...in chemistry
Overview
(11) Braunschweig, 23.05.13 © PTB2010
blood sample collected at a medical practitioner…
..and send to a clinical test laboratory..
…are the results reliable ?
…when are they available ?
…is the test expensive?
(12) Braunschweig, 23.05.13 © PTB2010
Problem...
…is the result true?
…what is the measurement uncertainty?
…would I get a different result from a different test laboratory?
…is it relevant?
“Your cholesterol level is too high,
the result from the test laboratory is
some 10 % above the normal level.”
well, ...he is
between
life and death... ..he can‘t
make up his mind
as always !!
(13) Braunschweig, 23.05.13 © PTB2010
100 200 300
100
200
Cholesterol, mg/dL
no
. o
f p
atie
nts
decision limit:
240 mg/dL
results of > 20.000 people
healthy cases (20%)
unnecesseraly treated
untreated (13%)
pathological cases
deviation +10 %
deviation -10 %
Mayo Clinic patients
data from: W. May (NIST) with kind permission
Consequences of inaccurate meas.: cholesterol
(14) Braunschweig, 23.05.13 © PTB2010
even small differences of results may have drastic consequences in clinical chemistry : • are the conclusions of statistical studies in part of the world applicable elsewhere? • do doctors in Germany, the US and elsewhere work on the same basis?
problems, questions...
results analytical measurements may have profound influence on
our daily living
they are the basis of national & international laws and regulations
they must be trustworthy and comparable on an international scale
(15) Braunschweig, 23.05.13 © PTB2010
legal framework in clinical chemistry...
legal requirements in laboratory medicine
• law on medical products and operator ordinance
• directive of the Federal Physicians Council for QA
• EU-IVD (in vitro diagnostic medical devices) directive 98/79/EC
(16) Braunschweig, 23.05.13 © PTB2010
directive of the Federal Medical Physicians Council in Germany (RiLiBÄK)
• measurement
frequency
• medical
relevance
list is continuously updated
selection criteria:
RMW- reference method value SW- setpoint value
priority analytes
analyte measured quantity type of result
max. deviation allowed
amount-of-substance or mass concentration
amount-of-substance or mass concentration
international units
measurands in human serum/plasma
uric acid
urea
human
(17) Braunschweig, 23.05.13 © PTB2010
medical testing laboratories (thousands)
within the quality assurance programme of the German health care system
medical testing laboratories (thousands)
within the quality assurance programme of the German health care system
PTB, DGKL
Primary standards and measurements
PTB, DGKL
Primary standards and measurements
Comparison measurements on “real life” samples
Accredited clinical calibration laboratories Accredited clinical calibration laboratories
(nominated as reference laboratories by the BÄK)
Test samples with traceable values for proficiency testing in the
framework of external quality assurance
+ accurate: calibration needed,multiplier
- expensive and time consuming
+ very accurate
- very expensive and time consuming
Comparison measurements for accreditation
- not so accurate
+ cheap, fast and reliable within legal requirements
Test samples with traceable values for proficiency testing in the
framework of external quality assurance (4x/year)
…up to several thousand measurements per day !!!
isotope dilution mass spectrometry (IDMS) isotope dilution mass spectrometry (IDMS)
primary ratio method: ≈ ± 1 % (k=2)
Comparison measurements on “real life” samples
primary & secondary methods: ≈ ± 5 % (k=2)
spectrophotometry, chromatographies (IC, HPLC, GC),
test kits: test kits: ≤ 13 % (k=2) (legal requirement for cholesterol)
test kits, immuno-assays, photometric methods
Test samples with traceable values for proficiency testing in the
framework of external quality assurance
legal requirements in laboratory medicine
(18) Braunschweig, 23.05.13 © PTB2010
clinical chemistry: application case
black:
acceptance-limits of DGKL
based on
IDMS reference method
coloured squares:
method-dependant limits
blue:
Liebermann-Burchard method
green:
CHOD-PAP method
red:
CHOD-Iodide method
from: L. Siekmann
Proc. Meas.Trac.,Gaithersburg, Nov.2000
with kind permission
YOUDEN diagram
(round robin test of DGKL for cholesterol (1987)
±13
%
(19) Braunschweig, 23.05.13 © PTB2010
legal requirements: reference laboratories
isotope dilution mass spectrometry (IDMS) isotope dilution mass spectrometry (IDMS)
primary ratio method: ≈ ± 1 % (k=2)
primary & secondary methods: ≈ ±
test kits:
Cholesterol in serum
Reference laboratories
±5%
spectrophotometry
IDMS
(20) Braunschweig, 23.05.13 © PTB2010
legal requirements: Key comparisons of NMIs (CCQM)
isotope dilution mass spectrometry (IDMS) isotope dilution mass spectrometry (IDMS)
primary ratio method: ≈ ± 1 % (k=2)
Comparison measurements on “real life” samples
primary & secondary methods: ≈ ± 5 % (k=2)
test kits:
test kits, immuno-assays, photometric methods
±1%
(21) Braunschweig, 23.05.13 © PTB2010
I. Metrology in Chemistry - what it means & why we need it?
II. How is chemistry integrated into the SI
- Chemistry and Meter Convention
III. How does it work ? - global traceability structures in chemistry an application case IV. Traceable …to what ?
- Reference methods in chemistry….and there future!
V. How to build up international metrological infrastructures?
...in chemistry
Overview
(22) © PTB2010
metrology of time: national (primary) standard
second
• definition:
• The second is the duration of 9 192 631 770 periods of the radiation corresponding to the transition between the two hyperfine levels of the ground state of the caesium 133 atom.
• Year of definition: 1967
• measurement uncertainty (so far): 10-15 (0,03 µs/year)
• practical realisation: caesium -fountain clock
state-of-the-art caesium atom clock with laser-cooled atoms
CSF1
(23) Braunschweig, 23.05.13 © PTB2010
primary method of measurement
reference measurement procedure used to obtain
a measurement result without relation to a measurement
standard for a quantity of the same kind
...
NOTE 2 Definitions of two subordinate concepts, which
could be termed “direct primary reference measurement
procedure” and “ratio primary reference measurement
procedure”, are given by the CCQM (5th Meeting,1999).
International Vocabulary of Basic and General Terms in Metrology (VIM):JCGM 2008
what is a primary method ?
(24) Braunschweig, 23.05.13 © PTB2010
Realisation of National Standards in Chemistry
measured quantities in chemistry
• Analytical Chemistry:
measurement methods for the
determination of the
concentration of an analyte in a
matrix (ratio measurement)
• Electrochemistry:
measurement methods for the
determination of electro-
chemical quantities
(pH, electrolytical conductivity)
(25) Braunschweig, 23.05.13 © PTB2010
B D
ion source E
• ion source
– plasma-ionisation
• analyser
– double focussing
• detector
– simultaneous measurements
– Faraday-cups
– high precision
– medium sensitivity
MS example: MC-ICP-MS (Neptune)
condensor: discrimination
quadrupole: energy focussing
magnet: mass discrimination
m/z
(26) Braunschweig, 23.05.13 © PTB2010
ID-MS: primary ratio method
internal standard („spike“):
388.7 g/mol
13C
OH
Primary ratio method:
Isotope dilution mass spectrometry (isotopic labelling): ex. Cholesterol (idealised!)
analyte:
386.7 g/mol
OH
13C- Cholesterol
(known)
Serum
(1g)
13C-
Cholesterol
(known)
un
kn
ow
n
(27) Braunschweig, 23.05.13 © PTB2010
signal distribution for a nat. isotopic
substance containing 27 C- Atoms
(as cholesterol is)
labeled material with 2 C- atoms
replaced by 13C (assuming 95%
success)
l.m.
analyte
Primary ratio method:
isotopic var. distr. over all atoms within molecule ex. cholesterol (more realistic)
Primary ratio method:
isotopic var. distr. over all atoms within molecule ex. cholesterol (more realistic)
ID-MS: primary method for small molecules
A. Henrion
(28) Braunschweig, 23.05.13 © PTB2010
sample
solution reference
solution
m/z m/z
same amount
of l.m. added
same ratio of
signal intensities:
same amounts
of nat. material
amount analyte
in sample soln.
equals amount
in ref. soln.
ID-MS: primary method for small molecules
Primary ratio method: practical procedure (exact matching) Primary ratio method: practical procedure (exact matching)
A. Henrion
(29) Braunschweig, 23.05.13 © PTB2010
Isotpe dilution mass spectrometry (ID-MS)
Calculation of the amount of substance na from the MS signal ratio R
na = nr (Rs – Rsr) (Rsp - Ra) / [(Rsr – Rsp) (Ra - Rs)]
a analyte
r reference
na amount of substance of analyte in sample solution
nr amount of substance of analyte in reference solution
Rs isotope signal ratio in sample and reference solution
Rsp isotope signal ratio in spike
Rsr isotope signal ratio in spiked reference solution
Ra isotope signal ratio in spiked sample solution
from: Andre Henrion, Fresenius J Anal Chem (1994) 350:657-658
ID-MS: primary ratio method
(30) Braunschweig, 23.05.13 © PTB2010
ID-MS: primary method for small molecules
A. Henrion
(Key-) features of IDMS
reliability by the principle used
(internal standard method)
high selectivity by the combination
sample clean-up/ chromatography/
mass spectrometry
precision better than 3%, many cases <1%
best way to accuracy
(31) Braunschweig, 23.05.13 © PTB2010
The future: What is needed?
Major application fields for Metrology in Chemistry:
• Medicine
• Environment
• Food
• forensics
• fundamental metrology
Experimental challenges: traceability for....
• large molecules (biomolecules)
• element species
• trace analysis
• fast (point-of-care) testing methods
• on-line, in-line measurements
(32) Braunschweig, 23.05.13 © PTB2010
directive of the Federal Medical Physicians Council in Germany (RiLiBÄK)
• measurement
frequency
• medical
relevance
list is continuously updated
selection criteria:
RMW- reference method value SW- setpoint value
pregnancy hormone
priority analytes: complex biomolecules
analyte measured quantity type of result
max. deviation allowed
amount-of-substance or mass concentration
amount-of-substance or mass concentration
international units
measurands in human serum/plasma
uric acid
urea
human
(33) Braunschweig, 23.05.13 © PTB2010
principle:
Molecular recognition of proteins
(antigen) by immunoglobulins
(antibodies)
merit:
highly selective recognition of
molecules with a specific
„key“-epitope
limit:
vulnerable to cross
reactions
antigen
(target-
protein)
epitope 2
antibody
diff. antigen
(cross reac.)
epitope 1
testkits with different „keys“:
very different results possible
quantification of proteins by
immuno-assays
testkit
A
B
C
19,9
6,7
0,9
ng/ml
115
489
27
# labs.
from: G.S.Bodor, Denver Health and Hospitals (1997)
example: troponin
T2.J11: traceability for complex biomolecules
(34) Braunschweig, 23.05.13 © PTB2010
...from small to large molecules...
cholesterol (386.7g/mol)
C- reactive protein
(~ 125.000 g/mol)
Unique challenges encountered with proteins:
Proteins are macromolecules
Structural heterogeneity of proteins
LODs for the measurement of proteins
A. Henrion
(35) Braunschweig, 23.05.13 © PTB2010
ID-MS: problems with complex molecules
Angiotensin I (peptid hormone)
a. rel. mass resolution: 5000
b. rel. mass resolution: 1000
product of adrenal gland for controlling
the blood pressure
A
from:
U. Bahr und M. Karas: “Massenspektrometrie Tutorial“
Inst. f. Pharmazeutische Chemie, Universität Frankfurt
Monoisotopice mass 1296,68518
Average mass 1297,50248
a.
b.
12C62H90N17O14 12C61
13C1H90N17O14 12C60
13C2 H90N17O14 12C59
13C3H90N17 O14
(36) Braunschweig, 23.05.13 © PTB2010
hGH
T6
T12 T12*
T6*
isotopically labelled
reference materials
+
+
problem: spectral resolution not sufficient for large molecules
solution: Quantifying enzymatic fragments
T2.J11: traceability for complex biomolecules
A. Henrion
(37) Braunschweig, 23.05.13 © PTB2010
challenge:
Identifying und Quantifying of protein fragments by ID-MS
preconditions:
- identification of a characteristic protein fragment
- quantitative hydrolysis process
A. Henrion
T2.J11: traceability for complex biomolecules
(38) Braunschweig, 23.05.13 © PTB2010
fragments used:
Application to hGH solution
of known concentration
(synthetic solution)
+ 3 %
- 3 %
(PTB) (LGC)
comparison of
different fragments
from:
C. Arsene et al.
Anal. Chem. 2008, 80, 4154
T2.J11: traceability for complex biomolecules
A. Henrion
(39) Braunschweig, 23.05.13 © PTB2010
5
10
15
20
25
30
µg/L
A
B
kit 44 (Lumineszenz) kit 66 (Photometrie)
kit 36 (Radioimmuno-)
kit 77 (‘Lumineszenz’)
IDMS-
reference
value
Test kit data:
Referenzinstitut für
Bioanalytik,
dgkl-rfb.de
12.3±0.5
determination of
T6 und T12
3 aliquote/sample
(A and B)
u (repeatability): 2.5%
U~ 5%
First ID-MS results on 22k growth hormone:
comparison to commercial test kits
6.9±0.4 IDMS reference
value:
Arsene, Henrion et
al. Anal Biochem
401(2010)228
A. Henrion
C. Arsene
R. Ohlendorf
H. Cakar
T2.J11: traceability for complex biomolecules
A. Henrion
(40) Braunschweig, 23.05.13 © PTB2010
in Germany, traceability is required & provided for...
Total protein
Enzymes most relev. enzyme activities
Metabolites & substrates cholesterol, creatinine, glucose, uric
acid, urea, triglycerides, bilirubine,
lactate Hormones cortisol, progesterone, aldosterone,
estradiol, estriol, testosterone, thyroxine
Elements Li, Na, K, Mg, Ca, Cl
Drugs digoxin, digitoxin, theophylline
T2.J10 "Tracebioactivity"
categories: examples:
(41) Braunschweig, 23.05.13 © PTB2010
Traceable measurements for biospecies
and ion activity in clinical chemistry PTB (GER coord.), DFM (DAN), INRIM (ITA), LGC (UK),
LNE (FRA), METAS (SUI), Metrosert (EST), SMU (SK),
SP (SWE), UME (TUR)
Challenge:
From element concentration to clinical activity
Problem
Medical diagnostics requires more precise
information:
not only the total amount of an analyt must be
known but it’s clinically active form
Solution
Si-traceable standards for biospecies an
ion activites of relevant elements
T2.J10 "Tracebioactivity" - speciation analysis
(42) Braunschweig, 23.05.13 © PTB2010
Standards required:
biospecies: Anticancer role of Selenium
• Se-species like methylselenol (CH3SeH)
are highly effective chemopreventive
against cancer.
Increased Se levels in combination with
chemotherapy improve its efficacy in anti-
cancer treatment
• but: narrow window between essentiality
and toxicity
Accurate knowledge of the level of specific
Se-species in blood serum is decisive for
there therapeutic behaviour
> 1,0 µg/g: toxic
< 0,1 µg/g: deficient
e s s e n t i a l Se-species and cancer cell
T2.J10 "Tracebioactivity" - speciation analysis
(43) Braunschweig, 23.05.13 © PTB2010
T2.J10: Quantifying species in serum
Sample preparation
chromatographic
separation
detection
IC, GC, HPLC
M
ICP-MS
total content species
content
extraction decomposition
sample
ICP-MS
t
conv. elemental analysis species analysis
+ spike:
Isotopically labelled
internal reference
C. Swart (EMRP)
D. Schiel
O. Rienitz
C. Frank
(44) Braunschweig, 23.05.13 © PTB2010
IGSM: ID-SERS Raman-spectrometry
a primary method for metrology in chemistry based on Raman-
spectrometry
motivation:
only on primary method for chemical analysis:
mass spectrometry (ID-MS)
solution:
Raman-spectrometry (ID-SERS)
• different physical mechanism
• sensitive for mass
• molecule identification, structural information
problems: detection limit & measurement uncertainty
(45) Braunschweig, 23.05.13 © PTB2010
Raman spectrometer „LabRAM ARAMIS“
(46) Braunschweig, 23.05.13 © PTB2010
ID-SERS Spectrometry: ex. Creatinine
measurement range isotope effect
Ra
ma
n s
ca
tte
rin
g /a
.u.
Raman shift / cm-1
R. Stosch
(47) Braunschweig, 23.05.13 © PTB2010
surface enhanced Raman scattering (SERS)
metal-nanoparticels
(Ag/Au)-colloids
signal enhancement up to 106
R. Stosch
(48) Braunschweig, 23.05.13 © PTB2010
- 6
- 4
2
0
2
4
6
E D C B
rel. d
ev.
/
%
ID-MS
3%
ID-SERS
ID-SERS Spectrometry: ex. Creatinine
from:
Surface-enhanced Raman scattering based approach for
quantitative determination of creatinine in human serum
R. Stosch, A. Henrion, D. Schiel, B. Güttler
Anal. Chem. 2005, 77, 2386-7392
institute
Creatinine in human serum:
ID-MS and ID-SERS
(49) Braunschweig, 23.05.13 © PTB2010
ID-SERS on nanostructured „Chips“
(50) Braunschweig, 23.05.13 © PTB2010
periodical Gold-nanoarrays
50 nm
Au-triangel-structure (SEM) FDTD-Simulations
gap size between particels 10 nm
structure optimisation by numerical simulation
5 10 20 nm
E 5 nm
(51) Braunschweig, 23.05.13 © PTB2010
10 20 30 40 50
100
120
140
160
180
200
(d)(c)
(b)
inte
nsity
/ a
. u
.
average particle separation / nm
(a)
(a) (b)
(c) (d)
50 nm
x
y
(52) Braunschweig, 23.05.13 © PTB2010
900 1000 1100 1200 1300 1400 1500
0
50
100
150
200
250
300
Inte
nsity,
a.
u.
Raman shift, cm-1
10
72
10 µm
Raman mapping
analyte:
4-mercapto-benzoic-acid (4-MBA)
(53) Braunschweig, 23.05.13 © PTB2010
600 700 800 900
0
5
10
15
900 950 1000 1050 1100
0
5
10
15
20
25
12.5
(b)
Inte
nsity (a
.u.)
(a)
12.5
16.64.2
Raman shift (cm-1)
22.0
Creatinine
100 µmol L-1
Urea
100 µmol L-1
(54) Braunschweig, 23.05.13 © PTB2010
±5 %
Int. Key Comparison (NMIs and Clinical Ref. Labs.)
F. Yaghobian (IGSM)
R. Stosch
S. Zakel
S. Wundrack
T. Weimann
B. Güttler
P. Mischnick
(55) Braunschweig, 23.05.13 © PTB2010
EMRP HLT05 Metalloproteins: Motivation
HLT05 Metalloproteine
Partner: LGC, LNE, BAM – DKfZ, Instand
• Nearly half the proteins need metals in active centre or as co-factor1
• Directives like the “Richtlinie der Bundesärztekammer” (directive of the German Medical Assembly) define method specific target value determined as the median for this method with method specific limits
• Reference measurement procedures and reference materials as required by JCTLM not available for many metalloproteins
• Reference materials (often lyophilised or spiked) show different behaviour compared to real clinical samples using analysis methods like immuno assays
(56) Braunschweig, 23.05.13 © PTB2010
Einsatzziel
Transferrin
transferrin
measurement method measurement procedure
comb. proteolyse – peptide analysis
HLT05 Metalloproteins
TOF-MS
HPLC-ICP-MS
SERS-Raman
HLT05 Metalloproteine
Partner: LGC, LNE, BAM – DKfZ, Instand
(57) Braunschweig, 23.05.13 © PTB2010
Overview
I. Metrology in Chemistry - what it means & why we need it?
II. How is chemistry integrated into the SI
- Chemistry and Meter Convention
III. How does it work ? - global traceability structures in chemistry an application case IV. Traceable …to what ?
- Reference methods in chemistry….and there future!
V. How to build up international metrological infrastructures?
...in chemistry
(58)
Developing Metrological
Infrastructures
for Water Analysis in Europe
River Elbe between Hamburg and Cuxhaven © Vidicom / Christian Irrgang
(59)
Water - the European perspective
Water in the European Union
The water framework directive -
a common legislation for at
least 27 states and more than
500 million people
implementation of the
directive under drastically
different and changing
conditions in different
countries
(60)
Motivation
- 20 % of all surface waters in the European
Union are heavily polluted.
- 65 % of the drinking water originate from
ground water resources.
- 60 % of the European cities overuse their
ground water resources.
- 50 % of the EU wetlands (and their biota)
are endangered because of overused
ground water
- The artificially watered areas in the EU
increased by 20 % since 1985.
(e.g., European Environmental Agency, report 1995)
EU Water Framework Directive 2000/60/EC (WFD)
(61)
Chemical status: Where do we come from ?
Status GDR 1990 - main rivers and
many surface waters
are heavily contaminated
- only 42% of the
population has access
to an adequate
sewage system
- only 20% of water
courses can be used
for drinking water.
- life expectancy in certain areas is as much as ten years below the
state average
(EU press release P/90/67 Date: 27/09/1990)
"silver lake" near Bitterfeld & Wolfen, 1990
(62)
Aims
• to establish a legal framework to protect and restore clean water
across Europe and to ensure its long-term and sustainable use
• to expand the scope of water protection to all waters: surface
waters, transitional waters, coastal waters and groundwater
• to achieve a "good status" for all waters by a set deadline (2015)
• to achieve a water management based on river basins
• to implement a "combined approach" of emission limit values and
quality standards
EU Water Framework Directive 2000/60/EC
(63)
WFD Quality standards: Chemical status
Good chemical status (aims and strategies)
- ... groundwater should broadly be that it should not be
polluted at all (European Quality standards - EQS - level)
- compliance with all the quality standards for chemical
substances at European level.
- prioritisation mechanism for hazardous chemicals:
ensuring a minimum chemical quality, in relation to very
toxic substances, everywhere in the Community
(64)
Chemical status: priority substances
selection criteria
- aquatic ecotoxicity and human toxicity via aquatic exposure
routes
- Intrinsic hazard (toxic, persistent and liable to bio-
accumulate)
- evidence from monitoring of widespread environmental
contamination
- other proven factors indicating possible widespread
environmental contamination (e.g., industrial production
rates)
Decision 2455/2001/EC of the European Parliament and the Council
(65)
Selected 33 priority substances or groups of substances: (WFD) 2000/60/EC & QA/QC Directive (2009/90/EC)
- 4 heavy metals
- 14 pesticides
- 15 organic compounds of industrial origin
(e.g. flame retardants)
review every four years
Chemical status: priority substances
(66)
EUROMET Project 924
A sustainable traceability system providing Europe-wide comparable
measurement results in water monitoring under the WFD
organized by BAM, LNE, IRMM, PTB
Task:
Comparison measurements for selected priority substances:
heavy metals (Ni, Pb, Cd, Hg)
Aims:
- provide reference points (National Standards, CMCs) of sufficient
quality (suitable for EQS-requirements) to serve the WFD
- establish links to expert* and monitoring laboratories in Europe
*pt-providers, potential calibration laboratories (PCL)
- assess comparability and measurement uncertainties in the field
- validate methods of expert laboratories
- feasibility of a metrological dissemination system in Europe
Lake Pielinen, Finland
(67) Braunschweig, 23.05.13 © PTB2010
Requirements of the QA/QC directive (2009/90/EC)
to assure comparable measurement results
(… pursuant to Directive 2000/60/EC)
- Methods have to be validated and documented in accordance to
EN ISO /IEC17025
- Minimum performance criteria for the analytical method:
Limits of quantification ≤ 0.3 * EQS
Uncertainty ≤ 0.5 * EQS
- Monitoring laboratories have to participate in PT shemes
- organized by accredited or internationally recognized organisations
- evaluated according to ISO Guide 43-1 or ISO 13528 or equ.
priority substances: measurement requirements
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Step 2: Validation of the measurement
procedure of the PCLs supported by NMIs
Step 3: Link of field laboratories and
PCLs in the framework of a PT scheme
NMIs
Monitoring Laboratories
Potential Calibration
Laboratories
Step 1: Link of NMIs and PCLs by
means of a comparison measurement
PCL: Potential Calibration Laboratories
EUROMET 924
EUROMET 924
(69) Braunschweig, 23.05.13 © PTB2010
Euramet 924 Step 3:
114 Test- and expert laboratories
4 NMIs (BAM, LNE, PTB, NCM)
Germany 33
Israel 2
Hungary 12
Bosnia-Herzegovina
1
Portugal 4
Slovenia 1
Czech 1
Croatia 4
Bulgaria 6
Austria 11
Italia 9
Romania 1
Norway 1
Sweden 4
France 18
Spain 5
Finland 1
Σ Countries:17 Labs: 114
EUROMET 924: step 3
(70) Braunschweig, 23.05.13 © PTB2010
NMIs:
PTB, BAM, LNE, IRMM
Calibration laboratories:
8 Germany
4 France
1 Sweden (NMI)
1 Norway
1 Finland
1 Romania (NMI)
1 Bulgaria (NMI)
1 Austria
2 Portugal
1 Italy
1 Hungary
2 Israel
1 Chile (NMI)
Metrology for European needs
Israel
(71) Braunschweig, 23.05.13 © PTB2010 (71) (71)
Target values for test laboratories
- Natural ground water (in mg/l, about Ca: 44, Na: 43,
K: 4, Mg: 8, heavy metals: maximal some 10 ng/l)
- Samples prepared and dispatched by PTB/IWW
Target uncertainty UTarget ≤ 0.5 * EQS
Limit of quantification βLOQ ≤ 0.3 * EQS
EQS βLOQ UTarget
in μg/l in μg/l in μg/l
Hg 0.050 0.017 0.025
Cd 0.090 0.030 0.045
Pb 7.2 2.4 3.6
Ni 20.0 6.7 10.0
(72)
Hg : CCQM K70 & EUROMET 924 step3
all participants: 66
βmean = 72.47 ng/l
RSD = 24.4 ng/l or 33.6 %
β RV = (72.4 ± 2.5) ng/l
test- and PCLs: 55
βmean = 72.9 ng/l
RSD = 26.6 ng/l or 36.5 %
β RV = (72.4 ± 2.5) ng/l
Metrology Inst. Expert Inst. Mon. Labs
(73)
EUROMET 924: subm. results - monitoring labs
concentration / µg/L
resu
lts r
etu
rned
/ %
(74)
• Organochlorine pesticides
• PBDE Polybromated Diphenylether
• PAH Polycyclic Aromatic Hydrocarbons
• TBT Tributyltin compounds
• SCCP 10 to C13 Chloroalkanes
CEN/TC230
Mandate 424 addressed to CEN:
Method development to support
WFD monitoring
critical pollutants:
priority substances for which suitable
measurement methods are not available
EMRP: WFDtraceability-project (2011 – 2014)
(EQS = 0,5 ng/kg for PBDEtotal)
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Organic analysis • Organic analysis
• Element analysis
• Elektrochemistry
• Clinical Chemistry
• Gas Analysis
•
•
•
• pure materials
• gas mixtures
• certif. reference materials
gas mixtures for
environmental
protection
Food safety: residues in food
• clinical analytes
- hormones, enzymes
- new diagnostic
marker
• clinical analytes
- hormones, enzymes
- new diagnostic
marker
the German network: partners for chemical standards
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Traceability for Chemistry in Germany
National Network in Germany
• Health (Clinical Cemistry: PTB, DGKL)
• Environment (air, water & soil: UBA, PTB, BAM)
• Food (Residues: BVL)
• Energy (natural gas: BAM)
• Forensics (breath alcohol testing, drugs of abuse (THC): PTB, BAM)
• Electrochemistry (pH, electrolyt. conductivity PTB)
• Inorganic Analyses (elements, element solutions: PTB, BAM))
• 15 accredited calibration laboratories
• legal authorities
• clinical reference laboratories of the BÄK
• air surveillance network of the Fed. States
• water surveillance network of the Fed. States
• Food surveillance network of the Fed. States
Dissemination (multiplicators)
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• PTB acts as legally responsible national authority in an
international metrological network established by CIPM/CCQM
• It shares and delegates its work on the national level in a network
with dedicated institutes responsible for a defined subject field
• It establishes a linked & harmonized traceability structures with this
national network to support and ensure international comparability.
• If this is all established, the final goal of all the traceability efforts can
be achieved, namely:
Tested once, accepted everywhere Tested once, accepted everywhere
traceability structures in Germany: summary
(78) Braunschweig, 23.05.13 © PTB2010
thank you...
...for your interest !
...and to my colleagues in PTB, Dep. 3.1
in particular:
Andre Henrion
Detlef Schiel
Petra Spitzer
Rainer Stosch
Olaf Rienitz
Olaf Werhahn