Accred Qual Assur (2001) 6:3-7

© Springer-Verlag 2001

Gunther Dube Metrology in chemistry - a public task

Abstract The importance of analy- uring devices. In fields in which the

Presented at Analytica Conference 2000,
11-14 April 200D, Munich, Germany
G. Dube
Physikalisch-Technische Bundesanstalt,
Bundesallee 100,38116 Braunschweig,
Germany
e-mail: gunther.dube@ptb.de
Tel.: +49-531-5923210
Fax: +49-531-5923015
tical chemistry is increasing in
many public fields, and the de-
mand for reliable measurement re-
sults is growing accordingly. A
measurement result will be reliable
only if its uncertainty has been
quantified. This can be achieved
only by tracing the result back to a
standard realizing the unit in which
the measurement result is ex-
pressed. The National Metrology
Institutes (NMIs) can contribute to
the reliability of the measurement
results by developing measuring
methods, and by providing refer-
ence materials and standard me as-
comparability of measurement re-
sults is of particular importance,
they establish traceability struc-
tures. Responding to the globaliza-
tion of trade and industry the In-
ternational Committee for Weights
and Measures (CIPM) agreed on
an arrangement on the mutual re-
cognition of calibration certificates
(CIPM MRA) issued by the NMIs.
Keywords Reliability .
Uncertainty . Traceability
National Metrology Institutes
CIPM MRA

be best achieved by cooperation between the two par-

Introduction ties.

In many fields in which quantitative analyses are called

for, analytical chemistry is confronted with new chal-
lenges. Particularly in such spheres, on which countries
spend a considerable part of their revenue like health
care, environmental protection and nutrition, reliable
measurement results are of great importance. "To
judge analytical methods and results critically, this be-
longs at all times to the analyst'S tasks" [1]. Therefore,
analytical chemists also use metrological ways of think-
ing and terms like traceability and uncertainty of meas-
urement results. On the other hand, metrologists un-
derstand their responsibility in determining amount-of-
substance measurements, and try to reach uniformity of
measurement to achieve comparability of the results. In
doing so, they make use of the worldwide metrological
infrastructure. The demand of the public for reliability
of the measurement results in analytical chemistry can
The need for reliability of measurement results
The need for reliability of measurement results is de-
monstrated by the following examples. In Germany the
expenditure for health care in 1994 amounted to
DM 344.6 billion [2]. This was 10% of the gross nation-
al product. One-third of this went into medical services:
10% of these was spent on laboratory services, i.e. for
the most part on measurements, and it is well known
that 30%went into repeating measurements [3]. Repeat
measurements are carried out only if the results do not
seem reliable. In this particular case, the financial loss
due to repetitions amounted to DM 3 billion.
The second example comes from the area of natural
gas. In Germany the import of natural gas has in-
creased over the last 30 years and in 1998 amounted to
 Metrology in chemistry . . a public task 9

Import of Natural Gas, Germany year, this error of 0.1 % leads to a price difference of
OM 20 million.
Ref.: BMWi, http://www.bmwi.de

3e+6 .-----------------------------------,
Uncertainty and traceability of measurement results
2e+6 It follows from these examples that the reliability of the
measurement results is of great public interest. Meas-
Q) urement results are reliable only if their uncertainty is
:; 2e+6 known and quantified. Uncertainty is a metrological
0

-
'ro'
.... term which is defined as follows: Uncertainty: parame-
Q)
ter, associated with the result of a measurement, that
c:: 1e+6 characterizes the dispersion of the values that could
>- reasonably be attributed to the measurand [5].
....
C)
Q)
c:: 1e+6 The uncertainty can be stated only if the traceability
W of the measurement result to a system of units is gua-
ranteed. Traceability is defined as follows [5]: Tracea-
5e+5
bility: property of a result of a measurement or the val-
ue of a standard whereby it can be related to stated ref-
erences, usually national or international standards,
Oe+O +---.----"'1' through an unbroken chain of comparisons, all having
1965 1970 1975 1980 1985 1990 1995
stated uncertainties.
Such a traceability system is demonstrated in Fig. 2.
Year
The International System of Units (SI) is at the top of
Fig.l Import of natural gas, Germany (Ref.: Bundesministerium the system. Its units are realized by standards. A meas-
flir Wirtschaft und Technologie, BMWI) urement is a process, in the course of which the measu-
rand is compared to a standard. For practical measure-
ments, usually a working standard not a primary stand-
ard is used. To state the uncertainty of the measure-
nearly 3 million terajoule (TJ) [4]. The data shown in ment result, the uncertainty of the value assigned to the
Fig. 1 are given in TJ, and that is why the calculation of working standard must be known. It results from the
the natural gas price is based on the energy consumed. uncertainty of the comparison measurement of the
This is the product of calorific value and volume. Fo! working standard with the reference standard. The un-
the determination of the energy, the calorific value H certainty of the value assigned to the reference stand-
of the natural gas must be known. The well-known ard results from the uncertainty of the comparison
method for the calorimetric determination of calorific measurement of the reference standard with the prima-
values is increasingly replaced by a new method. The ry standard. This chain of comparison measurements is
main feature of this method is the determination of the exactly what the definition of the term "traceability"
mole fractions of the gas components using gas chroma- means. If the traceability of a measurement result is
tography. The mole fractions Xj are multiplied by the
molar calorific values HO (t l ) of the gas components.
These products are summarized and multiplied by P2/
Responsibility
RT2 according to Eq. (1).
N
HO[tl V(t2P2)] = j~l XjX HO(t l) :;2 (1)
SI
...
Primary Method
CGPM

CIPM, NMI

where tlis temperature of combustion, V is volume, P2,

t2 is the temperature and pressure at measurement, Tis
the absolute temperature, HO is the molar calorific val- Secondary Method Accredited
ue, x is the mole fraction, R is the gas constant. Calibration
The effects that a wrong gas chromatographic result Laboratories

has on the natural gas price should be considered. If it

Routine Method Routine
is assumed that one component accounting for 10% of I Laboratories
the natural gas was determined incorrectly by 1%. The Working Standard
calculated energy is affected by an error of 0.1 %. If the
price of the natural gas amounts to OM 20 billion per Fig.2 Traceability scheme
\0 G. Dube
guaranteed, its uncertainty can be stated. From this
considerations it follows that metrology can provide the
tools, necessary to get reliable measurement results.
In analytical chemistry, traceability of measurement
results to SI units is not always possible and the tracea-
bility hierarchy ends below the level of the SI units. For
example, in the case of standard measuring devices, or
reference materials, the values are fixed by mutual
agreement or in the case of methods are generally
agreed upon. In these cases, the comparability of meas-
urement results is limited.
Tasks of the National Metrology Institutes (NMlsl
The tasks of the NMls are :
- Realisation, maintenance and dissemination of the
units
- Development and application of primary measure-
ment methods
- Establishment of traceability structures
- Guaranteeing the equivalence of measurement
standards.
In Germany, the Physikalisch-Technische Bunde-
sanstalt (PTB) is responsible for the national standards.
In chemistry, reference materials and standard measur-
ing devices are the national standards. To cover the
huge demand for reference materials, the PTB cooper-
ates with other competent national institutions on the
basis of agreements, first of all, with the Federal Insti-
tute of Material Research and Testing (BAM) and also
with companies which produce and distribute reference
materials. PTB also cooperates with other NMls within
the scope of joint projects aiming at the development of
new reference materials not yet available on the mar-
ket.
To trace back the values assigned to reference mate-
rials to the SI, the NMls develop and apply "primary
methods". It is the main feature of these methods
which are sometimes called "absolute methods" that
they do not make reference to standards of the same
unit in which the result is expressed. Examples are cou-
lometry, gravimetry and isotope dilution mass spec-
trometry [6, 7].
In cases, where traceability to the SI is not possible
or can be attained only with a relatively high uncertain-
ty, standard measuring devices form the highest refer-
ence points of the traceability chain. At PTB for exam-
ple, a standard measuring device was set up to provide
traceability of pH measurements [8]. It consists of a sys-
tem of reference electrodes, which form a electrochem-
ical cell. The electrolyte of the measuring cell is the pH
buffer solution to be measured. From the cell voltage
the pH value of the buffer solution is determined by a
well-defined measuring procedure. By the measure-
ment this solution gains the rank of a primary reference
Uncertainty Responsibility
•
SI CGPM
Primary Method CIPM;NMI
5x10E·3
Second ary Method Accredited Reference Labs
Producers Calibration Labs
1x 10 E-2 Control ;terial
Routine Method Clinical LaboratOfies
I
5x to E-2 Patient Sample
Fig.3 Traceability in clinical chemistry
material. The uncertainty of the pH value on this level
amounts to 0.002. The primary buffer solutions are
used by accredited calibration laboratories as reference
solutions for measuring the pH values of secondary
buffer solutions in an electrochemical comparison cell.
The uncertainty of the pH of these solutions is higher
than the uncertainty of the primary buffer solution and
amounts to 0.003. The secondary buffer solutions are
used in the routine laboratories for calibrating commer-
cial pH meters. The pH values measured by commer-
cial pH meters show an uncertainty of 0.01. This tracea-
bility chain guarantees that the uncertainty of the pH
values measured in the routine laboratories are correct-
ly stated. They thus are reliable. Other NMls also keep
such pH measuring devices, and it was possible to de-
monstrate by comparison measurements that the stand-
ard measuring devices of different countries can pro-
vide measurement results which agree very well [9].
The establishment and the support of traceability
structures is one of the most essential tasks of the
NMls. Traceability is of particular importance also in
clinical chemistry. It must be ensured that the results
obtained in the measurement of patient samples, are
reliable. Therefore, in 1988, the Federal Medical Asso-
ciation (Bundesarztekammer) in Germany issued
"Guidelines for Quality Assurance in Medical Labora-
tories" [10]. Although at present under revision, they
prescribe the use of quality control samples to check
the measurement results obtained in medical laborato-
ries. For control materials used in internal quality con-
trol the producer and for control materials used in ex-
ternal quality control a reference laboratory must make
sure that an uncertainty is stated for the assigned value.
This is possible only if the control materials are linked
to primary reference materials and to SI units. The link
to the SI can be provided by reference laboratories as
well as by the laboratories of control material produc-
ers, provided they have been accredited as calibration
laboratories. In Germany this accreditation can be pro-
 Metrology in chemistry - a public task II

vided by PTB and is carried out by the German Cali- Table 1 CCOM international comparisons, clinical diagnostic
bration Service (DKD). markers. NIST: National Institute of Standards and Technology,
USA; LGC: Laboratory of the Government Chemist, UK;
IRMM: Institute for Reference Materials and Measurements,
Belgium; SP: Sveriges Provnings- och Forskningsinstitut, Sweden
The International Committee for Weights and Measures
Mutual Recognition Arrangement (CIPM MRA) Reference Pilot lab Date
No.
The NMls are obliged by national law to realize, main- Cholesterol in serum CCOM-P6 NIST 199H
tain and disseminate the national standards. However, CCOM-K6 NIST 1999
they also take care of the uniformity of measurement Glucose in serum CCOM-PH NIST 1999
worldwide. The first activity for this was the signing of Creatinine in serum CCOM-P9 NIST 1999
Creatinine in serum CCOM-KI2 N 1ST 200!)
the Meter Convention in 1875. On the basis of this trea- Ca in serum CCOM-PI4 IRMM/SP 20m
ty, the General Conference of Weights and Measures Anabolic steroids in urine In preparation -
(CGPM) and CIPM work today. However, the NMls Hormones in serum In preparation -
are confronted today with new challenges [11]. The cal-
ibration certificates issued by them are generally valid
only in the country of issue and are not accepted world-
wide. This turned out to be a barrier to the internation- - Health
al trade. So, different activities have been launched by - Food
various institutions to overcome these obstacles. The Environment
contribution of the NMIs to these efforts is the "Mutual - Advanced materials
Recognition Arrangement" (CIPM MRA), which was - Commodities
signed by the presidents of 38 NMIs in October 1999 - Forensic matters
during the twenty-first session of the CGPM [12]. Its - Pharmaceuticals
objectives are: - Biotechnology
- To establish the degree of equivalence of national In the field of amount-of-substance measurements,
measurement standards maintained by NMls 70 comparisons have been planned. Some of them have
- To provide for the mutual recognition of calibration already been started. Up to now, the measurement pro-
and measurement certificates issued by the NMIs gramme for clinical chemistry has carried out the com-
- Thereby to provide governments and other parties parisons given in (Table 1) [13].
with a safe technical foundation for wider agree- The results of the key comparisons - including the
ments related to international trade, commerce and uncertainty statement - will be stored in an Internet-
regulatory affairs. accessible database. This will enable companies, ac-
The technical basis of the CIPM MRA is a system of crediting bodies, and institutions to evaluate the equi-
key intercomparisons. Furthermore, the NMls have to valence of the measurement results performed by the
prove that they work in accordance with a quality sys- NMIs. The database will make it easier for businesses
tem. The key comparisons are international compari- and organizations relying on these services to prove
son measurements. The Consultative Committee for compliance with the measurement-related require-
Amount of Substance (CCQM) of CIPM is responsible ments of regulations and standards. The database will
for the comparisons in the field of chemistry. It selects be an integral part of the infrastructure necessary to ex-
the substance systems, organizes the realization of the pand free trade and to eliminate technical barriers to
measurements and the evaluation of the measurement export.
results. The substance systems are chosen from areas of
public interest in which traceability is necessary. Prior- Acknowledgements Stimulating discussions with Mrs. P. Spitzer
ity areas are: and Dr. P. Ulbig are thankfully acknowledged.

References

I. Doerffel K (19H7) Preface to: Statistik
in der analytischen Chemie, 4th edn.
YCH, Weinheim, Germany
2. Bundesministerium flir Bildung und
Forschung, Bundesministerium flir
Gesundheit, Statistisches Bundesamt
(20UO) Die Gesundheitsberichterstat-
tung des Bundes; http://www.gbe-
bund.de
3. Semerjian HG (199H) Metrology: Im-
pact on national economy and inter-
national trade. In: Seiler E (ed) The
role of metrology in economic and
social development. PTB-Texte, Band
9, Braunschweig, pp 99-133
12 G. Dube
4. Bundesministerium fiir Wirtschaft
und Technologie (1999) Entwicklung
der Einfuhr Naturgas in die Bundes-
republik; HYPERLINK
http://www.bmwi.de
5. Deutsches Institut fiir Normung
(1994) Internationales W6rterbuch
der Metrologie, 2nd edn. Beuth, Ber-
lin Wien Ziirich
6. Quinn T (1997) Metrologia 34:61-05
7. Richter W (1997) Accred Qual Assur
2:354-359
H. Spitzer P, Eberhardt E, Schmidt I,
Sudmeier U (1996) Fresenius J Anal
Chern 356: 17H-IHI
9. Spitzer P (1997) Metrologia
34:375-370
10. Bundesarztekammer (19HH) Dt A.rzte-
blatt H5:099-706;(1994) 91 :211-212
11. Richter W (1999) Fresenius J Anal
Chern 305: 509-573
12. Comite international des poids et me-
sures (CIPM) (1999) Mutual recogni-
tion of national measurement stand-
ards and of calibration and measure-
ment certificates issued by national
metrology institutes. Bureau interna-
tional des poids et mesures (BIPM),
Sevres, France
13. BIPM (1999) Comite consultatif pour
la quantite de matiere (CCQM).
Report of the 5th Meeting (February
1999). Bureau international des poids
et mesures (BIPM), Sevres, France