CHAPTER 4

ON THE IMPORTANCE OF METROLOGY IN CHEMISTRY

E.Bulska1,2 and P.D.P. Taylor2

1
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warszawa, Poland
2
EC-JRC Institute for Reference Materials and Measurements, Retiesweg, B-2440,
Geel, Belgium

ABSTRACT
With growing globalisation of various human activities, also the results of chemical
measurements become directly or indirectly involve in this process. There is no doubt
that quality of chemical measurements is an important issue in modern society
influencing quality of life and border-crossing trade. On an international scale, the
world of chemical measurements is undergoing major changes. Over the last decade,
initiatives have been taken at the international level and across measurement sectors to
ensure that measurement science issues are applied in a systematic way. This is done to
improve the quality of chemical measurement results and thus make them acceptable
everywhere. In the past two major routes towards quality in chemical measurements
have been applied: use of quality management systems and use of accreditation. Only
recently, have the principles of measurement science (metrology) received the attention
they should. This does not replace the need for most aspects of QA (Quality Assurance),
but complements this, i.e. bringing a solid foundation to build on. Firstly applied in
physics, they are now recognised as a necessary tool in chemistry as well.
 Chapter 4

1 INTRODUCTION
The growing demand of the public for reliability of the measurement results in
analytical chemistry has been recognised over the last decade [1]. Following the paper
by de Bievre [2] the importance of this can be demonstrated by the following examples:
(i) In a food sector the quality of products often required to establish the content of toxic
substances in order not to exceed the legal limits. So the results of the chemical
measurement should allows to answer the question: Have the formal limits of
particular toxic substance if food or drink been exceeded (e.g. content of Cd in
milk) ?
(ii) In a clinical sector the diagnosis is often based on the results of the content of
particular substance in blood or urine. So the results of the chemical measurements
should allowed to answer the question: Have correct decision been made on
whether a patient must go on medication or just on a diet (e.g. cholesterol in
blood) ?
(iii) In environmental sector the results influence the value of the particular region in
respect of living conditions or tourists attraction. So the results of the chemical
measurements should allow answering the question: Was the reduction in value of
land reasonably estimated (e.g. because of the toxic pollutant in the soil) ?
Metrology is a science of measurements and obviously, measurements of different kinds
are carried out in analytical and bioanalytical chemistry. Chemical measurements are
essential in different fields (environmental, geology, medicine, biology etc.). Important
decision are often based on those (e.g. either food can be eaten, goods can be sold,
patient should be treated), in support of legislation (related to health care, trade),
production process and social problems [3]. There is strong evidence from different
ILC’s (Interlaboratory Comparisons) that the quality of such measurements results are
still unsatisfactory, probably because the metrological aspects of those measurements is
insufficiently stressed [4]. The international today’s society relies on a proper
measurement infrastructure, which in much extend depend on the properly trained
people. This requires the knowledge dissemination, concerning the chemical
measurements based on the metrological principles, which are considered to be most
important in this respect [5].
Still it is beliefs in various sectors that the implementation of metrology in
analytical chemistry means mainly the replacement of old terms with new ones, for
example the uncertainty replace the ‘precision’, and traceability replace the ‘accuracy’.
It should be therefore stressed that it is not just a replacement of wording but this cover
the major changes in general concept of understanding the measurement process. The
proper understanding of the metrological principle is also required by those who need to
work under the requirement of ISO 17025 [6].
This chapter contains a set of modules covering fundamental information
concerning the principle of metrology in chemistry. This covers a general introduction
to metrology in chemistry, uncertainty and traceability of measurement results and the
issue of validation of the measurement procedure as well as statistical tools used for
uncertainty evaluation are covered respectively. Also the topic related to the use of
CRM (Certified Reference Materials), types and aims of ILC’s (Interlaboratory
Comparisons).
As it was already stressed above, today’s society relies on a proper measurement
infrastructure, e.g. to realise the international trade, to implement regulation, to
guarantee consumer protection and at least but not least to support scientific research.
Key players in such an infrastructure are measurement service provides (national
metrology institutes, national and sector reference laboratories, control laboratories etc),

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national accreditation bodies and organisation responsible for education and training
[7]. This is realised via the European Programm TrainMiC (Training in Metrology in
Chemistry). The trainMiC (www.trainmic.org) platform intends to be open to all
organisations and people accepting basic principles of the metrology [8]. The status of
the metrology in chemistry in Poland is described in the European Commission Report
EUR 199915 EN [9]. This Report describes the activity performed by respective
governmental bodies: Central Office of Measurements; Polish Centre for Accreditation;
Polish Committee for Standardisation as well as various activities performed under the
responsibility of the ministries of the: (i) Environment; (ii) Agriculture and Rural
Development; (iii) Health; (iii) Economy; (iv) Labour and Social Affairs. Also the
activities of non-governmental bodies (Committee of Analytical Chemistry of Polish
Academy of Sciences; POLLAB; REFMAT) as well as selected education activity were
described. This exemplified in direct way how important is the metrological issue in the
activity of our society. The important conclusion form the Status Report is that in
Poland always the significant activity in respect of organisation and/or participation in
interlaboratories comparisons as well as in production of reference materials was
perform over the many years. Several examples are listed in the Appendix of that Status
Report.

2 METROLOGY IN CHEMISTRY
The aim of this chapter is to discusses the topic of what is metrology, why it is needed
as well as what is its position in analytical chemistry. The similarities and differences
between the metrology in physics and in chemistry will be stressed by focusing on the
fact that in physical measurement the issue is to compare quantities (e.g. lengths of
different tables) traceable to a unit (e.g. metre) as in chemical measurement the issue is
to compare an amounts of analyte (e.g. content of DDT in meat) traceable to a unit (e.g.
mol/kg). As a consequence of this the major impact in physical measurements comes
from the calibration of instrument, where as in chemical measurement additionally to
that, the measurement procedure calibration should be considered.
According to the metrological principles reliable measurements depend on
having defined standards for analytes, demonstrable traceability of results to the defined
standards and an understanding of the uncertainties of those processes. In trading
relationships, both the sides often repeat measurements and then, regulatory agencies
usually required their own independent check. This replication of effort well reflects the
current inability of chemical measurement to produce consistent results over distance
and time.
Metrology has been developed from physical measurement and emphasises
results traceable to defined reference standards, normally the International System of
Units (SI), and fully analysed uncertainty budgets based on the processes set out in the
Guide to the Expression of the Uncertainty of Measurement (GUM) [10]. This process
involved identifying each component of the measurement that contributes to
uncertainty, estimating the contribution of each component of uncertainty, than
combining these estimations to calculate the total uncertainty. Much of the
improvement in consistency of physical measurements has been achieved by use of the
uncertainty budget to better define and controls the measurement environment. The
situation with respect of chemical measurements is much more complex and difficult.
The comparison of the application of metrology in physic and chemistry is summarised
in Table 1.

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TABLE 1.
The comparison of the metrological issue in physical and chemical measurements

Metrology in Physics vs. Chemistry

Physics Chemistry
Measurement Comparing a quantity; Comparing a quantity of analyte;
e.g. temperature e.g. DDT in milk
Units m, s, K mol/kg, mg/kg
Influence by.. Often relies on direct Various factors affect the results
measurements
Major impact Equipment calibration Chemical treatment (e.g. extraction,
digestion); reference materials used;
…and equipment calibration
Dependent on.. To large extend “sample Strongly “sample dependent”
independent”
Example Length of the table Concentration of Pb in: Seawater;
Soils; Blood etc.

It is clear that chemical measurement has a fundamental difference from physical

measurement in that it does not take place under controlled and defined conditions.
Almost always, the primary objective of chemical measurement is to determine the
amount of components of interest, not the total composition of the samples. Total
composition will almost always remain unknown and therefore the total environment
under which the measurement is taking place cannot be defined and controlled.
Unknowns will always increase the uncertainty associated with any measurement.
In the last years much effort has been applied to introduce the metrology
concepts of physical measurement into the chemical measurement. For example:
- The Bureau International des Poids et Mesures (BIPM) has put in place a consultative
committee, the Consultative Committee on the Quality of Material (CCQM), to
strengthen the relationship of chemical measurements to its SI unit, the mole
(www.bipm.fr).
- EURACHEM and CITAC have developed a guide for quantifying uncertainty in
chemical analysis based on metrological principles and GUM to quantifying uncertainty
of measurement [11].
- ISO/IEC 17025:1999 is replacing ISO 25 guide as the standard against which
laboratories are accredited and supports these moves by having an increase emphasis on
this metrological approach [6].
In every days laboratory performance a chemical measurements depends on a
combination of the separation of the sub-samples from the material intend to be
analysed, physical measurements as well as chemical separation of the species of
interest. Therefore, understanding of the uncertainty of the chemical measurements
could not be possible without an understanding of the whole process. This also leads to
the fact that laboratory should document the whole procedure in a transparent way.
However, it is still possible to find the ‘traditional;’ beliefs that:
The result is correct, but there is no need to show why;
It is not necessary to state and demonstrate traceability;
It is not possible to write model equation;
The smaller the number behind ± the better laboratory works;
I did this for long time and I know my business.

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They are several evidence (e.g. Interlaboratory Comparisons results) that claim is not
the same as demonstration proofs [4]. Therefore a lot of attempt has been done in order
to shift the beliefs of analytical chemists into that based on the use of the metrology.
The way to improve the understanding of the advantages of the metrology when applied
into the chemical measurements can be summarise as follows:
Truth-value: the available informations are always limited; the ‘truth value’ only
exists theoretically, as it can only be approximated;
Realism: just do the best what you can in available infrastructure and conditions;
accept that it will never be perfect;
Transparency: document your work in open way, leaving nothing out;
Critical review: there are never problems, unless you look critically;
Communication: it is necessary and strongly recommended to use
standardised/unified language and practice across discipline and sectors.

The implementation of the metrology in chemical measurements, which is

nowadays strongly stressed in the ISO/IEC 17025:1999 leads to the points, which
always have to taken into consideration:
1. Choose a correct measurement procedure – look for validation and confirm that;
2. Described correctly the measurement procedure (measurement equation);
3. State reference to which results are traceable and demonstrate it;
4. Make an evaluation of the uncertainty of the results;
5. Choose suitable Certified Reference Materials (CRMs) or reference standards and
use them correctly.

3 TRACEABILITY IN CHEMICAL MEASUREMENTS

Good quality of analytical results is essential when important decisions have to be
made. It is well accepted that a key property of a reliable result is its traceability to
stated reference. The ability to compare results wherever they originate is an important
metrological principle. Traceability is the principal tool to test established comparability
of the results. This is achieved by linking the individual result of measurement to a
common, tabled reference or standard. Therefore the results can be compared through
their relation to that reference. This strategy of linking results to a reference is termed
‘traceability’. The International System of Units (SI) is at the top of the system.
According the VIM [12] definition (VIM, 6.10) “traceability is a property of the
result of a measurement or the value of a standard whereby it can be related to stated
reference, usually national or international standards, through an unbroken chain of
comparisons all having stated uncertainties”.
A measurement is a process, in the course of which the measurand is compared
to a standard. For practical measurements, usually a working standard, not a primary
standard is used. To state the uncertainty of the measurement results, the uncertainty of
the value assigned to the working standard must be known. In analytical chemistry,
traceability of measurement results to SI units is not always possible and the traceability
hierarchy ends below the level of the SI units. Even in the case of reference materials,
when the values are fixed by mutual agreement, the comparability of measurement
results is limited.

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TABLE 2.
Calibration hierarchy

Metrological Standards Institution Uncertainty

traceability
Primary std
International std. BIPM*)
National std. NMI**)
Reference std. Accredited Calib. Labs
Transfer std. Company
Travelling std. Calibration Centre
Working std. Test labs
*) Bureau International des Poids et Mesures
**) National Metrology Institutes

Traceability in chemistry is difficult because of the proper definition of the

measurand; matrix interferences; difference in composition and inhomogenity of the
samples; instability; complex sample treatment required; reliable results. Incorporating
traceability to the mole and uncertainty budgets into chemical analysis is more complex
than is their application to physical measurement. However the traceability to the same
stated reference is of essential importance for comparability of the results. Meaningful
comparison between measurements is only possible of the results is expressed in the
same units (measurement scale). Mostly used units belongs to the SI system (m, kg, s,
A, K, mol) and can be used separately or being their combination. But also traceability
can be perform to best internationally agreed reference scale (if no SI) such us:
• delta scale for isotopic measurements;
• pH scale;
• scale of octane numbers for petroleum fuel.
Several steps should be used in order to establish and demonstrate traceability in
chemical measurements. This can be undertake via: (i) specifying the measurand and
model equation; (ii) choosing the suitable measurement procedure; (iii) demonstration
through validation that the calculation and measurement conditions include all the
influence quantities that affect significantly the result; (iv) choosing reference standard;
(v) estimation uncertainty associated with the measurement.
To conclude it is clear that every link in the traceability chain must consist of
comparisons of an unknown value with a known value. In chemical measurements this
has to be done during the validation of the measurement procedure. The stated reference
might be a (SI) unit or a conventional reference scale (e.g. pH;delta scale for isotopic
measurements; the scale of octane numbers for petroleum fuel). A traceability chain
should be designed and then demonstrated with reliable uncertainty.
In practice, traceability in chemicalmeasurements is established either via a link to
values obtained by reference measurements or via link to values carried by reference
standards, which are themselves linked to values obtained by reference measurements.

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4 UNCERTAINTY OF MEASUREMENT RESULTS

Uncertainty is a metrological term, which is defined as follows: parameter, associated
with the result of a measurement that characterised the dispersion of the values that
could be reasonably is attributed to the measured.
Knowledge of the uncertainty of measurement results is fundamentally
important for laboratories, their clients and all institutions using these results for
comparative purposes. Competent laboratories known the performance of their testing
methods and the uncertainty associated with the results. The level of uncertainty that is
accepted has to be decided on the basis of fitness for purposes, the decision having been
reached in consultation with the client. Sometimes a large uncertainty may be
acceptable; sometimes a small uncertainty is required.
There are lots of mysteries about the uncertainty of results in the analytical
chemistry society. Also in most academic curricula of analytical chemistry, the random
and systematic error concept is still considered to be useful in order to evaluate the
quality of the measurement result. In most cases an uncertainty is considered to be a
very complicated (complex) approach. “It has to be done because it is required.” Indeed,
the uncertainty evaluation is required by the ISO 17025 but it is also a perfect and in
fact simply way to improve the knowledge about the measurement procedure used. The
analytical chemist should be convinced that evaluating uncertainty of the measurement
results yields an improvement of the quality of a measurement procedure. Repeating the
measurement 2, 10 or 100 times do not give all information to have reliable results!

Measurement results are reliable only if their uncertainty is known and quantified.

There are several reasons why the uncertainty become so important:

1. Firstly because it is required by ISO/IEC 17025:1999 and for accreditation;
2. The uncertainty of the result demonstrates the quality of the measurements;
3. It improve the knowledge about the measured
4. Inside laboratory the uncertainty can be used in order to document in transparent
way the measurement procedure;
5. For the end-user the uncertainty give the result with proper confidence;
6. The uncertainty allows the comparison of the results.

It is important to understand that a well-documented uncertainty statement underpins

the results and provides transparency of the applied procedure. This could be the best
defence in discussion, when the comparison of the results is required as well as when
the decision around the legal limits have to be made.
The proper evaluation of the measurement uncertainty of the result in routine
laboratories is getting more attention. It is generally accepted that the use of analytical
methods requires estimating the measurement uncertainty in order to compare the
results with the confidence requirement. Well-characterised uncertainties are also
fundamental to the implementation of traceability. The “Guide to the Expression of
Uncertainty in Measurement” (GUM) published by ISO [10] established general rules
for evaluation and expressing uncertainty for various kind of measurements. This
approaches requires the identification of all possible sources of uncertainty associated
with the applied procedure; the estimation of their magnitude either from experimental
or published data; finally the combination of all individuals to give standard and

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expanded uncertainties for the whole measurement procedure. It is commonly accepted

that uncertainty of measurement results evaluation according to the GUM is a useful
and acceptable concept to evaluate results of a measurement. It allows other (e.g.
assessors) to understand what and how things were done. It allows also the analyte to
combine prior knowledge and observation in a consistent and well-defined way and at
least but not lest it doesn’t requires measuring with smallest achievable uncertainty
It is also important to stress that according to GUM § 3.4.8. “…The evaluation
of uncertainty is neither a routine task nor a purely mathematical one; it depends on
detailed knowledge of the nature of the measured and of measurement…”.
Uncertainty arising from the repeatability of chemical measurement is a
characteristic of the method. Its calculation has similarities to the calculation of
uncertainty in physical measurement and many components are identical to those
involved in physical measurement, components such as uncertainty in mass and volume.
However, others such as purity of reference materials and recovery are rather unique to
chemistry, but once determined, can still be incorporated into the uncertainty budget
using the standard techniques developed for physical metrology and described in the
publication, GUM. The interpretation of this guide for analytical chemistry was done by
Eurachem in 1995 [8].
It is always important to know when should the evaluation of uncertainty be
perform:
When a procedure is introduced inside the laboratory;
When a critical factor changes in the procedure (instrument, operator..)
During or together with analytical procedure validation

This means that an individual evaluation process is not needed for every individual
result produced!!

The GUM approaches cover respective 10-steps, which leads to the proper evaluation of
the uncertainty:
1. Defined the measurand
2. Describe the model equation (for the measurement procedure)
3. Identify all possible sources of uncertainty;
Possible sources of uncertainty: recovery of analyte from a complex matrix; storage
conditions; reagent purity; assumed stoichiometry; measurement conditions; instrument
response; bias of instrument; instrument resolution; uncertainty of standards and
CRM’s; variation in repeated observation.
4. Estimate values for all input quantities using the type A and type B uncertainty;
Input quantities uncertainty (type A / B)
repeated observation (A)
validation (A and/or B)
manufacturers specification (B)
calibration certificates (B)
literature data (B)
5. Evaluate the standard uncertainty (1 standard deviation) of each input quantity;
Before combining, all uncertainty must be expressed/covered as “estimated” standard
uncertainty. When available as:
Standard deviation: use as is
Confidence intervals: convert
Stated range: convert
Expanded uncertainty: convert

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6. Calculate the value of the measurand (using the model equation);

7. Calculate the combined standard uncertainty of the result;
Assuming no correlation between input quantities the law of uncertainty propagation
can be used:
8. Calculate the expanded uncertainty (with a selected k);
The coverage factor usually used is k = 2, representing a coverage of about 95%, if the
distribution is normal. Expanded uncertainty give a more realistic range of possible
values.
9. Analyse the uncertainty contribution index
10. Document all steps in a Report

We expect that this module will convince that the uncertainty of measurement
results, evaluated according to the GUM, is a very useful approach since:
• it enables the analyst to combine prior knowledge and observations in a consistent
and well defined way;
• it does not require measuring with smallest achievable uncertainty, but rather is
focused on realistic evaluation of the analytical performance of the laboratory;
• Measurement procedure is a logical sequence of various steps done in a certain time
and space; according to the law of uncertainty propagation, only input quantities
contribute to the uncertainty result. Reproducibility should be considered as a part of
the total uncertainty.

5 BASIC STATISTIC FOR UNCERTAINTY EVALUATION

The analytical results provided by the laboratory is always based on the statistical
evaluation of the raw data. This covers mainly average of the set of data and standard
deviation. In fact what is needed to apply the GUM uncertainty, is based also on some
basic statistics. The important aspect of making the uncertainty budget is to use the law
of propagation, the tool which enable to combine the uncertainty of type A and type B
in a consist way. At last but not least the understanding of distribution patterns of the set
of data is required for uncertainty evaluation. It is important to be aware that different
kind of distribution (normal, rectangular or triangular) occurs and this influences the
conversion of the input quantities of type B (previous experiments, literature data,
manufactures information etc.) in a form of standard uncertainty.

Examples of distributions

I. Normal distribution is used when an estimate is made from repeated observation of

a randomly varying process.

An uncertainty is then given in a form of a standard deviation s, a relative standard

deviation s/xmean or a coefficient of variance CV%. An uncertainty is given in the form
of a 95% (or other) confidence interval.
U(x) = c / 2 for c at 95%
U(x) = c / 3 for c at 99.7%

II. Rectangular distribution is used when the informations are taken from a certificate
or other specification, which gives limits without specifying a level of confidence e.g.
Concentration of the calibration standard is quoted as 1000 ± 2 (mg/l)
The purity of the cadmium is given on the certificate as 99.99 ± 0.01 (%)

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2 a (= ± a)

The value is between the limits: [- a ….+ a ]. An estimate is made in the form of a
maximum range (± a) whit no knowledge of the shape of the distribution.

Assumed standard uncertainty is according to the equation:

s = u ( x) = a / 3

III. Triangular distribution is used when the available information concerning x is less
limited that for a rectangular distribution. Values close to the mean value x are more
likely than near to the extremes.

2 a (= ± a)

The manufacture quoted volume for the flask of 100 ± 0.1 (ml) at t = 20 oC. A
nominal value is most probable.

An estimate is made in the form of a maximum range (± a) described by a symmetric

distribution.

s = u ( x) = a / 6

6 VALIDATION OF A MEASUREMENT PROCEDURE

Validation of a measurement procedure can be regarded as one of the most important
part of the every day laboratory work. When choosing the most promising candidate
method for intended use, one should consider the experience of own laboratory, as well
as equipment ready to be applying, the time and cost involved in particular
measurements. Validation of the measurement procedure increases confidence for users
of the measurement procedure and measurement results, and provides information on
expected procedure performance characteristics.

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According to ISO/IEC 17025 validation is the confirmation by the examination

and provision of objective evidence that the particular requirements for a specific
intended use are fulfilled. Among much objective evidence expected, performance
characteristics of the measurement procedure are the most important. Performance
characteristics of the measurement procedure, e.g. working range, linearity (of the
procedure), sensitivity, detection limit, belong to one group of the validation
parameters. The second group of the validation parameters comprises the property of
the results obtained with this procedure, like traceability and uncertainty of the
measurement result.

TABLE 3.
Validation checklist

Performance parameters of a procedure (quantitative)

- working range;
- detection / determination limits;
- sensitivity
Properties of the results obtained with a validated procedure

- traceability

- uncertainty recovery;
robustness;
selectivity;
specificity;
repeatability;
reproducibility

It should be pointed out that in various documents different terminology for the
validation is used. For example ISO/IEC 17025 uses ‘method validation’; VIM uses
‘procedure validation’; and GLP uses ‘standard operation procedure’.
Besides the wording being use in all cases validation is consider as a study of the
procedure, not of the analyst or of the laboratory performance. Validation provides
information on the procedure performance. The intended use of the validation is
Compliance with regulations;
Maintain quality and process control;
Support national and international trade;
Support research.
In all cases the validation includes:
Specification of requirements;
Determination of the procedure characteristic;
Checking whether the requirements can be fulfilled by the procedure
Statement that the chosen measurement procedure is valid for the intended use.
Which methods (procedures) should be validated?
Non-standard methods;
In-house developed methods;
Standard methods used outside their intended scope;
Modified standard methods.

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There are many validation techniques recommended by international standards,

regulatory bodies, and other authorities. For scientific laboratories the systematic
assessment of the quantities influencing the result is highly recommended. Some parts
of the whole uncertainty budget should be compared to the validation study: precision
of the input quantities, recovery of the measurement procedure (bias!), robustness of the
input quantities.

TABLE 4.
Validation techniques recommended

I Evaluation of uncertainty = systematic assessment of the quantities influencing

the result
II Using of CRM for calibration and for evaluation of the accuracy of the results

III Participation in inter-laboratory comparisons

IV Comparison of results with that obtained with other procedure

V Systematic assessment of the factors influencing the result

There is a very tight connection between the development of the measurement

procedure (input parameters optimisation) and validation of the measurement procedure
for intended use. In all cases it is important to cover the whole analytical procedure
within the whole range of its application. Therefore three "golden" rules should be
fulfilled: a) validate whole measurement procedure (from sampling to measured signal);
b) validate procedure for use in all intended matrices; c) validate procedure for use in
intended concentration range. The analyst should record the results obtained within the
validation and the final conclusion whether the applied procedure is fit for the intended
use.
The validation should be as extensive as it is necessary to meet the need of the
given application or field of application. In many cases all procedure need to be
validated but with different degree of validation!

Examples
1. Determination of cholesterol in serum
Limit of determination is not important, especially the uncertainty is important, so the
attention should be put on that.
2. Survey of environmental contamination (towards finding the hot spots)
LOD and uncertainty size is not important.
Range and linearity is important
3. Doping control against the limit
LOD is important, uncertainty is extremely important
Range and linearity are not important.

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7 ON THE USE OF CERTIFIED REFERENCE MATERIALS

Certified reference materials (CRMs) and reference materials (RMs) are widely used in
analytical chemistry. Their proper application provides the most direct information
about the quality of and confidence in the obtained measurement results. CRMs are
used for calibration of an apparatus; for the assessment of the measurement method; for
establishing traceability of the measurement results; for the determining the uncertainty
of these results.
According to VIM the definitions are as follows:
Reference Material: “material or substance one or more of whose properties are
sufficiently homogeneous and well established to be used for the calibration of an
apparatus, the assessment of the measurement method, or for assigning values to
materials”
Matrix Reference Material: “a ‘natural’ substance more representative of laboratory
samples that has been chemically characterised for one or more elements, constituents
etc., with a known uncertainty”
Certified Reference Material: “reference material, accompanied by a certificate, one
or more of whose properties values are certified by a procedure which established
traceability to an accurate realisation of the unit in which the property values are
expressed, and for which each certified values is accompanied by an uncertainty at a
stated level of confidence.”

Certified reference materials (CRMs) are generally recognised as an excellent

means to check analytical accuracy. Users of these CRMs can compare their analytical
results for those materials with the certified value taking into consideration both the
uncertainty of the CRN and the uncertainty of the measurement. Therefore, reliable
estimates for CRM uncertainty are necessary.

Types of the CRM according to their use:

Pure substances for calibration (e.g. solution of Cd to prepare calibration solution
for AAS measurements)
Pure substance for matrix matching (e.g. high purity Cu to make a Zn/Cu calibration
series for ICP-OES)
Matrix CRMs (e.g. cholesterol in serum)

When looking for the quality of chemical measurement results today it is clear
that still the same “traditional” simple concepts exist in the analytical chemistry society.
In many cases it is still assumed that if one uses a quality management system, written
standards or certified reference materials (CRM), one automatically gets better quality
results? There is considerable evidence that this is not the case and that the selection of
appropriate CRMs by the user with respect to sample matrix, concentration range and
uncertainty of certified properties is essential.
The production of RM and CRM is not a trivial task and it should be perform
according to the ISO 35 document, where the integrated process of correct preparation,
homogeneity and stability demonstration, and accurate and traceable characterisation of
the material is described. For the high quality of RM or CRM the traceability and
uncertainty of certified value should be state and demonstrate. The selection of the
appropriate CRM’s by the user should be done with respect to sample matrix,
concentration range and uncertainty of the certified properties.

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Information and catalogues can be available via web:

IRMM www.irmm.jrc.be
BAM www.bam.de (also COMAR dbase)
NIST www.nist.gov
LGC www.lgc.co.uk
REFMAT www.refmat.org.pl

8 INTERLABORATORY COMPARISONS
The results from Interlaboratory Comparisons (ILC’s) are of crucial interest for a
laboratory as these provide clear information of its ability to demonstrate reliable results
to its customers. Participating to ILC enable to demonstrate ability to measure and in
case it is necessary should lead to improve the quality of results. Laboratories either
participate voluntarily or are forced by external requirements (e.g. legal, accreditation,
control bodies). In case of unsatisfactory performance, the result from participating to
the ILC either indicates that there was an unaccounted bias in the result or/and that the
uncertainty was underestimated. Therefore, participation to an ILC can help to make a
decision of the necessary action perform bias correction or/and reassess the magnitude
of the uncertainty estimates.
Most ILC’s schemes involved comparison of participant results with an assigned
value, which has been derived from a reference laboratory, a sub-group of participants,
consensus from the overall population of test results or by some other means. The
advantages and disadvantages in the use of consensus values and reference values have
been discussed recently by Van der Veen et all [13].
The organiser of ILC’s should preferably provide an expert commentary on
overall laboratory measurement performance against prior expectation or prior
requirement, taking uncertainty into account. If the laboratory reports the measurement
results with the corresponding uncertainty (which should always be done for ILC’s), its
performance can be evaluated based on both the reported numerical values and its
uncertainty. The organiser of ILC shall assign a value with an appropriately small
measurement uncertainty, while a participating laboratory can measure the same with
greater “fit-for-purpose” uncertainty, often customer and/or cost driven.
It is expected that each laboratory taking part in the interlaboratory certification
studies should return a GUM compliant uncertainty budget along with its results for the
measurand. In order to do this effectively participating laboratory must use well-
characterised methods, which they are familiar with.

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 Chapter 4

COMMON LANGUAGE

Terms Definition
Accuracy of Closeness of the agreement between the result of a
measurement measurement and a true value of measurand
Calibration Set of operation that establish, under specified conditions,
the relationship between values of quantities indicted by a
measuring instrument or measuring system, or values
represented by a material measure or a reference
materials, and the corresponding values realised by
standards [VIM 6.11]
Measurand Particular quantity subjected to measurement [VIM 2.1]
Measurement Set of operations having the object of determining a value
of a quantity [VIM 2.1]
Method of Logical sequence of operations, described generically,
measurement used in the performance of measurements [VIM 2.4]
Measurement procedure Set of operations, described specifically, used in the
performance of particular measurements according to a
given methods [VIM 2.5}
Model equation The equation used to calculate the result of a
measurement
Quantity Attribute of a phenomenon, body or substance that may be
distinguished quantitatively and determined quantitatively
[VIM 1.1]
Result of a Value attributed to a measurand, obtained by measurement
measurement [VIM 3.1]
Value (of a quantity) Magnitude of a particular quantity generally express as a
unit of measurement multiplied by a number [VIM 1.18]

EXAMPLES

Quality Analyte Measurand Unit Stated

reference
Concentration DDT Concentration ng/l SI
of DDT
Content Cd Content of Pb ng/kg SI
Activity Amylase Activity of Katal SI
amylase
pH H+ Concentration pH unit pH scale
(activity) of H+
Octane index Octane number Octane number
scale

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 Chapter 4

9 CONCLUSIONS
As the importance of the results of chemical measurements increased in various field of
public activity, a reliability of those results can be achieved only by tracing the results
back to a standard realising the unit in which the measurement result is expressed.
Therefore, analytical chemist should also use metrological way of thinking and terms
like traceability and uncertainty of the measurement results. The uncertainty can be
stated only if the traceability of the measurement result to a system of units is
guaranteed.

REFERENCES
[1]. Dube G., Accred Qual Assur, 6, 3 (2001)
[2]. De Bievre P., Fresenius J Anal Chem, 366, 1 (2000)
[3.] King B., Accred Qual Assur, 6, 236 (2001)
[4.] De Bievre P., and Taylor P.D.P, Fresenius J Anal Chem, 368, 567 (2000)
[5.] Bulska E., Taylor P., Anal. and Bioanal. Chem., in print (2003)
[6.] ISO/IEC 17025 (1999) General requirements for the competence of testing and
calibration laboratories, ISO, Geneva
[7.] Majcen N., Bulska E., Leiti I., Vassileva E., Papadakis I., Taylor P., Accred. Qual.
Assur., 7, 419 (2002)
[8.] Taylor P., Bulska E., Vassileva E., Majcen N., Suchanek M., Accred. Qual. Assur.,
in print (2003)
[9.] Bulska E., Lipinski J., Papadakis I., De Bievre P., Taylor P., Meterology in
Chemistry: Status report of Poland, EUR 19915 EN (2001)
[10.] ISO (1995) Guide to the Expression of Uncertainty in Measurement, ISO, Geneva
[11.] Quantifying Uncertainty in Analytical Measurements, EURACHEM (1995)
[12.] International Vocabulary of Basic and General Terms in Metrology, ISO (1993),
Geneva
[13]. Van der Veen A.M.H., Horvat M., Milacic R., Bucar T., Repinc U., Scancar J.,
and Jacimovic R., Accred Qual Assur, 6, 264 (2001)

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