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Accred Qual Assur (2010) 15:255–262
DOI 10.1007/s00769-010-0644-2
DISCUSSION FORUM
An approach for more precise statements of metrological
traceability on reference material certificates
R. Koeber • T. P. J. Linsinger • H. Emons
Received: 22 September 2009 / Accepted: 25 January 2010 / Published online: 17 February 2010

Springer-Verlag 2010
Abstract Metrological traceability of measurement results
is a key requirement for the comparability of such data in
time and space and with legal or product specifications.
Similarly, traceability of the certified values of a certified
reference material (CRM) is a prerequisite for their useful-
ness. Consequently, a statement on metrological traceability
of the certified value of the specified property is a require-
ment of the ISO Guide series on Reference Materials. The
establishment of the traceability of a value assigned to a
property of a reference material to a stated reference is piv-
otal to the use of the material. Metrological traceability is
related to a combination of four attributes that are assigned to
a clearly identified sample: description of the property,
description of the quantity/kind of quantity, a number with its
corresponding uncertainty and the measurement unit. The
first two items define the identity of the measurand, whereas
the latter two describe the value that is assigned to this
measurand. Therefore, the concept of traceability rests on
two anchor points, namely identity and quantity value. The
identity of a measurand can be defined by its structure alone
or by an operational/procedural definition, the quantity value
of the measurand can refer to the SI, or to an artefact, if
standards of arbitrary values have been used for the cali-
bration of equipment (e.g. WHO standards; international
units). The presented approach splits traceability statements
Presented at BERM-12, July 2009, Oxford, UK.
Papers published in this section do not necessarily reflect the opinion
of the Editors, the Editorial Board and the Publisher.
R. Koeber (&)
T. P. J. Linsinger
H. Emons
Institute for Reference Materials and Measurements (IRMM),
Joint Research Centre, European Commission,
Retieseweg 111, 2440 Geel, Belgium
e-mail: robert.koeber@ec.europa.eu
for CRMs into a description of the identity of the measurand
and the quantity value and provides a solution to overcome
the conflict as to whether a measurement result should be
declared as traceable to the SI or traceable to a method.
Keywords Metrological traceability
Certified
reference materials
Quantity value
Identity

Traceability statement
Measurand
Introduction
Metrological traceability and measurement uncertainty are
the two key concepts of metrology. The two concepts are
interlinked, as demonstrated by the definition of ‘‘metro-
logical traceability’’ as ‘‘property of a measurement result
whereby the result can be related to a reference through a
documented unbroken chain of calibrations, each contrib-
uting to the measurement uncertainty’’ [1]. This definition
clearly shows that only results with an appropriate uncer-
tainty statement can be traceable.
The concept of calibration directly leads to calibrants,
which must fulfil all requirements of certified reference
materials (CRMs), namely to have property values charac-
terised by a metrologically valid procedure [2] and such
calibrants can then be used to characterise secondary cali-
brants, leading to a calibration hierarchy. Whenever
possible, the property values of the CRMs shall be traceable
to an external reference. Although it is actually possible to
have ‘‘primary standards’’ defining a unit, this approach
causes problems whenever a batch representing this primary
standard is exhausted and needs to be replaced or whenever
stability of the current batch needs to be confirmed.
Usually, traceability is discussed in the context of
measurement results, with relevant documentary standards
123
256
[3] and guidelines [4] providing on how to establish
traceability for them. These documents emphasise the role
of calibration standards to achieve comparability of mea-
surements. The fact that about half of the interlaboratory
comparisons amongst metrology institutes (Key Compari-
sons under the CIPM Mutual Recognition Arrangement) do
not give consistent data [5] shows how challenging this
task is in practice. While in theory one single, traceable
measurement result would be sufficient to establish a
property value for a CRM, virtually all CRM producers feel
that the significantly higher impact of CRMs when com-
pared with single measurement results warrants additional
efforts. This means that CRM producers try to find evi-
dence for the absence of bias rather than being complacent
with the absence of evidence for a bias. Several approaches
for material characterisation with consequences for the
traceability of the assigned values have been described for
various types of CRMs.
Materials characterised by reference methods
This approach is conceptually simple. A reference method
exists that is internationally agreed and delivers results of
accepted quality. Measurements are performed using this
method and the traceability of the assigned value is the
same as the one of the measurement results. In principle,
two situations exist:
Measurands of rational methods [4] for which the ref-
erence method simply delivers results of a higher quality
but is not the only method available: this situation is typ-
ically encountered in the case of metrologically high-order
(or sometimes ‘‘primary’’) methods of measurement. As
other methods usually have higher measurement uncer-
tainties, nothing is gained by combining these results with
those from so-called primary methods (however, examples
have been reported where primary methods of measure-
ment give results with higher uncertainties than of routine
instrumental methods [6]). Nevertheless, IRMM requires
that also results from ‘‘primary methods’’ are confirmed by
independent methods to rule out the possibility of gross
errors. Conceptually, this approach using ‘‘reference
methods’’ also applies to materials prepared by gravimetric
weighing.
However, the concept of reference methods is of an even
higher importance for method-defined measurands. In this
case, the respective community (e.g. the International
Federation of Clinical Chemistry and Laboratory Medicine
(IFCC), or AOAC International) has agreed on a harmo-
nised method for a certain measurand (e.g. enzymatic
activity). This measurement procedure defines the measu-
rand and is hence at the top of the traceability chain.
Consequently, the ISO standard on metrological trace-
ability of results assigned to calibrators and control
123
Accred Qual Assur (2010) 15:255–262
materials for in vitro diagnostic devices [7] uses a hierar-
chical concept, where a value is assigned to a primary
calibrator using a primary reference procedure. Subsequent
secondary calibrators are then produced, whose values are
assigned by comparison with the primary calibrator.
Pure materials
‘‘Primary reference materials’’ are often misleadingly
understood to be substances with a very high purity.
Assignment of traceable purity values is conceptually
simple: all impurities need to be quantified and the purity is
obtained as 100% minus the sum of impurities. The
applicability of this approach has been demonstrated with
considerable efforts for some pure metals, where the
number of impurities is limited. For organic substances, the
potential number of impurities is virtually infinite. The use
of various methods and knowledge of the synthetic path-
way has been proposed to avoid overlooking major
impurities [8]. Still, the problem of different analytical
responses of the often unknown impurities exists. The ICH
guidelines on impurities in drug substances, therefore,
require identification, synthesis and calibration of all
impurities present above 0.1–1% (peak area percentage,
depending on the daily dose) [9]. Apart from these exam-
ples, there might be cases where even traces of impurities
would have to be assessed as they could show adverse
effects (e.g. inhibition).
Materials characterised by multiple methods
The certification of matrix materials for measurands of
rational methods (determining the total concentration of the
analyte in the test sample) poses a particular problem.
Strictly speaking, when a sample preparation step with a
phase transfer is involved, this sample preparation step
breaks the chain of direct comparisons/calibrations.
Because of the number of potentially unexpected effects
(rationalised as ‘‘matrix effects’’ or ‘‘interferences’’), it has
in fact become common practice to require that certified
values are determined from a combination of at least two
independent methods [10, 11]. Although it is recognised
that this concept does not provide traceability in a rigorous
way, it has, for the time being, been put forward as state of
the art [12].
Statement of the reference
Apart from the problems on how to establish traceability,
discussions arose on how to phrase the traceability state-
ment correctly. No disagreements existed for measurands
of rational methods, i.e. measurands which can be descri-
bed without reference to a specific method. Certified values
Accred Qual Assur (2010) 15:255–262
for these are either made traceable to the international
system of units (SI), to other systems of units or to an
artefact. In the latter case, assigned values are only
meaningful if they are themselves traceable to the (often
arbitrarily chosen) quantity value assigned to this artefact.
The discussion arose for method-defined properties, such
as impact toughness, dietary fibre or enzymatic activity.
The results for these measurands are only meaningful in
connection with a specific measurement procedure, but the
results are often expressed in SI units (J, kg, mol, s, etc.).
Clearly, results are only comparable if the measurement
procedure is strictly followed and if all input factors are
properly calibrated. Some CRM producers, amongst them
IRMM, therefore, emphasised the measurement procedure
by stating that the certified value is ‘‘traceable to method
XXX’’, whereas other CRM producers (e.g. BAM)
emphasised the calibration of input factors by stating
‘‘traceable to the SI’’. Arguments can be brought for both
approaches, not the least as the most recent edition of the
VIM explicitly foresees a measurement procedure as a
valid reference [1]. This led to the deplorable fact that not
even the traceability statements for similar measurands are
always comparable.
Despite the high importance which is now attributed to
and the problems with the establishment of traceability, the
issue has been touched only lightly in guidelines on CRM
production, which were developed several years ago. The
version of ISO Guide 34 from 2000 devoted only two
paragraphs on traceability and included a more extended
discussion on the subject in an informative annex. The
situation improved with the new version of ISO Guide 34
[13] giving a clear traceability requirements for the various
studies (homogeneity, stability, characterisation) during
CRM production. ISO Guide 35 expands on the issue, but
does not establish harmonised, internationally agreed rules
and requirements for establishing traceability [2].
ILAC Guide 12 [14] is a little bit more specific by
suggesting the use of other CRMs in the characterisation
exercise. This approach is different from the hierarchical
traceability chain, as the other (matrix) CRMs generally
only serve to demonstrate the traceability of measurement
results, but is not used to calibrate the measurement results.
Obviously, despite the generally acknowledged impor-
tance of the traceability of assigned values and the
difficulties encountered in demonstrating it, there are at
present neither clear rules available on how to establish
traceability in practice nor on how to report it.
In this paper, we propose an approach that can overcome
the conflict as to whether a measurement result should be
declared as traceable to the SI or traceable to a method. In
our opinion, this approach is able to give more precise
traceability statements on certificates of CRMs, resulting in
an added value for the user of such a material. This concept
257
is based on the traceability policy from ERM [15], but it is
explained from the perspective and with examples of
IRMM. When considering the range of approaches and
opinions published in the literature so far, we are aware
that there are different views from different angles on this
issue. However, in our opinion, the approach presented
here can overcome some of the problems that are associ-
ated with traceability statements for CRMs.’’
Traceability of chemical measurement results
The establishment of metrological traceability is usually
straightforward for many physical measurements. For
chemical measurements, the situation is usually more
complex and establishment of traceability statements is
confronted with many obstacles. In the field of chemical
analysis, the nature of analytes can range from elements
over small organic molecules to highly complex biological
macromolecules. Analytical methods are often challenged
to provide more information about specificity and have to
come up with information about the state in which the
analyte is present, e.g. by speciation of inorganic analytes,
discrimination between different isomers of organic mol-
ecules or isoforms of proteins.
Typical matrices can range from aqueous samples at the
one end to highly complex environmental or biological
samples, such as sediments, sewage sludge, whole blood or
tissue samples. As a consequence, the number of potential
interactions between the analyte and the matrix is huge.
This complex situation is not always evident to analysts
when the metrological correct term measurand is used. The
situation becomes even more demanding when the type of
analytical method comes into play. In chemical measure-
ments, various methods may exist that claim to cover the
same type of matrices and analytes. However, it is often not
clear whether different analytical methods determine really
the same measurand, which can depend on the combination
of matrix, analyte, and method. For example, is the sample
preparation able to disrupt all interactions between the
analyte molecule and the surrounding matrix or is only the
easily removable analyte fraction extracted and a remain-
ing residue still strongly bound to the sample? Analytical
laboratories might not be too concerned by this issue and
comparability between laboratories could be achieved
using the same (standard) method, but this point is actually
a crucial one for producers of reference materials.
CRM producers do not only provide a material, they
also have to provide certificates that state measurement
uncertainties and the traceability to a reference [16]. The
target uncertainty and the traceability of the certified
property value should be the subject of a proper planning of
a CRM project design [13]. In this context, it is not only in
123
258 Accred Qual Assur (2010) 15:255–262

the economic interest of the producer to develop a refer- Table 1 Example of certified values of a CRM (mass fraction of
ence material that is actually useful for a potential dietary fibre in dried apple; ERM-BC516) where the measurand and
customer. If the traceability of a CRM value is not the certified values depend on the method that was applied for the
determination
appropriate for a potential user, the material will not be
sold and used and hence the resources spent on such a Dietary fibre according to Certified Uncertainty
value (g/kg) (g/kg)
CRM would have been wasted and could have been better
used for other, more useful materials. There could be an AOAC 1990 985.29 [17] 164 4
even worse situation from the analyst’s point of view. If the Englyst (by GC) [18] 137 5
traceability statement of a CRM value would be incorrect, Uppsala 994.13 [19] 162 8
imprecise or misinterpreted, the use of the material could AOAC 1992 MES-TRIS 991.43 [20] 149 10
not be justified for a specific analytical problem and the Englyst (by colorimetry) [18] 134 5
conclusions that are drawn from the analysis of this CRM
could be wrong and lead to the laboratory astray. There-
standards are available whose units are chosen on an
fore, CRM producers should not only provide correct
arbitrary basis. Examples are the international units (IU) as
traceability statements, but formulate them also in such a
defined by the WHO for the measurement of vitamins,
way that the customer can judge if it fulfils the require-
hormones, vaccines and blood products. This concept is
ments for the purpose in question.
based on ‘biological equivalents’ where a conversion to the
Sometimes, there is a misconception that traceability
mass unit may sometimes be established.
can only be established to the SI. However, the ISO Guide
As already mentioned in the introduction, there can be
99 (VIM) explicitly defines two other possible anchor
cases for which there are different opinions on how to
points for linking traceability [1]. Apart from the preferred
express the traceability statement on CRM certificates.
link to the SI, traceability can be established using a
There is sometimes the perception that values obtained
measurement procedure (including the measurement unit
with ‘‘empirical’’ methods (i.e. for procedure-defined
for a non-ordinal quantity) or a measurement standard (i.e.
measurands) cannot be traceable to the SI. In the following
CRM) [1]. Although the use of the SI as the reference is
chapter, an approach is described that allows CRM pro-
commonly preferred, there are cases in chemical mea-
ducers to provide traceability statements on CRM
surements where this is not relevant.
certificates in a more concise manner.
For example, it might be metrologically ideal to express
the catalytic activity of an enzyme as a mass concentration
thus linking it directly to the SI unit ‘‘kilogram’’. In prac-
Splitting the traceability statement into two parts
tice, however, the mass of a protein has nothing to do with
its functional property, the biological activity. There is no
The certified (property) value is attributed to a quantity
proportionality between the mass of the protein and its
representing a property of the CRM [1]. Following the
primary, secondary and tertiary structure and the number of
terminology of ISO Guide 99, a ‘quantity’ is ‘‘a property of
relevant binding sites. The measurand in question needs a
a phenomenon/body/substance, to which a number can be
link to a specific method with specified parameters that
assigned with respect to a reference. This reference can be
serves as the reference here. This implies also that mea-
a measurement unit, a measurement procedure or a refer-
surement results which were obtained with different
ence material’’. Consequently, a quantity (e.g. amount-of-
methods can result in different quantity values for the
substance concentration of creatinium in a blood plasma
sample in question. If this is the case for certified values of
sample) would be the combination of the identification/
a CRM, the procedures that lead to the values in question
description of the property (creatinium) of a body/item
have to be specified. An example is given in Table 1.
(blood plasma) and the ‘base (or derived) quantity’
The CRM certificate specifies different certified values,
(amount-of-substance concentration). The IUPAC Provi-
all of them depending on the respective procedure that was
sional Recommendations on ‘‘Metrological Traceability of
used. The measurand ‘dietary fibre’, being the indigestible
Measurement Results in Chemistry’’ [22] describe this
portion of plant foods, depends on the definition by the
combination in the form of a sequence.
method. It is a sum parameter that comprises non-starch
polysaccharides, such as cellulose and many other plant System ) Component=analyte
ðblood plasmaÞ ðcreatiniumÞ
components, such as dextrins, inulin, lignin, waxes, chitins,
) Kind of quantity
pectins, beta-glucans and oligosaccharides [21]. The ðamount-of -substance concentrationÞ
measurand in this case covers a series of chemical structures.
The need to link traceability to an artefact is common in According to ISO Guide 99, the ‘measurement result’ is
fields such as clinical chemistry where measurement defined as ‘‘quantity value(s) being attributed to a

123
Accred Qual Assur (2010) 15:255–262
measurand’’ (with ‘measurand’ as the ‘‘quantity intended to
be measured’’). A certified value on a CRM certificate
belongs to a specified quantity and is the combination of a
number (with its uncertainty) and the measurement unit.
What has to be kept in mind is that traceability chains consist
of values, but how is it then possible to specify that a
particular value is based on a method-dependent procedure?
We can reduce all the components that define a measurement
result to the identity of the measurand and the respective
quantity value. For many chemical measurements, the
identity of the measurand is defined via the analyte,
typically a specific atom, ion, molecule or parts of the
latter. If its identity is additionally influenced by analyte–
matrix interactions which are not overcome by the
measurement procedure, a method-dependent measurand is
the consequence and such operationally defined identities or
measurands can also be the result of unspecific measurement
procedures where groups of atoms or molecules or other
entities cause the quantifiable signal. Exceptions exist in the
case of functional properties (see ‘‘How to transfer this
concept into practice’’). Note that only the ‘‘qualitative part
of the measurand’’, i.e. its identity is addressed here. The
quantitative part is covered and defined by the quantity value
which is described by the kind of quantity, a number and a
corresponding measurement unit.
The solution to the described problem of how to express
the traceability for CRM values is achieved by splitting the
traceability statement into two parts, namely the identity of
the measurand and the quantity value. By this, it is possible
to accurately describe if the identity of the measurand of a
reference material is defined by its structure alone or if it is
defined by a specific procedure. This is in the spirit of the
ISO Guide 99 (VIM), where in the definition of CRMs in
note 3 of clause 5.14 it is stated that ‘‘traceability covers
both ‘metrological traceability of a quantity value’ and
‘traceability of a nominal property value [1]’’. Further-
more, the traceability of the quantity value can be
expressed by linking it to the relevant reference in ques-
tion, i.e. to the SI or to another reference. Through this
concept, it is possible to allow that the certified properties
of CRMs are method defined and that their values are made
traceable to the SI at the same time.
The identity of the measurand can be structurally
defined or procedurally defined (i.e. by a method or func-
tionality). If it is structurally defined, all the respective
ions/atoms/molecules in the sample can be considered as
being chemically in an equivalent state (which does not
mean that they are identical) and their determination does
not depend on the method applied for such a measurand.
For example, the determination of lead in sediment could
be based on a sample preparation that digests the sample
completely followed by a subsequent detection of the lead.
Given that no losses occur, the analysis is quantitative and
259
no further specification of the measurand is needed. If the
identity of the measurand depends on the method, e.g. in
case of the determination of lead in aqua regia extracts of
sediments according to ISO 11446 [23] where the sample is
not entirely digested, the identity of the measurand has to
be specified by citing the method. Otherwise, the mea-
surement results could not be repeated or a certified value
of a reference material could be misleading if other
methods were used. Other examples can be found, for
instance, in bioanalysis where it can be crucial to determine
an analyte in a specific binding state in pharmacology/
toxicology. The measured in vivo concentration of a free
form of a substance and its potential conjugate or immo-
bilised form (e.g. through protein binding) could depend on
the method applied and the often abundant equilibria are
likely to be altered by the measurement procedures. Hence,
it is important to specify if the identity of the measurand is
method dependent or not.
There can be different reasons why a measurand is
defined by a specific method. For example, a procedure can
cover a group of analytes based on the composition and the
external interactions that these (often chemically similar)
substances share together. As a result, the measurand could
represent a sum parameter covering a range of different
chemical entities. A different case is encountered when
functional properties are addressed. Here, the measurand is
not defined by an explicit chemical structure, but depends
on the functional activity exhibited by the sample and such
measurands are, for instance, relevant for food or clinical
chemistry. One example is the previously mentioned case
of dietary fibre (Table 1). The measurand in question is the
pool of all chemical entities in the sample that show the
same behaviour under the analytical conditions applied
(extraction, gravimetry). In clinical chemistry, for instance,
enzymatic activity is a functional property that can com-
prise a mixture of different (although similar) molecules
that form part of a ‘‘family’’ and may even be totally or
partially unknown [24]. The quantitative result depends on
the functional assay that is used for the measurement. In
general, the quantity values depend on all these cases on
the experimental conditions under which the measurements
were performed.
The traceability of the quantity value can be based on
the link to the SI or to an artefact (or ‘measurement stan-
dard’ as defined in [1]) as laid down in ISO Guide 99. In
both cases, it is important to establish an appropriate cal-
ibration hierarchy using well-characterised calibrators.
When traceability is established to an artefact, it has to be
ensured that the whole calibration hierarchy is also based
on the artefact in question and such cases are common in
the health sector. An example for using arbitrary units is
the system based on IU as defined by the WHO Expert
Committee on Biological Standardization (ECBS). The
123
260
precise definition of one IU differs from substance to
substance and is established by international agreement for
each substance. It is a unit of measurement for the reactive
amount of a substance and is based on a measured bio-
logical activity or effect. Typical examples for which this
unit is used are vitamins, hormones, some medications,
vaccines, blood products, and similar biologically active
substances. The ECBS arbitrarily sets the number of IU
contained in a preparation, and specifies a procedure to
compare other preparations of that substance to the refer-
ence preparation. The goal in setting the standard is that
different preparations with the same biological effect will
be attributed to the same number of IU. For some sub-
stances, the equivalent mass of 1 IU is later established. If
that happens, the former IU definition for that substance is
officially abandoned, in favour of a newly established
mass. However, the unit count often remains in use,
because it is convenient for the scientific community.
Table 2 depicts some of the commonly used conversion
factors for some selected substances that are often referred
to the IU.
The traceability statement that is split into the identity of
the measurand and the quantity value can be expressed by
four possible combinations. In Table 3, an example for
each scenario is given. The case of total cadmium can be
regarded as the best-case scenario in which the measurand
is independent from a method and traceability of the
quantity value can be easily established to the SI with the
quantity expressed, e.g. as a mass fraction. The example of
dietary fibre was discussed in Table 1; although the
quantity value can be linked to the SI via spectrometric and
Table 2 International units, an example for a measurement standard
used as a reference point for metrological traceability
Substance Conversion
factor IU to lg
Vitamin A retinol 0.300
Vitamin B2 (riboflavin) 0.025
Vitamin C 50
Vitamin E (D-alpha tocopherol) 667
Androsterone 100
Insulin 45.45
Chlortetracycline 1.000
Doxycycline 1.149
Penicillium G sodium 0.598
Vancomycin 0.993
Only substances are given that can also be converted into mass
Note that the respective conversion factors change for every
substance
There are many other substances where no conversion is possible and
where the amount-of-substance concentration (‘potency’) expressed
in IU changes from material to material, depending on the biological
activity
123
Accred Qual Assur (2010) 15:255–262
Table 3 Examples for possible combinations of splitting the identity
of the measurand from the quantity value for stating traceability (for
details, see text)
Identity of the measurand
structurally operationally
defined defined
SI total cadmium dietary fibre
[kg/kg] [kg/kg]
Quantity
value artefact vitamin A coagulation time
(traceable to) [I.U.] [INR]
gravimetric approaches, the measurement result depends
on the definition of the method via the applied method. In
the case of vitamin A, a structurally well defined molecule,
references are often made to the IU although in this par-
ticular case a link to the SI is also possible via conversion
factors. However, despite this fact the use of IUs is still
widespread in clinical chemistry even though it is not
recommended from a strict metrological point of view. For
the coagulation time, an important parameter in clinical
chemistry, the available methods often differ in their ana-
lytical set-up, such as their reagents and standards, and
significant differences between routine methods were
reported [25]. As a measurement unit, the international
normalised ratio (INR) is used and is not expressed in SI
units, but is based on the coagulation time of a patient
sample in comparison with a ‘healthy control sample pool’
[26].
How to transfer this concept into practice
For the characterisation of CRMs, some specific points
have to be accounted. The selectivity of the methods used
is crucial, particularly when structurally defined measu-
rands are concerned. It is important to use the same method
for operationally (procedurally) defined measurands; i.e.
for homogeneity, stability and characterisation studies.
Appropriate method validation that confirms the fitness for
purpose is mandatory in any case. As stated in ISO Guide
35 [2], reference materials can be certified by measure-
ments in a single laboratory (using so-called primary or
reference methods) or involving multiple laboratories.
Excepting cases where a method-specific approach
obtaining method-specific assessed property values using a
network of laboratories was chosen, the use of at least two
independent methods is recommended for the certification
of matrix CRMs to prove the absence of a bias caused by
matrix effects and/or interferences. Although this concept
is implemented in the assignment of property values, it
should also be taken into consideration for making trace-
ability statements. In the case of matrix CRMs, statements
Accred Qual Assur (2010) 15:255–262
‘‘traceable to the SI’’ should only be made if at least two
independent methods were used for the characterisation
[10, 11]. In the opinion of the IRMM, this principle is also
applicable for major steps of an analytical method. Proto-
cols often contain separate parts such as sample preparation
(extraction, clean-up), separation (e.g. by chromatography)
and detection (e.g. by a spectrometric technique). For each
of these steps, matrix interactions could interfere with the
process. If different laboratories or measurement proce-
dures in a characterisation study have common parts that
cannot be considered independent, the measurand cannot
be considered as entirely structurally defined; the respec-
tive common parts of the method must be considered as
procedurally defined as only limited information on the
method independence is available. In Table 4, a certificate
of a CRM is depicted to give an example on how this can
be translated into practice.
The certified value as the mathematical product of a
number and the measurement unit has to be derived via
properly calibrated measurement systems and it is this
calibration hierarchy that needs to be described. As this is
usually too much information to be inserted on the first page
of a CRM certificate (and possibly even on the certificate at
all), this description of the traceability hierarchy may be
abbreviated, for example, in a footnote accompanying the
term ‘‘certified value’’ on page 1 of the certificate. Although
not mandatory for an ERM CRM, the certification report is
the best place to deliver all information concerning cali-
bration hierarchies and metrological traceability. The
following principles for the traceability statements on ERM
CRM certificates are applied: for ‘‘structurally defined’’
measurands quantified in total, footnotes are only required
Table 4 Example how to express metrological traceability applying
the proposed split into the identity of the measurand and the quantity
value
Mass fraction
Certified valueb (lg/kg) Uncertaintyc (lg/kg)
Compound feeding stuff
Aflatoxin B1a 12.9 1.8
Aflatoxin B2a 0.68 0.10
Aflatoxin G1a 5.2 0.8
a limitations apply. In the mentioned example, the customer
As obtained, after extraction, by reversed-phase chromatography
with post-column bromination and subsequent quantification by
fluorescence detection
b
Unweighted mean value of the means of accepted sets of data and
each set being obtained in a different laboratory. The certified value
and its uncertainty are traceable to the international system of units
(SI)
c
The certified uncertainty is the expanded uncertainty estimated in
accordance with the guide to the expression of uncertainty in mea-
surement (GUM) with a coverage factor k = 2, corresponding to a
level of confidence of about 95%
261
for the certified value stating the statistical parameters
(e.g. unweighted mean of…) and stating the metrological
traceability of these values, typically as ‘‘It is traceable to
the International System of Units (SI)’’. As for all certified
values of CRMs, respective uncertainties have to be
provided that are explained in another footnote. For oper-
ationally/method-defined measurands no footnote is needed
to specify the matrix or the kind of quantity as this is
unambiguously stated in the heading. A footnote is required
stating the definition of the certified property, typically like
‘‘as defined by the procedure according to ISO 12345’’ or:
‘‘as obtained by Soxhlet extraction and subsequent quanti-
fication by GC–MS’’. The footnotes for the certified value
and the uncertainty are the same as for the structurally
defined measurand mentioned above.
In Table 4, an existing example of an ERM certificate
from IRMM is given. In the characterisation of the feeding
stuff material certified for the mass fraction of aflatoxins,
results from 7 to 8 different laboratories were accepted
after technical scrutiny. As all methods employed used
reversed-phase liquid chromatography methods with post-
column bromination and fluorescence detection, method
independence cannot be guaranteed. As at least four dif-
ferent extraction solvents and techniques were used,
independence to the extraction method is given. Therefore,
the aflatoxin mass fractions as stated are defined by the
employed reversed-phase liquid chromatography methods
with post-column bromination and fluorescence detection.
This is reflected in footnote a in Table 4. The certified
values for the mass fractions of aflatoxins are traceable via
the common, certified calibrants used. The certified values
of the calibrants are traceable to the SI, as stated on the
respective certificate, due to the gravimetric preparation
employed. Therefore, the mass fractions of aflatoxins in the
CRM are traceable to the SI. This is stated in footnote b in
Table 4. In any case, metrological traceability for all the
measurements to the stated reference must be established to
claim it for the certified value.
What is now the important information for the user of
such a CRM? The footnote of the certified value reveals the
final reference of the traceability chain. The footnote of
the certified property gives the information as to whether
the CRM can be used regardless of the user’s method or if
is informed that he is free to use the extraction method
of choice. For the rest of the analysis protocol, high-
performance liquid chromatography in the reverse phase
mode with subsequent post-column derivatization by bro-
mination and fluorescence detection must be used. If this
condition is not fulfilled, the certified value (including the
characteristics of traceability and measurement uncer-
tainty) does not apply and the CRM cannot be taken for the
intended use.
123
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Summary
The approach to split traceability statements of CRMs into
a description of the identity of the measurand and the
quantity value provides a solution to overcome the conflict
as to whether a measurement result should be declared as
traceable to the SI or traceable to a method. It allows
providers of CRMs to better describe their reference
materials and has thus an added value for (potential) users
of these CRMs.
Acknowledgments Ulrich Panne (BAM) and Steve Wood (LGC)
and their co-workers are acknowledged for the fruitful discussions
resulting in the new ERM traceability policy.
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