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STMU 2015
Eurachem/CITAC Guide
Setting and Using Target Uncertainty in
Chemical Measurement
First edition
Acknowledgements
This document has been produced by the Eurachem/CITAC Measurement Uncertainty and Traceability
Working Group with the composition shown below. The authors are grateful to those other individuals and
organisations who have contributed comments, advice and assistance.
The production of the Guide was in part supported by Fundao para a Cincia e a Tecnologia, PT.
Editors
Ricardo Bettencourt da Silva Centro de Qumica Estrutural da Universidade de Lisboa, PT
Alex Williams Working Group Chair, UK
CITAC Representatives
Alan Squirrell ILAC
Ilya Kuselman National Physical Laboratory of Israel
Eurolab Representatives
Manfred Golze BAM, Germany
Recommended citation
This publication should be cited* as: R. Bettencourt da Silva, A. Williams (Eds), Eurachem/CITAC Guide:
st
Setting and Using Target Uncertainty in Chemical Measurement, (1 ed. 2015). Available from
www.eurachem.org.
*Subject to journal requirements
Setting and Using Target Uncertainty in Chemical Measurement
English edition
Copyright 2015
Copyright in this document is held by the contributing authors. All enquiries regarding reproduction in any
medium, including translation, should be directed to the Eurachem secretariat.
Setting the Target Measurement Uncertainty Eurachem/CITAC Guide
Contents
Contents i
Foreword 1
1 Introduction 2
2 Scope 2
3 Terminology 3
10 Examples 19
10.1 Defined compliance interval 19
10.2 Defined measurement performance characteristics 19
10.3 Defined decision risk 19
10.4 Proficiency tests 20
10.5 Measurement reproducibility 20
10.6 Magnitude of studied trends 20
10.7 Information from a different scope 20
10.8 Variation of target uncertainty with the quantity value 21
Bibliography 23
Foreword
The Eurachem/CITAC Measurement uncertainty and traceability working group prepared this
document to complete a sequence of guidelines that aims at promoting the production of measurement
results traceable to an adequate reference and, reported with reliable and sufficiently low uncertainty
for the intended use of the measurement. These features are essential for the adequate interpretation of
the measurement result which is discussed in the Eurachem/CITAC guide, Use of uncertainty
information in compliance assessment.
This document discusses how to set a maximum admissible uncertainty, defined in the third edition of
the International Vocabulary of Metrology as the target uncertainty, to check whether measurement
quality quantified by the measurement uncertainty is fit for the intended purpose.
This guideline is applicable to analytical fields where the target uncertainty is not set by the regulator
or the client, or a minimum difference of the studied parameter in the same or different items must be
detected in R&D work. This guide discusses how to set the target uncertainty for process development
and for applied or fundamental research using information about the smallest difference or system
trend that must be distinguished in a reliable way.
This guideline can also be useful for authorities and stakeholders that feel the need to define or
upgrade criteria for measurements quality. The setting of target values for the so called conventional
performance characteristics (precision, trueness, etc.) can miss the control of important uncertainty
components included in sound uncertainty evaluations.
The Eurachem/CITAC working group believes this document fills a gap in the current list of guidance
for measurements in chemistry and can contribute to ensuring measurements play their role in the
management of socio-economic interests and in the technological and scientific developments of
society.
1 Introduction
All measurements are performed with a goal, According to the latest edition of the
ranging from the assessment of the International Vocabulary of Metrology [1],
compliance of a product with a specification the upper limit of the uncertainty decided
to the characterization of a new material. The on the basis of the intended use of
adequate fulfilment of this goal depends on measurement results is designated target
the fitness of measurement uncertainty [1-4] uncertainty.
for its intended use. For example, the
The decision on the fitness of a measurement
assessment of the compliance of a gold alloy
procedure for the intended use depends not
with a specification for gold content must be
only on the measurement uncertainty, but also
performed with a low uncertainty due to the
on other information, such as the analytical
price of this component. The measurement of
range and the uncorrected recovery in some
glucose in blood should be affected by an
fields, or the cost and duration of analysis.
uncertainty low enough to allow the reliable
detection of deviations from the glucose In some analytical fields, the specification
values for a population of healthy individuals. and/or the legislation define the target
The characterisation of a meteorite must be uncertainty required for compliance
performed with an uncertainty small enough assessment [6, 7]. However, important
to distinguish the composition from other measurements in many other fields are
minerals. Therefore in setting the performed without this parameter having been
measurement requirements, in addition to set. The fact that the uncertainty is reported
specifying performance characteristics such as with the measurement result does not
recovery, repeatability and bias it is also guarantee its fitness for the intended use.
necessary to set a target value for the
uncertainty [5].
2 Scope
This document provides guidance to analysts, affect the decision about the measurement's
regulators and other end-users of analytical fitness for the intended use. Section 8 covers
information on setting the target measurement how the uncertainty might be reduced if the
uncertainty. estimated uncertainty turns out to be larger
than the target value and section 9 describes
Section 4 gives the inputs that are available to
how to use the target uncertainty to guide
help set the target uncertainty.
measurement procedure validation by
Sections 5 covers the use of this information suggesting target values for specific
to set the target value. performance characteristics.
Section 6 covers how to set the target Section 10 presents examples of setting the
uncertainty for a range of quantity values target uncertainty using the different types of
when it is initially defined for just some information and algorithms presented in
quantity values. previous sections.
The estimated uncertainty can vary due to the Section 3 (Terminology) discusses the
variability of uncertainty component relevant aspects of terminology used in this
estimation and section 7 covers how the guide.
uncertainty of the uncertainty estimation can
3 Terminology
This document uses terminology presented in minimum permissible quantity value. The
the latest edition of the International term specification limit or simply limit
Vocabulary of Metrology (VIM) [1]. will be used for either one of these cases.
The VIM (see entry 2.6 [1]) defines target In this document, the generic term quantity
measurement uncertainty as measurement is preferred to some specific examples like
uncertainty specified as an upper limit and concentration, mass fraction, depletion rate,
decided on the basis of the intended use of pH, etc.
measurement results.
The interpretation and application of VIM
Measurements are frequently performed to concepts to measurements in chemistry is
check if the measurand value (see entry 2.3 discussed in a Eurachem guide [2].
[1]) is above or below a maximum or
Where there is a defined maximum and/or a that usually remain unchecked since they do
minimum limit for the measurand, typically in not show up in conventional performance
a legislation or technical specification, this characteristics.
document should be checked for guidance
When target values are not defined for the
about the acceptable magnitude of the
relevant performance characteristics, the
uncertainty (section 5.1.1). This information
target uncertainty may be determined from
can also be available in guidelines and reports
how measurement performance is assessed
on the assessment of the compliance with the
from results of proficiency tests (section
legislation or specification. The origin of such
5.2.1) if the performance score is estimated
references and links to above-mentioned
considering the intended use of the
legislation and technical specification should
measurement. The results of collaborative
be checked.
studies or other interlaboratory comparisons
The target uncertainty can be inferred from can be used to define the target uncertainty
the compliance interval, defined by a (section 5.2.2) if it is concluded that the
minimum and a maximum limit (section agreement between results is adequate for the
5.1.2), or from the quantity value, above or purpose of the analysis. In some cases, it may
below a single limit, beyond which there be worthwhile to determine the target
should be a low probability of an incorrect uncertainty from a study of the economic
compliance decision (section 5.1.4). benefits of controlling products or processes
with a more expensive measurement
In some fields, target values of measurement
procedure that has a lower uncertainty
performance characteristics, such as limit of
(section 5.3).
detection, precision and mean analyte
recovery, are defined. In those cases, if these If a trend in the composition of a system
performance characteristics reflect the most needs to be studied or differences in analysed
relevant random and systematic effects items must be distinguished, the minimum
affecting measurements, they can be change of the quantity value to be
converted into a target uncertainty (section discriminated can be used to define the target
5.1.3). This target uncertainty is an additional uncertainty (section 5.4).
requirement to the defined performance
In some cases, the target uncertainty may have
characteristics, which has the advantage of
to be derived from one defined for technically
summarising in one parameter requirements
similar, or related, decision problems (section
for all sources of uncertainty, including some
5.5).
This section details how to use different types 5.1.2 Defined compliance interval
of references or data outlined in section 4 to
set the target measurement uncertainty. The In some analytical fields, the specification
sequence of presented types of data progresses limit is defined without guidelines about the
from the ideal source of the target uncertainty quality of measurements performed to check
to those less likely to be harmonised. compliance with that level.
If a single minimum or maximum
5.1 Legislation or product specification limit is defined, at least, the
specification measurement quality close to this level should
Ideally, the target uncertainty is explicitly set be assessed.
in a reference document (section 5.1.1). On If a compliance interval for the quantity is
other occasions, this value is implicit from defined (i.e. a minimum and maximum limit),
target values of other performance measurement performance within and close to
characteristics (section 5.1.3) or from the this interval should be assessed.
specification limit (sections 5.1.2 and 5.1.4).
The target uncertainty for checking
5.1.1 Defined target uncertainty compliance with a single specification limit
(minimum or maximum) should be defined
The ideal case is where the legislation or a considering the criteria discussed in the
specification defines the target uncertainty. following sections.
Unfortunately this is rarely the case at present.
Current examples include: If a compliance interval is defined for the
measurand, such as the content of an active
Commission Regulation (EC) 333/2007 [6] substance in a medicine or pesticide in a
defines the target standard uncertainty formulation for crop protection, the analyst
(designated maximum standard can infer that the uncertainty should be small
measurement uncertainty) for the enough to distinguish quantities within this
determination of Pb, Cd, Hg, inorganic tin, interval. If the compliance interval is defined
3-MCPD and benzo(a)pyrene in by a maximum Qmax and a minimum Qmin
foodstuffs. Defined target uncertainty is a quantity, the target expanded uncertainty, Utg,
function of the limit of detection and the should typically be 8 times smaller than the
maximum specification limit, Qmax, interval range:
(designated concentration of interest in
the Regulation). Q max Q min
Directive 2008/50/EC on ambient air
U tg = (1)
8
quality and cleaner air for Europe [7]
defines the target relative expanded The factor 8 is selected since, in theory, this
uncertainty for measurements of relevant would allow the simultaneous accommodation
parameters. Target uncertainty is different of four non-overlapping measurement results
for fixed and indicative measurements. reported with expanded uncertainty,
Fixed measurements are performed in considered the minimum discrimination
zones where the risk of pollutants ability within this interval. A value larger or
exceeding limits is high. Indicative smaller than 8 gives rise to an uncertainty
measurements are performed to enable the estimate that seems to be too strict or too
assessment of the geographical distribution flexible for the typical purpose of a
of the pollutants. compliance interval.
Usually, the target uncertainty is set for
measurement results close to the specification
limit.
random effects, u ratg , is estimated as stg (that The target combined uncertainty, u ctg ,
is, u ratg =stg). reflecting the combination of the estimation of
precision and uncertainty on bias, calculated
The permissible mean error E
tg
, defined as using uncertainty propagation law is:
the maximum range between the mean of
replicate measured quantity values and the
uctg = (u ) + (u )
tg 2
ra
tg 2
sy
(5)
reference value observed from the analysis of
where uratg can be estimated from target values
reference materials during validation, can be
used to estimate the target standard for the LOD, LOQ, coefficient of variation or
uncertainty associated with the uncorrected range of replicate measurements, or any other
tg
bias, u sytg , as parameter describing the same effect. The usy
tg can be estimated from the permissible mean
( u sytg = E l ), where l depends on the error or an equivalent parameter.
tg
assumed distribution for E . This formula is The comparison of the target uncertainty with
applicable when bias is estimated from a large the uncertainty on the measurement result is
number of measurements of reference discussed in section 7.
materials (Table 1).
Table 1: Measurement performance characteristics for which defined target values can be used to
estimate the target uncertainty.
Measurement performance
characteristic Description
Limit of Detection (LOD) The Limit of Detection (LOD) can be estimated under repeatability or
intermediate precision conditions. For instrumental methods of analysis
requiring daily calibration of the instrumentation, LOD estimated under
repeatability conditions is only applicable to the daily run. The LOD
estimated from the precision of measurements from different
calibrations can be applicable to a longer time scale. At this quantity
level, the measurement relative standard deviation is 33 % or 30 %, if
the LOD is calculated by multiplying the measurement standard
deviation by 3 or 3.3, respectively [10]. Since precision is constant in a
narrow quantity range, the standard deviation of measurements at the
LOD can be used to estimate precision between zero value and the
Limit of Quantification (LOQ) (approximately 3 or 3.3 times larger than
LOD). Only rarely is the uncertainty from systematic effects important
for measurements close to LOD (i.e. between the zero and two times
the LOD: [0, 2LOD]).
The standard deviation utilised in LOD calculations is LOD/3 or
LOD/3.3 depending on the convention used for estimating LOD.
Therefore if a target LOD, LODtg, is defined, the target standard
deviation for precision, stg, under the precision conditions specified in
the estimation of LOD is:
LOD tg LOD tg
s tg = s tg = (2)
3 or 3 .3
depending on how LOD is calculated.
Limit of Quantification The calculation of the Limit of Quantification (LOQ) is similar to that
(LOQ) performed to estimate LOD, where the multiplying factor of the
standard deviation is 10 instead of 3 or 3.3. At this concentration level,
systematic effects can be relevant.
The standard deviation obtained under the same precision conditions as
those used in the estimation of the LOQ, is LOQ/10. Usually, the
estimated standard deviation can be applied between LOD and two to
five times LOQ.
Similarly to Eq.(2), if a target LOQ, LOQtg, is defined:
LOQ tg
s tg = (3)
10
where stg is the target precision under the conditions specified in the
definition of the LOQtg.
Range of replicate Whenever a target range for results from duplicate measurements is
measurements defined, the confidence level and precision conditions used should be
checked. If a confidence level is not stated, a value of 95 % should be
assumed. Since the repeatability or intermediate precision limits,
estimated for a confidence level of 95 %, are
2.8 times larger than the standard deviation of measurements under the
same precision conditions, the target range can be converted to a target
standard deviation by dividing it by 2.8.
If the target value of the range of results from more than duplicate
measurements is defined, multiplying factors used to estimate the
critical range from the precision estimation should be used to calculate
the precision from the defined target range [11].
Coefficient of variation If a target coefficient of variation is defined without specifying the
precision conditions used (typically repeatability or intermediate
precision conditions), it can be assumed that the more informative
intermediate precision is reported. Many references to measurement
performance characteristics do not use the terminology of the latest, or
even previous, VIM editions, requiring a careful check of the meaning
of the terms. In the past, the term reproducibility was used for the
concept designated as intermediate precision in the latest VIM edition.
According to the latest edition of the VIM [1], reproducibility refers to
the agreement of results, of the same measurand, obtained from
different laboratories using the same or different measurement
procedures.
Some documents define precision requirements as a target value for two
times the standard deviation of results estimated under defined
conditions [9].
The repeatability standard deviation only reflects random effects under
specific environmental and operational (i.e. for an analyst/equipment
combination) conditions, and the intermediate precision will not reflect
systematic effects, relevant in some measurements, such as the so called
laboratory or
method bias [12].
Maximum permissible Some references define the maximum permissible bias affecting
error measurements. More frequently, maximum and minimum permissible
relative signed errors are defined. Relative errors are usually expressed
via recoveries (i.e. the ratio between estimated and expected quantity
values).
In some analytical fields, permissible single and mean recoveries are
defined for different situations [13]. Permissible recoveries for a single
test are defined to check the quality of measurements for a batch of
samples controlled through the analysis of a single recovery test. The
permissible mean recovery is used, during measurement procedure
validation, to check if bias is acceptable. Permissible error ranges are
wider for single recovery tests than for mean recovery tests.
Since mean error is an estimation of measurement bias, it can be used to
quantify approximately bias uncertainty component. If a maximum
( EMax ) and a minimum ( EMin ) mean error are defined, above and below a
null or mean value, the standard uncertainty of an uncorrected bias can
be calculated by reducing the confidence level of the half error range (
(E Max E Min ) 2 ) by dividing it by an adequate factor dependent on the
selected distribution of the range. If a triangular or rectangular
distribution with 100 % confidence level is considered, the factor 3 or
6 should be used respectively. The triangular distribution is preferable
whenever the mean error is expected to be more probable in the middle
of the interval [E Min ; E Max ]. Equation 4 gives an estimation of the target
standard uncertainty of the bias, u sytg , on measurements not corrected for
mean error:
EMax EMin
u sytg = (4)
2 6
For example, when checking compliance C1) Measurement distribution: The values
attributable to the measurand Q, derived from
against a maximum limit, Qmax, where the
decision rule requires a high probability that a measured quantity value q, have an
the limit is exceeded before declaring non- approximately normal distribution.
compliance, the guard band is added to Qmax. C2) A maximum limit, Qmax, is defined.
This means that a measurement result as large
C3) Decision rule: The product is considered
as (Qmax + ku) will lead to a declaration of
not compliant if there is, at least, a high
compliance [15] and a target value for u has to
probability P1 that the value of Q exceeds
be chosen so that this is acceptable (Figure 1).
Qmax, i.e. if the measured quantity value, q,
If a quantity value, qmax, in the analysed item minus an adequate multiple of its standard
larger than Qmax is defined, above which an uncertainty, ku, is above Qmax
max
item should be correctly declared as non- (i.e. (q-ku)>Q ). The multiplying factor, k,
compliant with a probability larger than P1, it of the standard uncertainty, u, will be
can be used to define the target uncertainty. typically the one-tailed Students t, t1, for the
A specific scenario of controlling the risk of confidence level P1 and degrees of freedom of
accepting an item where the compliance u [15]. The quantity ku is the guard band for
the compliance assessment and a maximum
decision is taken from the measured quantity
of a laboratory sample, but no allowance is value of u has to be specified to keep the size
made for how representative the measured of the guard band to an acceptable level.
value is in relation to a sampling target, is C4) Decision risk: One way of setting a
discussed below. In most regulations, a maximum value of u implicitly is to set a limit
compliance decision is taken from the result on the maximum measured quantity value,
of a measurement on a laboratory sample qmax, that is acceptable for the sample to be
collected following a regulated procedure and, declared compliant, e.g. qmax = Qmax(1+x). In
therefore, sampling uncertainty or setting the value of x it must be borne in mind
that for a measured quantity value of For the European monitoring of pesticide
Qmax(1+x) there is a 50 % probability that the residues in foodstuffs, is 25 % of the
value of Q exceeds this and a probability of reference value XRef [13].
(1-P1) that it exceeds Qmax(1+2x).
5.2.2 Measurement reproducibility
In this case, utg is estimated by the following
equation: Whenever measurement reproducibility, sR, or
reproducibility limit, R (where R=2.83sR)
q max Q max [11], is available in the standard procedure or
u =
tg
(6) in the report of an interlaboratory comparison
t1 for a particular method, which has been
If a minimum limit, Qmin, is the defined accepted as fit for its intended purpose, then
condition, the decision rule is equivalent to C3 sR can be used in setting the target standard
for values smaller than Qmin (i.e. (q+ku)<Qmin), uncertainty for the specific quantity value.
and a maximum value of u is set implicitly in This experimental data can be converted to a
a similar way, then utg is estimated by Eq.(7): target performance value if the estimated sR is
considered fit for the assessment of the
Q min q min agreement of results from various laboratories
u tg = (7) (e.g. through the calculation of the
t1
reproducibility limit). If sR is obtained from a
where qmix is the minimum measured quantity collaborative study where the agreement
value that is acceptable for the sample to be between measured quantity values is
declared compliant. acceptable, sR can be readily used in setting
u ctg ( u ctg =sR). However, if sR is estimated from
5.2 Proficiency or agreement results of laboratories for which it is
evaluation criterion concluded that serious lack of agreement of
If reference documents of the specification results is observed, this interlaboratory
limit(s) for the measurand do not define information will not be adequate to define
measurement quality requirements, this u ctg .
information can be inferred from how
The conditions under which the reproducibly
measurements are assessed in proficiency
study was carried out should be examined to
tests (5.2.1), or from the dispersion of results
determine if other uncertainty sources need to
from different laboratories when it is adequate
to assess the agreement of such results (5.2.2). be considered to estimate u ctg . In some cases,
reproducibility is estimated for the last stages
5.2.1 Proficiency tests of the measurement process and an
In most analytical fields, performance in assessment of the uncertainty of relevant pre-
proficiency tests is evaluated by calculating analytical and/or early analytical steps should
z-scores, z, estimated from the ratio between be made.
the measurement error and an assigned For rational measurements1, where bias
standard deviation: attributed to the physical-chemical principles
xi X Ref
z= (8)
1
Rational measurements are measurements of
where xi is the value reported by the measurands (rational measurands) defined
laboratory, XRef is the reference value and is independently of the measurement procedure used.
In contrast, empirical or operationally defined
the standard deviation defined for this
measurements are measurements of measurands
assessment. When is set by the proficiency (empirical measurands) defined for a specific
test provider to examine whether the methods measurement procedure.
being studied are fit for their intended use it The determination of total gold in a sample of
can be used to define the target standard mining product is an example of a rational
uncertainty ( u ctg = ). In the analysis of measurement since different procedures can be
used to measure the same quantity. Different
drinking water for major components, a of sample preparation procedures can be performed
7.5-10 % of XRef is generally used [16, 17]. prior to the quantification stage.
In order for the difference to be significant at If some systematic effects that affect the
a 99 % confidence level: determination of xA and xB are known to be the
same, those should not be included in the
AB = x A x B > estimation of ud. For instance, if the
(11) determination of lead content in a soil before
> td (u A )2 + (u B )2 and after a treatment is performed in the same
where AB is the range of values and td is the laboratory and using the same calibration,
critical value of Students t for a confidence some systematic effects affecting xA and xB
level of 99 % and the degrees of freedom individually will not affect AB. In that case,
associated with ud. instead of combining estimated uA and uB,
using Eq.(10), it is preferable to assess the
If xA and xB are estimated with a high number function AB with all their shared and
of degrees of freedom, kd is approximately 3. independent variables (Example 4).
Assuming that uA and uB are equal (uA=uB=u) Numerical methods for combining uncertainty
since xA and xB are similar, the measurement components, such as the Kragten and Monte
results are not metrologically compatible, and Carlo methods [4] are particularly useful in
therefore can represent different quantity these complex situations.
values, if the following condition is valid:
AB > 3 2 u (12) Example 4:
If the same calibration is used to measure
Therefore, the target standard uncertainty, utg, spectrophotometrically the Chemical
required to distinguish a minimum range, min, Oxygen Demand (COD) of a wastewater
between xA and xB, is (min/(32)); i.e. u should before and after a specific treatment, and
be, at least, (32=4.2) times smaller than min both sample solutions are diluted to be
to distinguish this minimum range. measured in a similar concentration range,
If ud is expected to be associated with a low the bias associated with calibration cancels
number of degrees of freedom, kd must be in the estimated trend of the COD value.
adjusted accordingly.
If the target uncertainty is, or can be, defined These frequent trends [22-23] suggest that a
only for some quantity values and the target relative uncertainty set at a quantity
measurement performance must be checked value is feasible above that level, and a target
over an interval of quantity values, the uncertainty is applicable down to five times
expected variation of the uncertainty with the below this level (Example 8). In many cases,
quantity can be used, together with the value the target uncertainty can even be applicable
of utg defined for some specific quantities, to further below since uncertainty tends to
define utg for the whole interval. decrease with quantity reduction.
The uncertainty, U, tends to slightly increase
with the quantity, being approximately
Example 8:
constant over narrow quantity intervals. For
simplicity, in many cases, it can be assumed If target uncertainty is defined for the
that uncertainty is constant between five times quantity value Q, the same target
less (Q/5) and five times more (5Q) than a uncertainty can be used below Q, and the
quantity value Q (i.e. from Q/5 to 5Q) (Figure respective target relative uncertainty can be
2a). used above Q:
The defined target uncertainty can be used to Trueness tests involve the determination of
guide the validation of the measurement measurement error (i.e. measured quantity
procedure by suggesting target values for the value minus a reference quantity value).
various performance characteristics, Unlike trueness, error is a quantitative
determined prior to uncertainty evaluation, property. The error observed during
such as repeatability, intermediate precision, measurement linearity evaluation or during
limit of quantification or mean recovery. The the analysis of a reference material should be
algorithms used to convert these performance not larger than half the target standard
data into an uncertainty component should be uncertainty. The criteria for the observed
used in this assessment (Table 1). errors seem to be less strict than for precision
but reflect how this component contributes to
Usually, the in-house validation or
the uncertainty (Table 1).
verification of a procedure involves the
assessment of repeatability, intermediate
precision, trueness, linearity, limit of
Example 9:
quantification and uncertainty.
For the determination of the chemical
The repeatability standard deviation should
oxygen demand of wastewaters to check
not be larger than 1/5 to 1/3 of the target
compliance with Directive 91/271/EEC, a
standard uncertainty to allow for the expected
target relative standard uncertainty of 10 %
contribution of the other uncertainty
is defined [23] for the limit of 125 mg L-1
components.
[26]. Therefore, at 125 mg L-1 the target
The intermediate precision standard deviation, standard uncertainty is 12.5 mg L-1. Since
a major uncertainty component in most uncertainty should be approximately
measurements in chemistry, should not be constant between 25 mg L-1 and 625 mg L-1
larger than 1/3 to half [24] the target standard (i.e. five times less and more than
uncertainty. 125 mg L-1), the u is 14 % at 89 mg L-1
(0.14=12.5/89). Hence the maximum value
The target uncertainty can guide the definition
for the limit of quantification would be
of the target limit of quantification if this limit
is estimated under intermediate precision 89 mg L-1.
conditions. Since the coefficient of variation
in the LOQ is 10 % [25], the quantity value
The present criterion for the various
where this precision is expected should
performance characteristics should be only
correspond to the LOQ. Assuming that the
indicative since the smaller magnitude of an
squared intermediate precision constitutes half
effect can allow a more flexible assessment of
the squared standard uncertainty, the expected
the other ones.
relative standard uncertainty in the LOQ is
14 % (0.14 = (0.1)2 + (0.1)2 ). Accordingly,
the predictive models of the uncertainty close
to the LOQ can be used to define the target
value for the limit (Example 9).
10 Examples
The following sections present examples of error (i.e. measured quantity value minus a
the definition of the target measurement reference quantity value) and precision as
uncertainty in scenarios previously described. defined in the Directive is twice the
repeatability or intermediate precision
10.1 Defined compliance interval standard deviation.
In the European Union, the quality of bathing For Cd in drinking water, the parametric value
water in running or still, fresh water or (that is, the upper limit) is 5 g L-1, and and
seawater, is regulated by Directive are 0.5 g L-1
-1
76/160/EEC [27] which is the basis of (= =10 %5 g L ).
national monitoring programmes. This
According to Eq.(5):
legislation establishes limits for
microbiological and physical-chemical
parameters, and some pollutants. The pH of uctg = (u ) + (u )
tg 2
ra
tg 2
sy =
bathing water should be between 6-9 but 2 2
provisions exist for exceeding these limits
= + = (13)
under certain conditions. Therefore, the 6 2
determination of the pH in bathing water
should be capable to distinguish pH values = 0.32 g L-1
within this interval. According to the
If, for example, the standard uncertainty of the
methodology proposed in section 5.1.2, the
measurement, u, is 0.39 g L-1, the
expanded uncertainty should be smaller than
measurement does not meet this requirement,
or equal to [(9-6)/8]=0.38 pH units
which is in addition to the mandatory
(i.e. U =0.38). This performance is easily
tg
performance requirement set by the Directive.
achievable by potentiometric determinations
In fact, if u is larger than u ctg , at least one of
with a combined glass electrode.
the performance requirements of the
10.2 Defined measurement legislation has not been achieved. However, if
performance characteristics the quantitative Cd results are taken as the
mean of two duplicates performed by two
In the European Union, the monitoring of the analysts, the u(mean) becomes smaller than u ctg
quality of drinking water must be supported
(u(mean)= 0.31 g L-1) (see section 8). The
by measurements performed by procedures
reporting of duplicate measurement results
fulfilling requirements presented in Council
from two analysts makes the precision of the
Directive 98/83/EC [9]. This directive sets
final result adequate in relation to the
maximum values for the Limit of detection,
performance criterion specified in the
Trueness and Precision defined
Directive. In this case it can be decided that
differently from the latest edition of the VIM
non-compliance of cadmium content in
[1]. These defined maximum values for the
drinking water, according to Directive
performance characteristics are multiples of
98/83/EC, is based on the mean of duplicate
the parametric value, that is, the regulatory
measurements performed by two analysts.
limit for the measurand of interest.
In Directive 98/83/EC, trueness is defined 10.3 Defined decision risk
as the difference between the mean value
estimated from a large number of repeated Good manufacturing practices of
measurements and the conventional true value gold/silver/copper alloys, to be used in gold
and since this is not known it requires some artefacts, are known to produce gold contents
interpretation. The precision is twice the with deviation from the target composition of
relative standard deviation of measurements not larger than 5 [28] due to the
performed within and between batch. Using uncertainty of known purity and weighing of
VIM terminology [1], trueness is related to pure metals. Therefore, deviations in gold
content of these alloys larger than 5 are the stated reproducibility standard deviation is
only expected if poor manufacturing practice 0.6 mg kg-1. Therefore, for measurement
is followed or in fraud situations. Artefacts results in the range 1 to 25 mg kg-1, the target
can be marked for 19.2 karat (e.g. 800 standard uncertainty can be taken as
gold) if the gold content is proved to be above 0.6 mg kg-1.
this limit, compliance assessment being
performed without allowance for the
uncertainty. Only if the measured gold content
10.6 Magnitude of studied trends
is above 800 , is the product compliant for
19.2 karat. To make sure there is a chance of The optimisation of a wastewater treatment
at least 99 % of deciding a product with a gold scheme, by changing conditions in a pilot
content at least 5 above 800 (i.e. plant, is controlled by the percentage
805 ) is compliant, the determination reduction of the chemical oxygen demand
should be performed with a standard (COD) with the treatment. If COD reductions
uncertainty not larger than 2.1 of 5 % are considered relevant, the
[utg=5 /t1=5 /2.33=2.1 ] (section 5.1.4), determination of the COD reduction should be
where t1=2.33 is the one-tailed critical value carried out with a standard uncertainty not
of Students t for a high number of degrees of larger than 1.2 % (i.e. 1.2 %=5 %/4.2) (see
freedom and a confidence level of 99 %. section 5.4). The uncertainty of COD
reduction determinations, to be considered in
10.4 Proficiency tests comparing different treatment schemes,
should only take into account the uncertainty
The adulteration of vegetable oil with mineral
components responsible for deviations of
oil has been detected in products
compared COD reductions. For instance, if
commercialised in Europe. This situation
portions of the same wastewater are treated in
triggered the setting up of a proficiency test
competing treatment schemes, the uncertainty
for the determination of mineral oil content in
of the determination of the input COD value
sunflower oil [29], by the Institute for
should be excluded from these calculations.
Reference Materials and Measurements
Similarly, if the same reference is used in both
(IRMM) of the European Commission, in
COD determinations, the uncertainty
order to assess the quality of measurements
associated with this reference will not affect
performed in Europe. The provider of this
the ratio.
proficiency test evaluated laboratory
proficiency through the calculation of a
10.7 Information from a different
z-score determined using the median of
participants results and an assigned standard scope
deviation of 25 % of the median. This EU Directive 2008/50/EC [7] on ambient air
reference standard deviation was defined in an quality defines maximum limits for several
international workshop and, therefore, is contaminants in air, and target uncertainties
expected to reflect the position of a for their measurements. Air quality
representative number of experts. measurements are divided into fixed and
For these measurements, the target relative indicative, where the quality requirements
for indicative measurements are less strict
standard uncertainty, u tg , is 25 %.
than for fixed ones.
10.5 Measurement reproducibility This directive suggests complementing the
quantification of contaminants with the
The use of pentachlorophenol (PCP) for the determination of the anthropogenic or natural
preservation of leather was banned or origin of aerosols. The mass fractions of some
restricted in several European countries due to ions in the water soluble portion of the
its high toxicity and persistence. The ISO aerosols are key parameters to identifying
17070 standard [30] describes a procedure for their origin. However, no specification limits
the measurement of PCP in leather. This or target measurement uncertainties are
standard gives values for the reproducibility in defined for these parameters in the Directive.
various mass fractions, estimated from a
collaborative test. For example, at 5 mg kg-1,
Since the mass fraction of a specific ion in the Table 2: Standard deviation, sR, and relative
water soluble portion of aerosol is not being standard deviation, sR , of the reproducibility
compared with any specification limits, of measurements of PCP mass fraction, wPCP,
quality requirements for indicative in leather following the ISO 17070 standard
measurements of contaminants would seem to [30].
be an adequate reference for measurements of
these low toxicity agents. wPCP sR sR
(mg kg-1) (mg kg-1)
The indicative measurements of the various (%)
parameters have a target relative expanded 5.0 0.6 12.0
uncertainty ranging between 25-50 %.
Therefore, a target relative expanded 6.7 0.8 11.9
uncertainty of 40 % seems to be adequate to 16.8 2.1 12.5
determine the mass fraction of the water
soluble chloride, nitrate and sulphate in
aerosols [22]. Since the relative uncertainty tends to
If the variability of the uncertainty estimation decrease with the quantity value and the
process is considered, it can be decided that u uncertainty tends to be constant over a short
can be smaller than 48 % quantity interval, the following model of the
variation of the target uncertainty can be used
( u
max
=1.240=48 %). (Table 3).
10.8 Variation of target uncertainty
with the quantity value
The identification and quantification of
pentachlorophenol (PCP) in leather can be
performed by following the ISO 17070
standard [30]. In this document, the
repeatability and reproducibility, estimated in
a collaborative study, are reported for three
PCP mass fractions. Table 2 presents the
reproducibility observed at these mass
fractions3.
Measurements described in Table 2 are
considered fit for the intended use, and the
respective performance data adequate to
define the target uncertainty as described in
section 5.2.2.
3
Example 10.5 discusses the use of reproducibility
data observed at one level to define the target
uncertainty.
Table 3: Model of the variation of the target Table 4: Model of the variation of the
standard uncertainty, utg, or relative target maximum permissible estimated standard
standard uncertainty, utg, with the mass uncertainty, umax, or relative standard
fraction of PCP, wPCP. uncertainty, umax, with the mass fraction of
PCP, wPCP.
wPCP utg utg
(mg kg-1) (mg kg-1) (%) wPCP umax umax
(mg kg-1) (mg kg-1) (%)
1 5.0 0.6 -
1 5.0 0.72 -
5.0 16.8 - 12.5
5.0 16.8 - 15
16.8 () - 12.5
16.8 () - 15
- Maximum value of sR (Table
2).
The target uncertainty estimated using the
reproducibility standard deviation at three
Since the estimation of the uncertainty is mass fractions is more accurate than the target
variable, the maximum permissible estimated value estimated using information at one level
standard uncertainty, umax, is 1.2 times larger (see section 10.5).
than the target uncertainty, utg. Table 4
presents the umax in a wide mass fraction
interval.
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