The First

International Proficiency Testing Conference

Sinaia, România
11th − 13th October, 2007

NORDTEST HANDBOOK FOR CALCULATION OF MEASUREMENT

UNCERTAINTY BASED ON
QUALITY CONTROL AND METHOD VALIDATION

Bertil Magnusson1, Håvard Hovind2, Mikael Krysell3, Teemu Näykki 4, ...

1
SP Technical Research Institute of Sweden, Box 857, 501 15 Borås, Sweden,
2
NIVA, Norway, 3Eurofins A/S, Denmark, 4SYKE, Finland.
1
bertil.magnusson@sp.se, ...

Abstract

The aim with this handbook is to provide a practical, understandable and common
way of measurement uncertainty calculations based on already existing quality
control and method validation data for test procedures in routine use. To illustrate the
approach the estimation of measurement uncertainty for some routine methods in
environmental laboratories are presented.
The approach follows the general ISO and EA guidelines for measurement
uncertainty and uses the possibility of grouping the individual uncertainty components
into different categories. The first category is the intermediate precision within a
laboratory, here called reproducibility within laboratory, u(Rw) and the second
category is the method and laboratory bias, u(bias). The third category is the
reproducibility from interlaboratory studies, u(R). The error model used is a
simplification of the model presented in the ISO guide 21748.
However the first and most important step is always definition of the measurand and
specification of the required measurement uncertainty. Starting with this information
the handbook then tries to cover all steps in the analytical chain from the arrival of the
sample in the laboratory until the data has been reported. It is important to notice that
vital parts of the total measurement uncertainty are not included, e.g. sampling,
sample transportation.
It is recognised that while the recommendations presented do form a valid approach
to the evaluation of measurement uncertainty for many purposes, other suitable
approaches may also be adopted especially the EURACHEM/CITAC Guide
(www.eurachem.com) which, in the second edition, also stresses the use of method
validation data. Another good source is the Eurolab guide 2007 (Measurement
Uncertainty revisited, www.eurolab.org).
The English version of the handbook [1] is available at www.nordicinnovation.net,
Nordtest, Tecn. Report TR537.

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 Bertil Magnusson, Havard Hovind, Mikael Krysell, Teemu Näykki: Nordtest handbook for
calculation of measurement uncertainty based on quality control and validation data

Key words

Measurement Uncertainty, Quality Control, Validation

1 INTRODUCTION

There are several ways that a laboratory can choose to estimate measurement
uncertainty for results from a method in routine use. We propose a model where
either the reproducibility within-laboratory (Rw) is combined with estimates of the
method and laboratory bias, or the reproducibility sR is used more or less directly,
ISO Guide 21748. The alternative way is to construct a detailed fish-bone diagram
and calculate/estimate the individual uncertainty contributions. This approach may
prove very useful when studying or quantifying individual uncertainty components. It
has been shown, though, that in some cases this methodology underestimates the
measurement uncertainty, partly because it is hard to include all possible uncertainty
contributions in such an approach. By using existing and experimentally determined
quality control (QC) and method validation data, the probability of including all
uncertainty contributions will be maximised.

2 FLOW SCHEME FOR UNCERTAINTY CALCULATIONS

The flow scheme presented forms the basis for the method outlined in this handbook.
The flow scheme, involving 6 defined steps, should be followed in all cases. The
example with NH4-N in water shows the way forward for calculating the measurement
uncertainty using the flow scheme. For each step, there may be one or several
options for finding the desired information.
Background for the NH4-N example – automatic photometric method: The laboratory
has participated in 6 interlaboratory comparisons recently. All results have been
somewhat higher than the nominal value. The laboratory therefore concludes that
there may be a small positive bias. On average, the bias has been +2.2 %. This bias
is considered small by the laboratory and is not corrected for in their analytical
results, but exists, and is thus another uncertainty component. The data from the
interlaboratory comparisons are shown in Table 1.
Table 1 - Results for a laboratory from interlaboratory comparisons of NH4-N in water.
Exercis Nominal Laboratory Bias sR Number
e value result xi of labs
xref
mg/L mg/L % %
1999 1 81 83 2.4 10 31
2 73 75 2.7 7 36
2000 1 264 269 1.9 8 32
2 210 213 1.4 10 35
2001 1 110 112 1.8 7 36
2 140 144 2.9 11 34
X + 2.18 8.8 34
RMS (Root Mean Square) 2.25 - -

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 Bertil Magnusson, Havard Hovind, Mikael Krysell, Teemu Näykki: Nordtest handbook for
calculation of measurement uncertainty based on quality control and validation data

For this method, the main sources of uncertainty are contamination and variation in
sample handling, both causing uncertainty components. These uncertainty sources
will be included in the calculations below.

Table 2 - Flow scheme for uncertainty calculations

Step Action Example – Ammonium NH4-N
1 Specify Measurand Ammonium is measured in water according to
EN/ISO 11732 /11/. The customer demand on
expanded uncertainty is ± 10 %

2 Quantify Rw comp. A: Control limits are set to ± 3.34 %

A control sample (95 % confidence limit)
B possible steps not
covered by the control B: The control sample includes all analytical steps.
sample

3 Quantify bias From interlaboratory comparisons over the last 3

components years the bias results were 2.4; 2.7; 1.9: 1.4; 1.8:
and 2.9. The root mean square (RMS) of the bias is
2.25 %. The uncertainty of the nominal values is
u(Cref) = 1.5 %.
(see Table 1)

4 Convert components
to standard
uncertainty u(x)
Confidence intervals and similar distributions can be converted to standard
uncertainty [2,3].
u(Rw) = 3.34/2 = 1.67 %
1
u(bias) = RMSbias + u(Cref ) 2
2

= 2.252 + 1.5 2 = 2.71 %

5 Calculate combined Standard uncertainties can be summed by taking

standard the square root of the sum of the squares
uncertainty, uc uc = u(Rw ) 2 + (u(bias)) = 1.672 + 2.712 = 3.18
2

6 Calculate expanded The reason for calculating the expanded uncertainty

uncertainty, U = 2 ⋅ u c is to reach a high enough confidence (app. 95 %) in
that the “true value” lies within the interval given by
the measurement result ± the uncertainty.
U = 2 ⋅ 3.18 = 6.36 ≈ 6 % or 7 %.
The measurement uncertainty for NH4-N will thus be reported as ± 6 % or 7 % at this
concentration level.

1
u(bias) denotes the uncertainty contribution from the bias estimate to the measurement uncertainty. It
is not the uncertainty of the bias value.

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Bertil Magnusson, Havard Hovind, Mikael Krysell, Teemu Näykki: Nordtest handbook for
calculation of measurement uncertainty based on quality control and validation data

Summary table for uncertainty calculations

The results of the calculations done in the flow scheme will then be summarised in a
summary table.
Ammonium in water by EN/ISO 11732
Measurement uncertainty U (95 % confidence interval) is estimated to ± 7 %. The
customer demand is ± 10 %. The calculations are based on control chart limits and
interlaboratory comparisons.

Value Relative Comments

u(x)
Reproducibility within-laboratory, Rw
Control sample Rw Control limits is 1.67 %
X = 200 µg/L set to ± 3.34 %
Other --
components
Method and laboratory bias
Reference material bias --
Interlaboratory bias RMSbias= 2.25 % 2.71 % u(bias) =
comparisons u(Cref) = 1.5 % RMSbias + u(Cref )2
2

Recovery test bias --

Reproducibility between laboratories
Interlaboratory R -- 8.8 % Data - see Table 1
comparisons
Standard method -- 8% EN/ISO 11732
R
at level 200 µg/l

Combined uncertainty, uc is calculated from the control sample limits and bias
estimation from interlaboratory comparisons. The sR from interlaboratory
comparisons [4] using the same method can also be used if a higher uncertainty
estimation is acceptable.

Measurand Combined Uncertainty uc Expanded Uncertainty U

Ammonium 1.67 2 + 2.712 = 3.18 % 3.18 · 2 = 6.4 ≈ 7 %

3 THEORETICAL PART OF THE HANDBOOK

In the following sections of the handbook the components within-laboratory

reproducibility and bias are treated in detail as well as obtain measurement
uncertainty from interlaboratory data.

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 Bertil Magnusson, Havard Hovind, Mikael Krysell, Teemu Näykki: Nordtest handbook for
calculation of measurement uncertainty based on quality control and validation data

4 EXAMPLES PART OF THE HANDBOOK

In this section are given some examples of uncertainty calculations and also an
example with the concentration dependence of measurement uncertainty.

5 CONCLUSIONS

This handbook has now been used for several years and has been found to give
reliable estimates of measurement uncertainty for methods in routine use where a
quality control is in place and validation data for the bias estimate can be obtained.
It is full compatible with the GUM principles, however not giving and details of the
magnitude of different uncertainty sources that would be needed for further
optimization of the method but this approach combining within-laboratory
reproducibility with bias uncertainty covers most of the individual uncertainty
components.

REFERENCES

[1] Nordtest technical report 569, www.nordicinnovation.net

[2] BIPM, IEC, IFCC, ISO, IUPAC, IUPAP, OIML (1995). Guide to the expression
of uncertainty in measurement. (GUM). ISO, Geneva
[3] EURACHEM/CITAC (2000). Quantifying Uncertainty in Analytical
Measurement (QUAM). 2nd Internet edition. 2000. www.eurachem.ul.pt, last
accessed April 2006
[4] ISO (2004) ISO/TS 21748 Guidance for the use of repeatability, reproducibility
and trueness estimates in measurement uncertainty estimation. ISO, Geneva

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