Use of

Measurement Uncertainty
Information in
Compliance Assessment of
Chemical Results

D.Theodorou

Athens, October 2008

What is not uncertainty !

• Accuracy: accuracy is not a quantifiable term

• Error: result of a measurement minus the
true value of the measurand

idealized concepts
What is uncertainty

a parameter associated with the result of a measurement, that

characterizes the dispersion of the values that could reasonably be
attributed to the measurand
(ISO Guide to the Expression of Uncertainty in Measurement)

Result: 20 ± 3 mg
The true amount is
between 17 and 23 mg

Uncertainty = tolerance interval

Uncertainty of Chemical Measurements

There is always experimental variations when we make a measurement

Typical Sources of Uncertainty in

Chemical Analyses
•Sampling
Storage Conditions
Instrument effects (e.g. calibration, accuracy,
carry over effects)
Reagent purity
Assumed stoichiometry (e.g. incomplete or Type A &Type B
side reactions)
Combined
Measurement conditions (e.g temperature, contributions Uncertainty
humidity)
Sample effects (e.g. recovery - matrix effects)
Computational effects (e.g calibration model,
coverage factor, k
truncation / round off)
Blank correction
Operator effects Overall Estimate
Random effects
of Uncertainty
Eurachem/CITAC Guide
or Expanded
Uncertainty
Expanded Uncertainty U,
coverage factor k

U=k∙uC

k=2 k=3
95,45% 99,73%

U U U U
Typical Uncertainty Statement

Total cadmium content (Cd): 328 μg·kg-1

Measurement Uncertainty: 27 μg·kg-1 (8,2%)

The stated uncertainty is an expanded measurement

uncertainty (U). It was obtained by multiplying the
combined standard uncertainty uc with a coverage factor
k equal to 2. This corresponds approximately to a 95 %
confidence interval.
Procedures for the Estimation of
Measurement Uncertainty
• ISO Guide to the expression of measurement uncertainty (ISO GUM)
• EURACHEM Guide to quantifying uncertainty in analytical measurement

• Use of collaborative trial data – ISO 5725 critical differences

• ISO/TS 21748 – Guide to the Use of Repeatability, Reproducibility
and Trueness Estimates in Measurement Uncertainty Estimation
• Concept established by Commission Decision 2002/657/EC implementing
Council Directive 96/23/EC concerning the performance of analytical
methods and the interpretation of results
• AOAC INTERNATIONAL approach
• Internal quality control approach
• NMKL (Nordic Committee on Food Analysis) approach
• Microbiological Analyses (ISO/TS 19036, Niemelä Guide)
• Monte Carlo Simulation (ISO GUM Supplement 1)
Why is it important?

repeatability uncertainty
12,5

12

11,6 11,6 11,6

11,5
mg/kg

11

10,6 10,6 10,6

10,5

10
Lab A Lab B Lab A Lab B Lab A Lab B

Uncertainty = Confidence Informed Decision

Uncertainty and limiting values

Many analyses are made to assure that limiting values are not exceeded (e.g. for
drinking water quality)

Without information about the measurement uncertainty it may appear to be

very easy to make decisions, but these decisions may be incorrect
Uncertainty and limiting values

AN EXAMPLE

Drinking water -> Pb content

Parametric value: 10 μg/l (COUNCIL DIRECTIVE

98/83/EC)

Laboratory uncertainty at that level: ± 0,8 μg/l

(Expanded uncertainty, 95% confidence interval)
Uncertainty and limiting values

12

11,2
Pb content (μg/l)

10,4
10
9,6

8,8

8
(i) (ii) (iii) (iv)
Result less Result above Result below Result plus
uncertainty limit but limit limit but limit uncertainty
above limit within within below limit
uncertainty uncertainty
Uncertainty and limiting values
12

Straightforward Approach

Pb content (μg/l)
10,4
10
9,6
1. If possible use a method producing
more accurate results
2. Report the result and uncertainty with 8
(ii) (iii)
a statement that compliance (or non-
compliance) could not be
demonstrated
(for a suggested statement see UKAS Guide, M3003, The
Expression of Uncertainty and Confidence in Measurement)
Uncertainty and limiting values
12
Detailed Approach
• Set up probability based decision

Pb content (μg/l)
10,4
rules 10

• Select a decision limit (critical 9,6

value) taking into account what the

end user expects: 8
(ii) (iii)

Upper limit
Decision
i. low probability of false rejection, α Limit
guard band

Acceptance zone Rejection zone

Decision Upper limit

ii. low probability of false acceptance, β Limit
guard band

Acceptance zone Rejection zone

Uncertainty and limiting values

High confidence of correct rejection

Decision limit DL is chosen so that the risk of false rejection (α) is less than 2,5%.

Upper Limit

DL
guard band,
g = 2∙uc= U95%

2,5% of the values under the curve U95%

are inside the specification limit

Acceptance Zone Rejection Zone

Uncertainty and limiting values

High confidence of correct acceptance

Decision limit DL is chosen so that the risk of false acceptance (β) is less than 2,5%.

Upper Limit

DL
guard band,
g = 2∙uc= U95%

U95%
2,5% of the values under the curve
are outside the specification limit

Acceptance Zone Rejection Zone

EURACHEM / CITAC Guide

USE OF UNCERTAINTY INFORMATION IN COMPIANCE

ASSESSMENT, Edition 1(2007)

The Guide describes many aspects of the matter.

It covers cases of:
- Simultaneous upper and lower limits
- Uncertainties depending on the value of the measurand
- Asymmetric distributions of the measurand
- Standard uncertainties with effective degrees of freedom

Different decision rules are compared.

Conclusions

-Need for consistent way of reporting test results

-Uncertainty: quantitative measure of the reliability of a result

-Decisions for compliance or non-compliance with a specification

should take into account uncertainty

-When the state of compliance is not clear, appropriate judgments

should be based on probability-based decision criteria

-Decision criteria should be based on risks associated with making

wrong decision i.e. false rejection or false acceptance
Thank you for your attention !!!

Dimitris Theodorou, MSc, MBA

dtheodorou@priority.com.gr
PRIORITY S.A.
Business Consultant
Laboratory Accreditation Dept.