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Producing reliable measurements in analytical chemistry can be rather demanding.
Some would say an uphill struggle. Comparable to mountain walking. Hard work, but then
the satisfaction of reaching the top is absolutely great. And so is the view.
As with all human endeavour, it always helps to know what you are doing, thus theoretical
knowledge forms the basis. Likewise in analytical chemistry. Understanding the measurement
science, the metrology, is important. That is why in the international standard ISO/IEC-17025
General requirements for the competence of testing and calibration laboratories section five deals
with technical requirements such as traceability, validation and uncertainty. The European Life
Long Learning Programme TrainMiC, created in 2001, produced material for teaching the
theory.
As excellence in theory does not necessarily mean mastering practice, a need for developing
practical examples later arose. This is what you can find in this book, which is intended as a first
of a series of such compilations.
Inspired by the NORDTEST Trollbook, we also decided to have a mascot. For each volume,
a different one, which would be taken from the treasure of European fairy tales and legends.
For this first volume, the fairy tale character of Kekec (pronounced as Kekets) was chosen. Kekec
is a brave, clever and cheerful shepherd boy who lives in Slovenian mountains. He always brings
good to the people that surround him and he helps those that are in trouble. And in that sense,
that is what is the intention of this book.
We hope it succeeds in doing so.
Nineta Majcen
Philip Taylor
ISBN 978-92-79-12021-3
PRACTICAL EXAMPLES ON TRACEABILITY, MEASUREMENT UNCERTAINTY AND VALIDATION IN CHEMISTRY
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The mission of the JRC is to provide customer-driven scientific and technical support for the
conception, development, implementation and monitoring of EU policies. As a service of the
European Commission, the JRC functions as a reference centre of science and technology for
the Union. Close to the policy-making process, it serves the common interest of the Member
States, while being independent of special interests, whether private or national.
Practical Examples on
Traceability,
Measurement Uncertainty
and Validation
in Chemistry
Volume 1
Edited by
Nineta Majcen, Philip Taylor
Authors:
Ljudmila Benedik
Steluta Duta
Koit Herodes
Monika Inkret
Veselin Kmetov
Allan Knnapas
Ivo Leito
Bertil Magnusson
Urka Repinc
Philip Taylor
Emilia Vassileva
EUR22791/2 EN - 2010
Practical Examples on
Traceability,
Measurement Uncertainty
and Validation
in Chemistry
Volume 1
Second edition
Edited by
Nineta Majcen, Philip Taylor
Authors:
Ljudmila Benedik
Steluta Duta
Koit Herodes
Monika Inkret
Veselin Kmetov
Allan Knnapas
Ivo Leito
Bertil Magnusson
Urka Repinc
Philip Taylor
Emilia Vassileva
The mission of the JRC-IRMM is to promote a common and reliable European

measurement system in support of EU policies.
European Commission
Joint Research Centre
Institute for Reference Materials and Measurements
Contact information
Address: Retieseweg 111, B-2440 Geel, Belgium
E-mail: philip.taylor@ec.europa.eu
Tel.: +32 (0)14 571 605
Fax: +32 (0)14 571 863
http://irmm.jrc.ec.europa.eu/
http://www.jrc.ec.europa.eu/
Legal Notice
Neither the European Commission nor any person acting on behalf of the Commission
is responsible for the use which might be made of this publication.
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Freephone number (*):
00 800 6 7 8 9 10 11
(*) Certain mobile telephone operators do not allow access to 00 800 numbers or these calls may be billed.
More information on the European Union is available on the Internet (http://europa.eu).

Cataloguing data can be found at the end of this publication.
/X[HPERXUJ3XEOLFDWLRQV2IFHRIWKH(XURSHDQ8QLRQ
JRC 59026
EUR 22791/2 EN
ISBN 978-92-79-12021-3
ISSN 1018-5593
doi: 10.2787/10402
European Union, 2010
Reproduction is authorised provided the source is acknowledged
Printed in
TABLE OF CONTENTS
INTRODUCTION ..................................................................................................................5
HOW TO USE THE BOOK ...................................................................................................6
ABOUT THE AUTHORS .....................................................................................................11
CHAPTER 1..........................................................................................................................17
Analysis of Gold Alloys by Flame Atomic Absorption Spectrometry
Veselin Kmetov, Emilia Vassileva
CHAPTER 2..........................................................................................................................51
Determination of Calcium in Serum by Spectrophotometry
Steluta Duta, Philip Taylor
CHAPTER 3..........................................................................................................................81
Determination of Radium in Water by -Spectrometry
Ljudmila Benedik, Urka Repinc, Monika Inkret
CHAPTER 4....................................................................................................................... 121

Determination of Polar Pesticides by Liquid Chromatography Mass Spectrometry
Allan Knnapas, Koit Herodes, Ivo Leito
CHAPTER 5....................................................................................................................... 157

Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and
Spectrometric Detection
Bertil Magnusson
APPENDIX 1 ..................................................................................................................... 193

TrainMiC Exercises (white pages)
APPENDIX 2 ..................................................................................................................... 209
Briefing of the trainees on the example session
Practical examples on traceability, measurement uncertainty and validation in chemistry
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Chapter 1
Analysis of Gold Alloys by Flame Atomic

Absorption Spectrometry
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TrainMiC example summary form (blue page)

A short introduction to the analytical procedure (slides)
All input needed to do the three exercises (yellow pages)
The solved exercises (green pages)
17
TrainMiC example summary form
I. General information about the example
18
Measurand
Mass fraction of Au in gold alloys ()
Example number
Ex-06
Authors of the example
Analytical procedure
Determination of gold in jewellery gold alloys by flame atomic

absorption spectrometry
Customers requirement
U = 9 (k = 3)
II. Attached files
2 - Yellow
1-I
File number, type

and name
Ex-06-1-I-Aualloys-FAAS-2006Ver1.ppt
About the analytical procedure: short introduction
PART I
PART II
Ex-06-2-Y-Aualloys-FAAS-2006Ver1.doc
PART III
3 - Green
PART IV
EX-06-3-G-Aualloys-FAAS-2006Ver1.doc
File is
attached
Yes No
Content of the file
Description of the analytical procedure

The customers requirements
concerning the quality of the
measurement result
Validation of the measurement
procedure relevant equations and
measurement data
Measurement uncertainty of the result
relevant equations and measurement
data
Each
participant
receives own
copy and
may keep it
9
9
Establishing traceability in analytical

chemistry
PART II
Single laboratory validation of

measurement procedures
Building an uncertainty budget
Addendum 1: By spreadsheet approach
Addendum 2: By dedicated software
Given by the
lecturer
PART I
PART III
Remark
III. History of the example

Version
Uploaded on the webhotel
Short description of the change
April 2007
1
2
19
A short introduction to the analytical procedure
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All input needed to do the three exercises yellow pages
Determination of gold in jewellery gold alloys by Flame Atomic
PART I ...................................................................................................................................25
PART II .................................................................................................................................33
The customers requirements concerning the quality of the measurement result
PART III ................................................................................................................................34
Validation of the measurement procedure relevant equations and
measurement data
PART IV ................................................................................................................................35
Measurement uncertainty of the result relevant equations and measurement
data
24
PART I. Description of the analytical procedure
Task description
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ISO/TC 174. rev.N71. Gouda 1992 Determination of gold in gold jewelry
allows ICP solution spectrometric method using yttrium as internal
standard
2.
CNR-PRO Art Project (1998) Tecniche spettrometriche alternative alla
copellazione per il saggio delle leghe dioro
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Figure 3. Flow chart of the analytical procedure for determination of gold in gold
alloys
26
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27
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Atomic absorption measurement

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28
Table 1. Instrumental parameters for ASDI-FAAS determination of Au

FAAS parameters
Values
ASDI parameters
Au spectral line [nm]

Au spectral slit [nm]
242.8
0.7
Ql- aspiration rate 6.4 mL min-1 checked by BDW

Injection time 5 s; Injection volume 0.530 L
Au hollow cathode lamp current [mA]
10
Washing time 10 s; Total replicate time 15 s
Air/C2H2 units
Observation high [mm]
50/18
6
Smoothing Savitzky-Golay 24 points

Ensemble summation N signal profiles
Working range g g-1

Deuterium BG corrector
3743
OFF
Pseudo plateau 3 s
Sampling mode (St1 _ sample _ St2 ) N
Readings points [s]
50
Total time for one set 66 s
29
Calculations
Concentration of initial standard solution made up from pure gold
C_ Au 999.9 =
m_ pureAu Au_ purity

G _100
104
C_ Au 999.9
FRQFHQWUDWLRQRILQLWLDOVWDQGDUGVROXWLRQPDGHXSIURPSXUHJROG>JJ@
m_ pureAu
PDVVZHLJKHGRISXUHJROG>J@
GB
PDVVRIWKHVROXWLRQLQWKHYROXPHWULFDVNPDGHXSWRJZLWK
1+CO>J@
Au purity
WKHSXULW\RIJROGVWDWHGLQWKHFHUWLFDWH>@

FRQYHUVLRQ IDFWRU IURP WR J J HTXDOLVHG IRU VWDQGDUG DQG

VDPSOHVLQ1+CO
Concentration of calibration standard solutions

C _ St1 = C Au _999.9
G _100
C _ St 2 = C Au _999.9
G_0.43
G _100
C _ St1
C _ St 2
CRQFHQWUDWLRQRI$XZRUNLQJVWDQGDUGVROXWLRQV>JJ@
CBStIRUORZJJDQGCBStIRUKLJKJJ
C Au _999.9
CRQFHQWUDWLRQRI$XVWDQGDUGVROXWLRQ$X>JJ@SUHSDUHGIURP
SXUHJROG
G_0.37
G_0.43
G_100
30
G_0.37
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DGGLQJ1+COLQSRO\SURS\OHQHYLDOV>J@
Bracketing calibration
Cx =
C st1 ( A_ St 2 A _ X ) + C St 2 ( A x A St1 )
A St 2 A St1
CRQFHQWUDWLRQRI$XLQWKHDQDO\VHGVROXWLRQ>JJ@
Cx
C St 2
CRQFHQWUDWLRQ RI WKH ORZHU FDOLEUDWLRQ VWDQGDUG VROXWLRQ XVHG IRU

EUDFNHWLQJFDOLEUDWLRQ>JJ@
CRQFHQWUDWLRQ RI WKH KLJKHU FDOLEUDWLRQ VWDQGDUG VROXWLRQ XVHG IRU
EUDFNHWLQJFDOLEUDWLRQ>JJ@
A St1
$EVRUEDQFHPHDVXUHGIRUWKHORZHUFDOLEUDWLRQVWDQGDUGVROXWLRQCB6W
A_ St 2
$EVRUEDQFHPHDVXUHGIRUWKHKLJKHUFDOLEUDWLRQVWDQGDUGVROXWLRQCB6W
C St1
$EVRUEDQFHPHDVXUHGIRUWKHDQDO\VHGVDPSOHVROXWLRQ
A_ X
Calculation of Au mass fraction (W_) in analysed sample

WB=
1 V_ 50 1 Gvials _12

Cx
1000 m_ 0.1 R GP _ 0, 4
WB
QDOFRQFHQWUDWLRQRI$XLQWHVWHGMHZHOOHU\JROGDOOR\ZZ>@
YROXPHRIWKHVROXWLRQLQWKHYROXPHWULFDVN>PL@
V_ 50
PDVVRIDQDO\VHGDOOR\VDPSOH>J@
m_ 0.1
Gvials _12
ZHLJKWRIQDOVDPSOHVROXWLRQSUHSDUHGLQYLDOV>J@
GP _ 0.4
PDVVRI$XVDPSOHVROXWLRQWDNHQIURPVB>J@
FRUUHFWLRQIRUUHFRYHU\
Combined model equation for calculation of Au content ()

WB =
1 V _ 50 Gvials _ 12 CAu_999.9 GP _0.37 ( A_ St 2 A _ X ) + GP _0.43 ( A X A St1 ) 1
A St 2 A St1
R
G_10
1000 m _ 0.1 GP _ 0.4
31
Calculation of signal standard uncertainty estimated as standard deviation

u_ A =
u_ A _ one _ set
N
u_ A
u_ A _ one _ set
32
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6WBVDPSOHB6W
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B6W
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PART II. The customers requirements concerning quality of the

measurement result
([SDQGHGPHDVXUHPHQWXQFHUWDLQW\k
33
PART III. Validation of the measurement procedure relevant

equations and measurement data
TKHSURFHGXUHKDVEHHQGHYHORSHGLQWKHODERUDWRU\WKXVDIXOOYDOLGDWLRQPXVWEH
SHUIRUPHG
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See Part I
MHDVXUHPHQWGDWD
Recovery:
CXSHOODWLRQPHWKRG
$'I)$$6
Repeatability:

34
PART IV. Measurement uncertainty of the result relevant

CDOFXODWH FRPELQHG DQG H[SDQGHG XQFHUWDLQW\ k IURP WKH IROORZLQJ
PHDVXUHPHQWGDWD
Input
quantity
Value
Unit
Standard
uncertainty
Remark
V_ 50
50
mL
0.0379
Volume of analysed solution
V_100
100
mL
0.0697
Volume of stock standard solution
m_0.1
0.1001
0.0002
Mass of analysed alloy sample
Gvials _12
12.0030
0.0008
Mass of sample solution prepared in vials
GP _ 0.4
0.4015
0.0009
Mass of Au sample solution taken from V_50

flask
m_ pureAu
0.1004
0.0002
Mass weighed of pure gold
Au_ purity
99.99
0.0058
The purity of gold stated in the certificate
G p _0.37
G p _0.43
0.3701
0.4302
0.0006
Masses of the stock Au standard solution

transferred for the preparation of calibration
solutions C_St1 and C_St2
G_10
10.0321
0.0008
Mass of calibration standard solutions
A St1
A_ St 2
0.5203
0.6041
AU
0.0010
0.0011
Absorbance measured for calibration

standard solutions
AX
0.5488
AU
0.0011
Absorbance measured for the analysed

sample solution
1.002
0.0025
Recovery
35
The solved exercises green pages
TrainMiC Exercises
Determination of gold in jewellery gold alloys by flame atomic
absorption spectrometry
EXERCISE 1:
Establishing traceability in analytical chemistry
EXERCISE 2:
Single laboratory validation of measurement procedures
Part I: General issues
Part II: Parameters to be validated
Part III: Some calculations and conclusions
EXERCISE 3:
Addendum I: By spreadsheet approach
Addendum II: By dedicated software
36
ESTABLISHING TRACEABILITY IN ANALYTICAL CHEMISTRY

EXERCISE
1. Specifying the analyte and measurand
Analyte
Gold
Measurand
Gold mass fraction in jewellery alloys after aqua regia dissolution
Units
(g/1000 g)
2. Choosing a suitable measurement procedure with associated model equation

Measurement
procedure
Type of calibration
standard addition
standard curve
internal standard
Model equation
1. Standard solutions
1.1. Stock standard solution - prepared from pure gold
C Au _999.9 =
m pureAu Au_ purity

G _100
104
1.2. Calibration standard solutions

C _ St1 = C Au _999.9
G p_0.37
G_ 100
C _ St 2 = C Au _999.9
G p_0.43
G_ 100
2. Bracketing calibration
Cx =
C St1 ( A_ St 2 A_ X ) + C St 2 ( A x A St1 )
A St 2 A St1
3. Calculation of Au content (W_) in analysed sample

W _0 =
1 V_ 50 Gvials _12
1
Cx
1000 m_ 0.1
GP _ 0.4
R
4. Calculation of signal standard uncertainty

u_ A =
u_ A _ one _ set
N
37
5. Calculation of recovery
R=
Wobserved
Wref
6. Combined model equation for calculation of Au mass fraction ()

WB =
1 V_ 50 Gvials _ 12 m pureAu Au purity
104
1000 m_ 0.1 GP _ 0.4

G_100 V _100
(G
P _0.37
( A_ St 2 A _ X ) + GP _0.43 ( A X A St1 )
A St 2 A St1
) 1
V _ 50
YROXPHRIDQDO\VHGVROXWLRQ>PL@
V _100
YROXPHRIVWRFNVWDQGDUGVROXWLRQ>PL@
m_ 0.1
PDVVRIDQDO\VHGDOOR\VDPSOH>J@
Gvials _12
PDVVRIVDPSOHVROXWLRQGLOXWHGLQYLDOV>J@
GP _ 0.4
PDVVRI$XVDPSOHVROXWLRQWDNHQIURPVBDVN>J@
m_ pureAu
Au_ purity
G p _0.37 or G p _0.43
G_100
PDVVZHLJKHGRISXUHJROG>J@
WKHSXULW\RIJROGVWDWHGLQWKHFHUWLFDWH>@
PDVVHV RI WKH VWRFN $X VWDQGDUG VROXWLRQ WUDQVIHUUHG IRU WKH
SUHSDUDWLRQRIFDOLEUDWLRQVROXWLRQV6WDQG6W>J@
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AX
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UHFRYHU\
DEVRUEDQFHPHDVXUHGIRUWKHDQDO\VHGVDPSOHVROXWLRQ
3. List the input quantities according to their influence on the uncertainty of the
result of the measurement (first the most important ones). At this point, your
judgement should be based on your previous experience only.
38
Recovery 28.5 % to the expanded uncertainty
Absorption of analysed gold sample contributing 19.8 % to the expanded uncertainty
Mass of analysed gold sample contributing 11.8 % to the expanded uncertainty
Mass of stock solution taken for the preparation of first standard solution contributing 12.1 % to the
expanded uncertainty
Volume of the analysed solution contributing 3.4 % to the expanded uncertainty
4. List the reference standards needed and give also the information regarding
traceability of the reference value
For the analyte
1
Name/Chemical Formula/Producer:
Pure Gold certified by Non-Ferrous Metallurgical

Plant Plovdiv Bulgaria
For the other input quantities

1
Quantity/Equipment/Calibration:
e.g. mass/balance/calibrated by NMI, U = xx
(k = 2), see also data yellow sheet
Balance calibrated by NMI
Volumetric flask class A quality
Absorbance relative measurement. Not direct part of

the traceability chain.
5. Estimating uncertainty associated with the measurement

Are all important parameters included in the
measurement equation?
Yes
Other important parameters are:
Within-lab reproducibility
No
6. How would you prove traceability of your result?

1
Comparing the results with independent method (cupellation)
39
7. Any other comments, questions
40
SINGLE LABORATORY VALIDATION

OF MEASUREMENT PROCEDURES
EXERCISE
PART I: GENERAL ISSUES

1. Specify the measurement procedure, analyte, measurand and units
The measurement procedure
Analysis of gold alloys by AAS
Analyte
Gold
The measurand
Gold in jewellery alloys containing gold 14 0.5 carats after aqua

regia dissolution
Unit
2. Specify the Scope

Matrix
Gold in 5 % NH4Cl
Measuring range
37-43 g g-1
3. Requirement on the measurement procedure

Intended use of the results:
Quality of products from precious metals alloys

LOD
LOQ
Repeatability
Mark the customers requirements

and give their values
Measurement uncertainty
Trueness
Other-state
4. Origin of the measurement procedure

VALIDATION
New in-house method
Full
Modified validated method
Partial
Official standard method
Confirmation/Verification
41
PART II: PARAMETERS TO BE VALIDATED
5. Selectivity/Interference/Recovery
Where yes, please give further information e.g. which CRM, reference method
CRM/RM: analysis of available CRM or RM
Further information:
Spike of pure substance
Pure gold 99.99 % certified from non-ferrous metallurgical plant Plovdiv, Bulgaria
Compare with a reference method
Comparison with cupellation method
Selectivity, interferences
Test with different matrices
Other please specify

Test for recovery with RM jewellery gold alloy marked 585
6. Measuring range
Linearity
Upper limit
LOD
LOQ
7. Spread precision
Repeatability
Reproducibility (within lab)
Reproducibility (between lab)
8. Robustness
Variation of parameters
42
9. Quality control
Control charts
Participation in PT schemes
10. Other parameters to be tested

Working range and testing of homogeneity of variances
Recovery
Residual standard deviation
Standard deviation of the method
Coefficient of variation of the method
43
PART III: SOME CALCULATIONS AND CONCLUSIONS
11. Calculation of parameters requested by the customer

Parameters requested to be
validated
Calculations
LOD
LOQ
Repeatability
2.4
Within-lab reproducibilty
Trueness
8.3 (k = 3)
Other - please state

Recovery
1.0002 0.0025
12. Does the analytical procedure fulfil the requirement(s) for the intended use?
Parameter
(the same as stated in question3)
Value obtained
during
validation
The requirement
is fulfilled
Yes/No
9 (k = 3)
8.3 (k = 3)
yes
Value requested by the

customer
LOD
LOQ
Repeatability
Within-lab
reproducibility
Trueness
Measurement
uncertainty
Other
The analytical procedure is fit for the intended use:

Yes
No
For measurement uncertainty and traceability refer to the corresponding reportsheets
44
BUILDING AN UNCERTAINTY BUDGET

EXERCISE
1. Specify the measurand and units
Measurand
Gold mass fraction in jewellery alloys after aqua regia dissolution
Unit
(g/1000 g)
2. Describe the measurement procedure and provide the associated model

equation
Measurement procedure:
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GLUHFWO\GLVVROYHGLQWRDYROXPHWULFDVNRIPLE\PLIUHVKO\SUHSDUHGaqua regia
TKHDVNLVKHDWHGRQFHUDPLFKRWSODWHIRUPLQ'XULQJWKLVSURFHVV$JSUHFLSLWDWHV
DV$JCO$JCOLVGLVVROYHGE\DGGLQJRIJ1+COWRWKHFRROHGVROXWLRQDQGYROXPH
LVPDGHXSWRWKHPDUNPLZLWK%':DWC
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FRQLFDOYLDODGGLQJ1+COLQRUGHUWRNHHSWKHVROXWLRQKRPRJHQHRXVZLWKQDO
ZHLJKWRIJJUDYLPHWULFDOO\FRQWUROOHG
PURFHGXUDO EODQN DQG JROG UHIHUHQFH PDWHULDO DUH VXEMHFW WR H[DFWO\ WKH VDPH VDPSOH
SUHSDUDWLRQDQGPHDVXUHPHQWSURFHGXUHVDVWKHDQDO\VHGVDPSOH
Model equation:
1. Concentration of initial standard solution made up from pure gold
C Au 999.9 =
m pureAu Au purity
G _100
104
C _ St 2 = C Au _999.9
G_0.43
G _100
2. Concentration of calibration standard solutions

C _ St1 = C Au _999.9
G_0.37
G _100
3. Bracketing calibration
Cx =
C St1 ( A_ St 2 A_ X ) + C St 2 ( A x A St1 )
A St 2 A St1
4. Calculation of Au mass fraction (W_) in analysed sample

WB =
1 V_ 50 1 Gvials _ 12

Cx
1000 m_ 0.1 R GP _ 0.4
45
5. Calculation of signal standard uncertainty

u_ A =
u_ A _ one _ set
N
6. Calculation of recovery
R=
Wobserved
Wref
7. Combined model equation for calculation of Au mass fraction ()

WB =
1 V _ 50 Gvials _ 12 CAu_999.9 GP _0.37 ( A_ St 2 A _ X ) + GP _0.43 ( A X A St1 ) 1
A St 2 A St1
R
G_100
1000 m _ 0.1 GP _ 0.4
3. Identify (all possible) sources of uncertainty

Uncertainty of concentration of reference solutions
Uncertainty of measurements of absorption of standard and sample solutions
Mass of analysed gold sample
Volume of the analysed solution
Recovery
Other:
Other:
4. Evaluate values of each input quantity
46
Input quantity
Value
Unit
Remark
V _ 50
50
mL
V _100
100
mL
m_ 0.1
0.1001
Gvials _12
12.0030
GP _ 0.4
0.4015
Mass of Au sample solution taken from V_50 flask
m pureAu
0.1004
Au_ purity
99.99
G p _0.37 ; G p _0.43
0.3701; 0.4302

G_100
10.0321
AU
A St1 ; A_ St 2
0.5203; 0.6041
AU
AX
0.5488
AU
1.002

Absorbance measured for calibration standard
solutions
Absorbance measured for the analysed sample
solution
Recovery
5. Evaluate the standard uncertainty of each input quantity

Input quantity
Standard
uncertainty
Unit
Remark
V _ 50
0.0379
mL
V _100
0.0697
mL
m_ 0.1
0.0002
Gvials _12
0.0008
GP _ 0.4
0.0009
Mass of Au sample solution taken from V_50 flask
m pureAu
0.0002
Au_ purity
0.0058
G p _0.37 ; G p _0.43
0.0006; 0.0006

G_10
0.0008
A St1 ; A_ St 2
0.0010; 0.0011
AU
AX
0.0011
AU
0.0025
Absorbance measured for calibration standard

solutions
Absorbance measured for the analysed sample
solution
Recovery
6. Calculate the value of the measurand, using the model equation

7. Calculate the combined standard uncertainty (uc) of the result and specify units
Using:
MDWKHPDWLFDOVROXWLRQ
6SUHDGVKHHWDSSURDFK
CRPPHUFLDOVRIWZDUH
47
Input
quantity
Value
Standard
uncertainty
Unit
Remark
W_
583.5
2.8
Au mass fraction in jewellery alloys
8. Calculate expanded uncertainty (Uc) and specify the coverage factor k and the
units
k
9. Analyse the uncertainty contribution and specify the main three input quantities
contributing the most to Uc
1
Recovery contributing 37.6 % to the expanded uncertainty
Absorption of analysed gold sample contributing 26.1 % to the expanded uncertainty
Mass of analysed gold sample contributing 14.9 % to the expanded uncertainty
10. Prepare your uncertainty budget report

k
WKHUHSRUWHGXQFHUWDLQW\LVDQH[SDQGHGXQFHUWDLQW\FDOFXODWHGXVLQJDFRYHUDJHIDFWRURI
k ZKLFKJLYHVDOHYHORIFRQGHQFHRIDSSUR[LPDWHO\
48
Further readings
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CI%-2PUHFLRXVPHWDOVFRPPLVVLRQThe Precious Metals Book
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LQMHZHOU\VDPSOHVFresenius J. Anal. Chem.
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LQGXFWLYHO\ FRXSOHG SODVPD PDVV VSHFWURPHWU\ J. Anal. Atom. Spectrom.

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Addendum I. Measurement uncertainty calculation:

spreadsheet approach (Excel)
Chapter 2
Determination of Calcium in Serum by

Spectrophotometry
u
u
u
u

51
52
Measurand
Concentration of calcium in human serum (mg dL-1)
Example number
Ex-10
Standard WHO procedure
Standard WHO procedure
II. Attached files
3 - Green
2 - Yellow
1-I
File number, type

and name
Ex-10-1-ICa-serumPhotometry2006-Ver1.ppt
Ex-10-2-YCa-serumPhotometry2006-Ver1.doc
Ex-10-3-GCa-serumPhotometry2006-Ver1.doc
File is
attached
Yes No
Content of the file
PART I
PART II
The customers requirements concerning

the quality of the measurement result
PART
III
Validation of the measurement procedure

relevant equations and measurement data
PART
IV

relevant equations and measurement data
PART I

chemistry
PART II

Bulding an uncertainty budget
PART
III
Remark
Given by the
lecturer
Each
participant
receives own
copy and
may keep it

Version
April 2007
53
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54
Analysis of GoldofAlloys
Determination
Calcium
by Flame
in Serum
Atomic
by Spectrophotometry
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Determination of concentration of calcium in serum by
molecular absorption spectrometry.
The quality of the results should comply with the requirements
in the WHO procedure
PART I ...................................................................................................................................57
PART II .................................................................................................................................60
PART III ................................................................................................................................61
measurement data
PART IV ................................................................................................................................62
data
56
Laboratory task
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S7.5
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QC
Distilled water (mL)
0.1
Standard (mL)
0.1
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0.1
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59

measurement result according to WHO*
Clinical interpretation:1
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60

Within-laboratory reproducibility (between day precision)
Model equation
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5
(c
i , obs
CV =
cQC
n ( n 1)
100
cQC
CV
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QXPEHURIUHSURGXFLEOHPHDVXUHPHQWV
Measurement data
Input quantity
Value standard deviation

(3 replicates)
1st day:
ci,obs
(i = 15) day
3 replicates/day
8.990 0.057
rd
3 day:
9.210 0.105
4th day:
9.230 0.086
5th day:
9.110 0.120
cQC
8.2410.52
Unit
9.16 0.05
mg dL-1
9.280 0.021
nd
2 day:
Mean value
standard deviation
9.38 0.38
mg dL-1
no units
CV =
61
PART IV. Measurement uncertainty of the result: relevant

equations and measurement data2
IV.1. Preparation of standard solutions2
IV.1.1 Preparation of calcium stock standard solution, cstock
cstock = ( m M Ca P ) 100 / V500 M CaCO3
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Input quantity
Value
Standard uncertainty
Unit
625.0
0.2
mg
MCa
40.078
0.002
g mol-1
0.9999
0.0058
mass fraction
V500
500.00
0.15
mL
MCaCO3
100.0869
0.0024
g mol-1
IV.1.2 Preparation of calibration standard solutions, ci:

V
ci = cstock i
V100
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62
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Input quantity
Value
Unit
cstock
50.05
0.02
mg dL-1
Vi
20.000
0.043
mL
V100
100.000
0.058
mL
IV.2 Calibration one point calibration

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Input quantity
Value
Unit
c_10
10.000
0.023
mg dL-1
Ax
0.323
0.004
no units
A-10
0.338
0.002
no units
Ablank
0.052
0.004
no units
IV.3 Calculation of calcium concentration in serum sample

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V
c
cCa = cx f V x
int
VI
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Input quantity
Value
Unit
cx
9.486
0.303
mg dL-1
Vf
0.100
0.002
mL
Vint
0.100
0.002
mL
63
TrainMiC Exercises
Determination of calcium concentration in human serum by
molecular absorbtion (spectro)photometry
The quality of results should comply with WHO procedure
requirements
EXERCISE 1:
EXERCISE 2:
EXERCISE 3:
64

Analyte
Calcium
Measurand
Total concentration of calcium in human serum
Units
mg dL-1

Measurement
procedure
To determine the calcium concentration in human serum, a serum sub-sample is

mixed with reagent colour and buffer solution, according to WHO standard operation
procedure. The absorbance of calcium calibration solutions and serum sample are
measured by visible spectrophotometry at 540 nm. From the calibration data the
concentration of calcium in human serum is calculated.
Type of calibration
standard curve
standard addition
internal standard
Model equation: calcium concentration in serum

V
cCa = ( m M Ca P ) 100 / V500 M CaCO3 (Vi / V100 ) ( Ax Ablank ) / ( A10 Ablank ) f V
int
cCD
M
WRWDOFDOFLXPFRQFHQWUDWLRQLQVHUXPVDPSOH>PJGL@
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V
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65
1
Matrix effect - recovery
Instrumental signal (absorbance)
Concentration of standard solutions - purity of CaCO3
Volume of the glassware (pipettes, volumetric flasks)
Mass
4. List the reference standards needed and state the information regarding
For the analyte
1
CaCO3 purity, Merck, min. 99.99 %
CaCO3 molar masses/IUPAC

1
e.g. mass/balance/calibrated by NMI, U=xx
Absorbance/(Spectro)photometer/Calibrated against
traceable optical standard (i.e. PTB)
Volume/Laboratory glassware (pipettes, volumetric

flasks/calibrated by manufacturer (i.e. Hirschmann
Laborgerate )
Mass/Analytical balance/calibrated by manufacturer

against traceable mass standards
66
Are all important parameters included

in the model equation?
Yes
Matrix effect
No

1
Via traceable calibration data
Via traceable volumetric measurements
Via traceable mass measurements
67

To determine the calcium concentration in human serum, a serum

sub-sample is mixed with reagent colour and buffer solution,
according to WHO standard operation procedure. The absorbance
of calcium calibration solutions and serum sample are measured by
visible spectrophotometry at 540 nm. From the calibration data the
concentration of calcium in human serum is calculated.
Analyte
Calcium
The measurand
Total calcium concentration in human serum
Unit
mg dL-1
2. Specify the scope

Matrix
Human serum
Measuring range
1.012.0 mg dL-1

Intended use of the results
Calcium concentration in serum result is intended to be used for clinical

interpretation
Parameters to be validated
Value requested by the customer
LOD
LOQ
Repeatability
Mark the customers
requirements and give
their values
Trueness
Measurement
uncertainty
Other-state
68
8 % as CV, by WHO procedure

2 % as CV, the actual state-of-art

VALIDATION
New in-house method
Full
Partial
69
Further information: ROCHE-Control serum type Precipath U
6. Measuring range
Linearity
Upper limit
LOD
LOQ
7. Spread precision
Repeatability
8. Robustness
70
9. Quality control
Control charts

R squared
Standard deviation of the analytical procedure
Coefficient of variation of the analytical procedure
71

validated
Calculations
LOD
LOQ
Repeatability
5
(c
i , obs
CV =
cQC
n ( n 1)
cQC
100 = 1.27 %
Trueness
Parameter
Value requested by
the customer
(the same as stated in question 3)
Value obtained
during validation
The requirement
is fulfilled
Yes/No
1.27 %
YES
LOD
LOQ
Repeatability
Within-lab
reproducibility
8 % as CV, by WHO procedure

2% as CV, the actual state-of-art
Trueness
Measurement
uncertainty
Other

Yes
No
For measurement uncertainty and traceability refer to the corresponding sheets

72

Measurand
Total calcium concentration in human serum
Unit
mg dL-1

equation
Measurement procedure
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Model equation: calcium concentration in serum

V
int
cCD
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PDVVRICDC2>PJ@
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V
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V
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VI
VLQW
73

Uncertainty of measurements of peak area
Method bias
Matrix effect
Other: Uncertainty of absorbance measurements
Other: Uncertainty of volume measurements

Input quantity
Value
Unit
625.0
mg
MCa
40.078
g mol-1
0.9999
mass fraction
V500
500.00
mL
MCaCO3
100.0869
g mol-1
Vi
20.000
mL
V100
100.000
mL
Ax
0.323
no units
A-10
0.338
no units
Ablank
0.052
no units
Vf
0.100
mL
Vint
0.100
mL
Remark
74
Input quantity
Standard
uncertainty
Unit
0.2
mg
MCa
0.002
g mol-1
0.0058
mass fraction
V500
0.15
mL
MCaCO3
0.0024
g mol-1
Remark
Vi
0.043
mL
V100
0.058
mL
Ax
0.004
no units
A-10
0.002
no units
Ablank
0.004
no units
Vf
0.002
mL
Vint
0.002
mL

V
int
cCD PJGL
Using:
6SUHDGVKHHWDSSURDFK
Input quantity
Value
Standard
uncertainty
Unit
625.0
0.2
mg
MCa
40.078
0.002
g mol-1
0.9999
0.0058
mass fraction
V500
500.00
0.15
mL
MCaCO3
100.0869
0.0024
g mol-1
Vi
20.000
0.043
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V100
100.000
0.058
mL
Ax
0.323
0.004
no units
A-10
0.338
0.002
no units
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0.052
0.004
no units
Vf
0.100
0.002
mL
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0.100
0.002
mL
CRPPHUFLDOVRIWZDUH
Remark
ucCD PJPRO
75
units
U(cCa) = k u (cCa) = 0.606 [mg dL-1], k = 2
1
Volume serum measurements
Concentration of serum sample from calibration data
76
Further readings
Guide to the Expression of Uncertainty in Measurement *8M VW HG
*HQHYH6ZLW]HUODQG
EurachemCitac Guide C* Qualtifying Uncertainty in Analytical Measurement
QGHG
6WDQGDUG RSHUDWLRQ SURFHGXUH IRU COLQLFDO FKHPLVWU\ 'HWHUPLQDWLRQ RI FDOFLXP E\
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FOLQLFDOFKHPLVWU\*(RIMIRMM
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DSSOLFDEOHVSUHDGVKHHWWHFKQLTXHAnalyst
77
Addendum I: Measurement uncertainty calculation:

Preparation of the standard solution
78
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Calibration
Calculation of calcium concentration in serum sample

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&
Chapter 3
Determination of Radium in Water

by a-Spectrometry
u
u
u
u

81
82
Measurand
Activity concentration of Ra-226 in water (Bq L-1) (by -spectrometry)
Example number
Ex-08
Determination of radium isotopes by BaSO4 coprecipitation for the

preparation of alpha-spectrometric sources
J.C. Lozano, F. Fernandez and J.M.G. Gomez, Journal of Radioanalytical and
Nuclear Chemistry 223 (1997) 12, 133137
Directive 98/83/EC on the quality of water intended for human

consumption
II. Attached files
1-I
File number, type and

name
EX-08-1-I-Ra226-waterAS-2006-Ver1.ppt
Content of the file

About the analytical procedure: short
introduction
2 - Yellow
PART I
PART II
EX-08-2-Y-Ra226-waterAS-2006-Ver1.doc
PART III
3 - Green
PART IV
Description of the analytical

procedure
measurement result
procedure relevant equations
and measurement data
Measurement uncertainty of the
result relevant equations and
measurement data
File is
attached
Yes No
9
9
9
9
Establishing traceability in
analytical chemistry
PART II

Addendum 1: By spreadsheet
approach
Addendum 2: By dedicated
software
PART III
Given
by the
lecturer
Each
participant
receives
own copy
and may
keep it
PART I
EX-08-3-G-Ra226-waterAS-2006-Ver1.doc
Remark

Version
April 2007
83
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Determination
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87
Determination of activity concentration of Ra-226 in drinking
water.
in the revised Directive 98/83/EC on the quality of water
intended for human consumption
PART I ..................................................................................................................... 89
PART II .................................................................................................................... 96
PART III ................................................................................................................... 97
measurement data
PART IV ................................................................................................................... 98
data
88
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Determination of radium isotopes by BaSO4 coprecipitation for the preparation of
alpha-spectrometric sources
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1. Scope
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2. Principle
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Figure 4. Experimental protocol for determination Ra-226 in water
3. Apparatus

90
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4. Reagents

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5. Sample preparation procedure

The radiochemical separation procedure of Ra-226 with lead coprecipitation
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6. Preparation of standard discs

6.1 Preparation of a Ba-133 standard disc
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6.2 Preparation of a Ra-226 standard disc

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93
8. Gamma and alpha counting

Gamma
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mRa-226SS ARa-226SS
RRa-226Std
9.2 Alpha spectrometer efficiency determination

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9.3 Activity concentration of Ra-226 in the sample (Bq L-1)

A Ra-226
ARD
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tRa-226
e det
PRa-226
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measurement result
Extract from the Directive 98/83/EC, Draft annex 2005/04/20 on the
quality of water intended for human consumption
Reference concentration for radioactivity in drinking water*
Origin
Nuclide
Reference concentration
Natural
Ra-226
0.5 Bq L-1
This table includes the most common natural and articial radionuclide Reference concentrations for other radionuclides can be
calculated using the dose coefcients for adults laid down in Annex III Table A of Directive 96/29/Euratom or more recent information
recognised by the competent authorities in the Member State, and by assuming an intake of 730 litres per year.
Performance characteristics and methods of analysis

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Parameter
Limit of detection
Notes
Ra-226
0.04 Bq L-1
Note 1
Note 2
Note 1: the limit of detection should be calculated according to ISO 11929-7, Determination of the detection limit and decision thresholds
for ionizing radiation measurements - Part 7: Fundamentals and general applications, with probabilities of errors of 1st and 2nd kind of
0.05 each
Note 2: measurement uncertainties should be calculated and reported as complete standard uncertainties, or as expanded standard
uncertainties with an expansion factor of 1.96, according to the ISO Guide for the Expression of Uncertainty in Measurement (ISO, Geneva
1993, corrected reprint Geneva, 1995)
96

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Equation
LLD =
tBkg
2.71 + 4.65 Bkg

det Rchem Vsample
Measurement data
Input quantity
Unit
Value
Rchem
radiochemical yield (recovery)
0.803
det
efficiency of alpha detector
0.2453
Bkg
peak area of background of alpha detector at the Ra-226 alpha energy
tBkg
time of measurement of background
Vsample
volume of the sample
97

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Equations
u ( ARa-226 )
ARa-226
u ( Rchem )
Rchem
u ( edet )
edet
u (Vsample )
u (PRa-226 ) u ( e det )
=
+
+
PRa-226 e det
Vsample
2
u (PBa-133Std )
=
+
PBa-133Std
u (mBa-133Std )
mBa-133Std
u (mRa-226SS )
u (PRa-226Std )
=
+
P
mRa-226SS
Ra-226Std
u (ARa-226 ) = k (ARa-226 )
98
u (Rchem )
+
Rchem
u PBa-133sample
+
PBa-133sample
u (ARa-226SS )
+
A
Ra-226SS
u mBa-133sample
+
mBa-133sample
u ( RRa-226Std )
+
R
Ra-226Std
peak area of Ra-226 in standard disc
radiochemical yield (recovery)
efficiency of alpha detector
radium standard disc recovery
PRa-226 Std
Rchem
det
RRa-226Std
-
peak area of Ba-133 in barium

standard disc
PBa-133 Std
peak area of Ba-133 in the sample
PBa-133 sample
peak area of Ra-226
Bq g-1
Unit
PRa-226
time of measurement of Ba-133 in

barium standard disc
time of the sample measurement (s)
tBa-133 sample
tBa-133Std
time of measurement
activity concentration of Ra-226 in

standard solution
tRa-226
ARa-226 SS
mRa-226 SS
mass of added Ba-133 in barium

standard disc
mass of added Ra-226 in standard
solution
mass of added Ba-133 in the sample
mBa-133 sample
mBa-133Std
volume of the sample
Vsample
Input quantity
Measurement data
12 785
5090
10 914
7516
3000
3000
300 000
2729
0.010
0.112
0.301
1.0
Value
113
71
104
87
0.001
0.001
0.001
0.002
(u)
Standard
uncertainty
Type of
uncertainty
normal
rectangular
Type of distribution
triangular
99
TrainMiC Exercises
Determination of activity concentration of Ra-226 in drinking
water.
The quality of the results should comply with the requirement
in the revised Directive 98/83/EC on the quality of water
EXERCISE 1:
EXERCISE 2:
EXERCISE 3:
100

Analyte
Ra-226
Measurand
Activity concentration of Ra-226 in water (drinking, surface, waste, )
Units
Bq L-1

Measurement
procedure

alpha-spectrometrical sources
Lozano et al., Journal of Radioanalytical and Nuclear Chemistry
Type of calibration
mixed standard source
standard addition
internal standard
Model equation
TKHDFWLYLW\FRQFHQWUDWLRQRIRDLQVDPSOH%TLLVFDOFXODWHGE\
A Ra-226 =
tRa-226
e det
PRa-226
Vsample
Rchem
ARD
DFWLYLW\FRQFHQWUDWLRQRIRDLQWKHVDPSOH>%TL@
PRD
SHDNDUHDRIRD
tRD
GHW
RFKHP
Rchem =
PBa-133sample
tBa-133Std mBa-133Std
PBa-133Std
RHFRYHU\REWDLQHGE\JDPPDVSHFWURPHWU\LVFDOFXODWHGDVIROORZV
RFKHP
P%DVDPSOH
SHDNDUHDRI%DLQWKHVDPSOH
t%DVDPSOH
m%DVDPSOH
P%D6WGD
101
t%D6WG
WLPHRIPHDVXUHPHQWRI%DVWDQGDUGGLVF>V@
m%D6WG
$OSKDVSHFWURPHWHUHIFLHQF\LVFDOFXODWHGDVIROORZV
GHW =
tRa-226Std
PRa-226Std
mRa-226SS ARa-226SS
RRa-226Std
GHW
RRD6WG
PRD6WG
SHDNDUHDRIRDRIVWDQGDUGGLVF
tRD6WG
WLPHRIPHDVXUHPHQWRIRDVWDQGDUGGLVF>V@
mRD66
PDVVRIDGGHGRDVWDQGDUGVROXWLRQ>J@
ARD66
RDDFWLYLW\FRQFHQWUDWLRQLQVWDQGDUGVROXWLRQ>%TJ@
1
Uncertainty of volumes
Uncertainty of weighing
Uncertainty of measurement, using alpha and gamma detectors
For the analyte
102
Standard Radionuclide Source, Analytics, SRS 67978-121
Ba-133 standard solution, Czech Metrological Institute,

Cert. No: 931-OL-137/99
Ra-226 standard solution, NIST SRM 4967

1
(k = 2) see also data yellow sheet
Graduated and mixing cylinders, volumetric flask/with

established traceability
BLAUBRAND tolerance
Mass/calibrated balance/with established traceability

Sartorius

model equation?
Yes
Uncertainty of measured background of detector,

uncertainty of measured blank reagents (minor
contributions)
No

1
Analysis of matrix CRM
Participation in a proficiency testing scheme
103

The measurement
procedure

alpha-spectrometric sources
J.C. Lozano, F. Fernandez and J.M.G. Gomez
Journal of Radioanalytical and Nuclear Chemistry 223 (1997) 12, 133137.
Analyte
Ra-226
The measurand
Activity concentration of Ra-226 in drinking water
Unit
Bq L-1

Matrix
Drinking water
Measuring range
0.0110 Bq L-1

Compliance to the requirements in the revised water directive 98/83/EC on

the quality of water intended for human consumption

0.04 Bq L-1
LOD
LOQ
Mark the customers
their values
Repeatability
Trueness
Other-state

VALIDATION
104
New in-house method
Full
Partial
spiking of samples with pure substances and calculation of recovery
6. Measuring range
Linearity
Upper limit
LOD
LOQ
7. Spread precision
Repeatability
105
8. Robustness
9. Quality control
Control charts

R square
106

Parameters requested to
be validated
Calculations
LLD =
LOD
2.71 + 4.65 14.26092744

= 0.000245 Bq L-1
420 730 0.2453 0.803 1
LOQ
Repeatability
Trueness
Parameter

customer
LOD
0.04 Bq L-1
LOQ
Repeatability
Value obtained
during validation
The requirement
is fulfilled
Yes/No
0.00025 Bq L-1
YES
Within-lab
reproducibility
Trueness
Measurement
uncertainty
Other

Yes
No
107

Measurand
Activity concentration of Ra-226 in water (drinking, surface, waste, )
Unit
Bq L-1

equation
'HWHUPLQDWLRQRIUDGLXPLVRWRSHVE\%D62FRSUHFLSLWDWLRQIRUWKHSUHSDUDWLRQRIDOSKD
VSHFWURPHWULFVRXUFHV
-CLR]DQR))HUQDQGH]DQG-M**RPH]
-RXUQDORIRDGLRDQDO\WLFDODQG1XFOHDUCKHPLVWU\223
Model equation:
TKHDFWLYLW\FRQFHQWUDWLRQRIRDLQWKHVDPSOH%TLLVFDOFXODWHGE\
A Ra-226 =
108
tRa-226
det
PRa-226
Vsample
Rchem
ARD
$FWLYLW\FRQFHQWUDWLRQRIRDLQWKHVDPSOH>%TL@
PRD
SHDNDUHDRIRD
tRD
GHW
RFKHP
RHFRYHU\PHDVXUHGE\JDPPDVSHFWURPHWU\LVFDOFXODWHGDVIROORZV
Rchem =
PBa-133sample
mBa-133Std
tBa-133Std
PBa-133Std
RFKHP
P%DVDPSOH
PHDNDUHDRI%DLQWKHVDPSOH
t%DVDPSOH
m%DVDPSOH
P%D6WG
t%D6WG
WLPHRIPHDVXUHPHQWRI%DLQEDULXPVWDQGDUGGLVF>V@
m%D6WG
$OSKDVSHFWURPHWHUHIFLHQF\GHWHUPLQDWLRQLVFDOFXODWHGDVIROORZV
GHW =
tRa-226Std
PRa-226Std
mRa-226SS ARa-226SS
RRa-226Std
GHW
RRD6WG
PRD6WG
SHDNDUHDRIRDLQVWDQGDUGGLVF
tRD6WG
WLPHRIPHDVXUHPHQWRIRDVWDQGDUGGLVF>V@
mRD66
PDVVRIDGGHGRDVWDQGDUGVROXWLRQ>J@
ARD66
RDDFWLYLW\FRQFHQWUDWLRQLQVWDQGDUGVROXWLRQ>%TJ@

Uncertainty of measurements of peak area (alpha and gamma detectors)
Method bias
Matrix effect
Other: Uncertainty of volume measurements
Other: Uncertainty of weighing
Other: Uncertainty of measured background of alpha and gamma detectors
Other: Uncertainty of measured blank reagents, filters, discs
109

Input quantity
Value
Unit
PRa-226
7516
tRa-226
300 000
det
0.2453
Vsample
1.0
Rchem
0.803
Remark

Input quantity
Standard
uncertainty
Unit
PRa-226
87
tRa-226
det
0.01392
Vsample
0.0020
Rchem
0.0142
Remark
Constant

A Ra-226 =
A Ra-226 =
tRa 226
PRa-226
e det Vsample
7516
300 000 0.2453 1
1
Rchem
1
= 0.127 Bq L-1
0.803
7. Calculate the combined standard uncertainty (uc ) of the result and specify units
Using:
110
6SUHDGVKHHW$SSURDFK
Input quantity
Value
Standard
uncertainty
Unit
PRa-226
7516
87
tRa-226
300 000
det
0.2453
0.01392
Remark
CRPPHUFLDO6RIWZDUH
Vsample
1.0
0.0020
Rchem
0.803
0.0142
u ( ARa-226 )
ARa-226
u ( ARa-226 )
ARa-226
u (Vsample )
u (PRa-226 ) u ( edet )
=
+
+
PRa-226 edet
Vsample
2
87 0.01392
0.0020
=
+
+
7516 0.2453
1
u (Rchem )
+
Rchem
0.0142
+
= 0.00806
0.803
units
u (ARa-226 ) = k (ARa-226 )
U = 2 0.00806 = 0.016 Bq L-1
contributing the most to uc
1
Mass of Ra-226 standard solution
Peak area of Ba-133 in the standard disc
Peak area of Ra-226 of the sample

See the attached Excel calculations and calculations done using the software
GumWorkbench
111
Further readings
(CCRXQFLO'LUHFWLYHRI-XO\UHODWLQJWRWKHTXDOLW\RIZDWHULQWHQGHG
IRUKXPDQFRQVXPSWLRQOfc. J. Eur. Commun.L
(CCRXQFLO'LUHFWLYH(CRI1RYHPEHUTKHTXDOLW\RIZDWHULQWHQGHG
(8R$T2M CRXQFLO RHJXODWLRQ (XUDWRP 1R RI -XO\
DPHQGLQJRHJXODWLRQ(XUDWRP1ROD\LQJGRZQPD[LPXPSHUPLWWHGOHYHOV
RI UDGLRDFWLYH FRQWDPLQDWLRQ RI IRRGVWXIIV DQG RI IHHGLQJVWXIIV IROORZLQJ D QXFOHDU
DFFLGHQW RU DQ\ RWKHU FDVH RI UDGLRORJLFDO HPHUJHQF\ Ofc. J. Eur. Commun. L

(8R$T2M (XURSHDQ CRPPLVVLRQ RHFRPPHQGDWLRQ (8R$T2M
Ofc. J. Eur. Commun. L
Guidelines for Drinking Water Quality, Recommendation YRO QG HG
:+2*HQHYD
Guidelines for Drinking Water Quality, Recommendation YRO UG FXUUHQW HG
LQFOXGLQJWKHUVWDGGHQGXP:+2*HQHYD$YDLODEOHIURPKWWSZZZZKRLQW
ZDWHUBVDQLWDWLRQBKHDOWK
-CLR]DQR))HUQDQGH]DQG-M**RPH]'HWHUPLQDWLRQRIUDGLXPLVRWRSHVE\
%D62FRSUHFLSLWDWLRQIRUWKHSUHSDUDWLRQRIDOSKDVSHFWURPHWULFVRXUFHVJ. Radioanalyt.
Nucl. Chem.
< 6SDVRYD 6 PRPPp L %HQHGLN DQG 8 :lWMHQ 8QFHUWDLQW\ %XGJHW IRU RD
$FWLYLW\ FRQFHQWUDWLRQ LQ:DWHU E\$OSKD 6SHFWURPHWU\ Acta. Chim. Slov.

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RD LQ ERWWOHG GULQNLQJ ZDWHU E\ DOSKD VSHFWURPHWU\ LQ C' Proceedings of the 7th
International Conference on Nuclear and Radiochemistry 1RC $XJXVW
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112

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Addendum I: Measurement uncertainty calculation, spreadsheet approach (Excel)

113
114

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Addendum II: Measurement uncertainty calculation

GumWorkbench
Model equation:
ARD= PRDtRDGHW VVDPSOHRFKHP
RFKHP P%DVDPSOHW%DVDPSOHm%DVDPSOHt%D6WGm%D6WGP%D6WG
GHW= PRD6WGtRD6WGmRD66 ARD66RRD6WG
List of quantities:
Quantity
ARa-266
Unit
-1
Bq L
edet
Vsample
Activity of Ra-266 in sample

Area of Ra-266
PRa-266
tRa-266
Definition
Time of measurement
Efficiency for alfa detector
Volume of the sample
Rchem
Radiochemical yield (recovery)
PBa-133sample
Area of Ba-133 in sample
tBa-133sample
Time of measurement of the sample
mBa-133sample
Mass of Ba-133 in the sample
tBa-133Std
Time of measurement of Ba-133 standard disc
mBa-133Std
Mass of Ba-133 standard disc
PBa-133Std
Area of Ba-133 in standard disc
PRa-226Std
Area of Ra-266 in standard disc
tRa-226Std
Time of measurement of the standard disc
mRa-226SS
Mass of Ra-226 standard solution
ARa-226SS
Activity of Ra-226 in standard solution
RRa-226Std
Radium standard disc recovery
PRa-266:
T\SH$VXPPDULVHG
MHDQ
6WDQGDUG8QFHUWDLQW\
tRa-266:
CRQVWDQW
9DOXHV
117
Vsample:
T\SH%WULDQJXODUGLVWULEXWLRQ
9DOXHL
+DOIZLGWKRIOLPLWVL
PBa-133sample:
T\SH$VXPPDULVHG
MHDQ
6WDQGDUG8QFHUWDLQW\
tBa-133sample:
CRQVWDQW
9DOXHV
mBa-133sample:
T\SH%UHFWDQJXODUGLVWULEXWLRQ
9DOXHJ
+DOIZLGWKRIOLPLWVJ
tBa-133Std:
CRQVWDQW
9DOXHV
mBa-133Std:
9DOXHJ
+DOIZLGWKRIOLPLWVJ
PBa-133Std:
T\SH$VXPPDULVHG
MHDQ
6WDQGDUG8QFHUWDLQW\
PRa-226Std:
T\SH$VXPPDULVHG
MHDQ
6WDQGDUG8QFHUWDLQW\
tRa-226Std:
CRQVWDQW
9DOXHV
118
mRa-226SS:
9DOXHJ
+DOIZLGWKRIOLPLWVJ
ARa-226SS:
T\SH$VXPPDULVHG
MHDQ
6WDQGDUG8QFHUWDLQW\
RRa-226Std:
T\SH$VXPPDULVHG
MHDQ
6WDQGDUG8QFHUWDLQW\
Uncertainty budgets:
ARa-266: Activity of Ra-266 in sample
Quantity
Value
Standard
Uncertainty
Distribution
Sensitivity
Coefficient
Uncertainty
Contribution
Index
PRa-266
7516.0
86.0
normal
17 10-6
1.5 10-3 Bq L-1
3.3 %
tRa-266
300.0 103 s
Vsample
1.00000 L
2.04 10-3 L
triangular
-0.13
-260 10-6 Bq L-1
0.1 %
104
normal
-12 10
-1
-1.2 10 Bq L
2.3 %
577 10-6 g
rectangular
0.42
240 10-6 Bq L-1
0.0 %
-6
-3
PBa-133sample
10 914
tBa-133sample
3000.0 s
mBa-133sample
0.301200 g
tBa-133Std
3000.0 s
mBa-133Std
0.112800 g
577 10-6 g
rectangular
-1.1
-650 10-6 Bq L-1
0.7 %
PBa-133Std
5090.0
71.0
normal
25 10-6
1.8 10-3 Bq L-1
4.9 %
PRa-226Std
12785
113
normal
-9.9 10-6
-1.1 10-3 Bq L-1
2.0 %
tRa-226Std
2000.0 s
mRa-226SS
0.010220 g
577 10-6 g
rectangular
12
7.2 10-3 Bq L-1
79.9%
ARa-226SS
2729.0
10.7
normal
47 10-6
500 10-6 Bq L-1
0.4 %
RRa-226Std
0.9344
0.0150
normal
0.14
2.0 10-3 Bq L-1
6.5 %
ARa-266
-1
0.12719 Bq L
8.04 10 Bq L
-3
-1
119
det: Efciency of alfa detector

Quantity
Value
Standard
Uncertainty
Distribution
Sensitivity
Coefficient
Uncertainty
Contribution
Index
PRa-226Std
12 785
113
normal
19 10-6
2.2 10-3
2.2 %
tRa-226Std
2000.0 s
mRa-226SS
0.010220 g
577 10-6 g
rectangular
not valid!
-0.014
normal
-90 10
-960 10
0.4 %
-0.26
-3.9 10
7.2 %
ARa-226SS
2729.0
10.7
RRa-226Std
0.9344
0.0150
normal
edet
0.2453
0.0146
-6
90.1 %
-6
-3
Rchem: Radiochemical yield (recovery)

Quantity
Value
Standard
Uncertainty
Distribution
Sensitivity
Coefficient
Uncertainty
Contribution
Index
PBa-133sample
10 914
104
normal
74 10-6
7.7 10-3
28.8 %
tBa-133sample
3000.0 s
mBa-133sample
0.301200 g
577 10-6 g
rectangular
-2.7
-1.5 10-3
1.2 %
tBa-133Std
3000.0 s
mBa-133Std
0.112800 g
577 10-6 g
rectangular
7.1
4.1 10-3
8.3 %
-160 10
-0.011
61.7 %
PBa-133Std
5090.0
71.0
normal
Rchem
0.8030
0.0143
-6
Result:
120
Quantity
Value
Expanded
Uncertainty
Coverage factor
Coverage
ARa-266
0.127 Bq L-1
0.016 Bq L-1
2.00
95 %
Chapter 4
Determination of Polar Pesticides by Liquid

Chromatography Mass Spectrometry
u
u
u
u

121

Measurand
Concentration of imazalil and thiabendazole in tangerines by liquid

chromatography-mass spectrometry
Example number
Ex-04
122
Determination of concentration of imazalil and thiabendazole in

tangerines by liquid chromatography-mass spectrometry. The sample
preparation procedure is modified AOAC 985.22 procedure. The
measurement procedure is an in-house developed procedure.
The quality of the results should comply with the requirements given
in the EU Directives 93/58/EEC and 00/42/EEC on pesticide residues
analysis
II. Attached files
1-I
File number,
type and name
Ex-04-1-IPesticidesFood-LCMS2006-Ver1.ppt
2 - Yellow
PART II
PART III
3 - Green
PART IV
Ex-04-3-GPesticidesFood-LCMS2006-Ver1.doc
PART I
Ex-04-2-YPesticidesFood-LCMS2006-Ver1.doc
File is
attached
Yes No
Content of the file

The customers requirements concerning
the quality of the measurement result
measurement data
relevant equations and measurement
data
Given by the
leacturer
9
Each
participant
receives own
copy and may
keep it
9
9
9
PART I

chemistry
PART II

PART III
Remark

Version
0
1
April 2007
123
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127
Determination of concentration of imazalil and thiabendazole
in tangerines by liquid chromatography mass spectrometry.
in the EU directives 93/58/EEC and 00/42/EEC/ on pesticide
residues analysis
PART I ............................................................................................................................... 129

PART II .............................................................................................................................. 133
The customers requirement concerning quality of the measurement result
PART III ............................................................................................................................. 135
measurement data
PART IV ............................................................................................................................ 137
data
128
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129
Laboratory sample is homogenized using appropriate equipment
50 g aliquot of homogenized sample is extracted with 100 mL of acetone using high

speed blender. Before the extraction standard solution can be added for recovery studies
Mixture is vacuum filtered through filter paper, the extraction vessel is rinsed and
filter cake is washed with approximately 30 mL of acetone
The volume of the extract is measured and a 50 mL aliquot is taken for further
purification through liquid-liquid extraction
In a separatory funnel the aliquot is extracted for 1 min with 100 mL of petroleum
ether and dichloromethane mixture (1:1)
The lower (water) phase is drained into volumetric cylinder, the upper organic layer
is filtered/dried through approximately 3 cm layer of anhydrous Na2SO4 in a funnel
The water phase is saturated in the separatory funnel with NaCl and extracted twice
for 1 min with 50 mL of dichloromethane. The lower (organic) layer is also
filtered/dried through the same Na2SO4 layer
The combined extract is brought down to couple of millilitres using rotary

evaporator, taking care not to evaporate to dryness
The extract is brought to almost complete dryness in slow flow of N2, then the
residue is reconstituted with 10 mL of methanol
If necessary the extracts are diluted in order to fit in the calibration range
Figure 5. Flow chart of the analytical procedure
130
3. Interferences
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4. Reagents
1000 mg kg-1 individual pesticide standard solutions
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5. Sampling and pre-treatment

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131
6. Calculation
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132
PART II. The customers requirement concerning quality of the

measurement result
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IPD]DOLOPJNJIRUFLWUXV'LUeFWLYe((C

TKLDEeQGD]ROePJNJIRUFLWUXV'LUeFWLYe(C
Extract from the EU Quality Control Procedures for Pesticide Residues Analysis,
SANCO/10232/2006

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133
Table 3. Recommended maximum permitted tolerances for relative ion intensities

using a range of spectrometric techniques
134
Relative intensity
(% of base peak)
EI-GC-MS
(relative)
CI-GC-MS, GC-MSn, LC-MS, LC-MSn

(relative)
>50 %
10 %
20 %
>2050 %
15 %
25 %
>1020 %
20 %
30 %
10 %
50 %
50 %

Equations
R=
wexp
wtheor
100 %
STDEV =
n x 2
AVERAGE =
( x)
n(n 1)
n
STDEV
RSD =
100 %
AVERAGE
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135
Measurement data
Imazalil
Thiabendazole
wexp
(mg kg-1)
wtheor
(mg kg-1)
0.06427
R
(%)
R
(%)
Imazalil
Thiabendazole
Peak area
Peak area
wexp
(mg kg-1)
wtheor
(mg kg-1)
0.05597
0.03120
0.04244
3 996 669
300 802
0.07516
0.05871
0.03281
0.04452
3 459 066
281 164
0.04812
0.05821
0.03181
0.04413
3 838 651
230 775
0.10238
0.07342
0.04095
0.05567
3 727 188
274 366
0.04201
0.06088
0.03400
0.04616
3 414 893
296 724
0.05741
0.06241
0.03331
0.04732
3 553 740
258 916
AVERAGE recovery
AVERAGE recovery
AVERAGE mass fraction
STDEV of recovery
STDEV of recovery
STDEV of mass fraction
RSD of recovery (urel_rec)
RSD of recovery (urel_rec)
RSD of mass fraction

(urel_meth)
* The recovery determinations were carried out two per day on three consecutive days.
136

Equations
2
2
+ urnd
uw = usys
urnd =
2
2
+ urel_meth
urel_rec
100 %
d = w wref
uref =
udev =
s
n1
d2
n
2
2
usys = uref
+ udev
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137
Measurement data
138
Imazalil
Thiabendazole
urel_rec
27 %
2%
urel_meth
10 %
6%
1.3350 mg kg-1
3.5230 mg kg-1
wref
1.2975 mg kg-1
3.2863 mg kg-1
0.0530 mg kg-1
0.5571 mg kg-1
nl
Comments
The relative standard deviation of recovery
calculated from parallel measurement results (two
measurements per day on three consecutive days)
The relative standard deviation of results obtained
for the same solution from repeated injections of
the same solution
consensus value of interlaboratory comparison

measurement
TrainMiC Exercises
Determination of concentration of imazalil and thiabendazole
in tangerines by liquid chromatography-mass spectrometry.
in pesticide residues analysis directives and guidelines
EXERCISE 1:
EXERCISE 2:
EXERCISE 3:
Addendum I. By spreadsheet approach
Addendum II. By dedicated software
139

Analyte
Residues of imazalil and thiabendazole
Measurand
Acetone-extractable imazalil and thiabendazole residues in tangerines
Units
mg kg-1 (ppm)
Measurement
procedure
50 g of homogenized sample is extracted with 100 mL of acetone using high speed

blender. Mixture is filtered and the volume of extract is measured.
50 mL of the extract is extracted with 100 mL dichloromethane petroleum ether
mixture (1:1), the organic layer is filtered through a layer of sodium sulphate (for
drying purpose). Water phase is saturated with NaCl and extracted twice with 50
mL of dichloromethane. Organic extracts are dried as before. Solvent is evaporated
to almost dryness and the sample is dissolved in 1020 mL of methanol. Sample is
filtered through a syringe filter and analysed using LC-MS system.
Sample preparation procedure is based on the AOAC official method 985.22
Organochlorine and Organophosphorus Pesticide Residues Gas Chromatographic
Method. The modifications were made in order to cut down sample size and thus
solvent consumption. Also changes were made in the solvent of final extract to suite
LC-MS system. LC-MS analysis method was developed within laboratory.
Type of calibration
standard curve
Standard addition
internal standard
Model equation
w=
w
wF
V
140
wc V10 Ve
V50 m
PDVVIUDFWLRQRIe[WUDFWDEOeSeVWLFLGeLQVDPSOePJRISeVWLFLGeSeUNJRI
VDPSOe>PJNJ@
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Ve
V
1
Mass fraction of extractable pesticide in analysed extract (wc, mg kg-1)
The full volume of acetone extract (Ve, mL)
The volume of final extract in methanol (V10, mL)
The volume of acetone extract to be purified (V50, mL)
The density of methanol (, g mL-1)
The mass of homogenized sample (m, g)
For the analyte
1
Name/ChemicalFormula/
Producer:
Name/ChemicalFormula/
Producer:
Imazalil (solid substance)/C14H14Cl2N2O/Dr. Ehrenstorfer

Value including uncertainty (with units):
Imazalil: purity 97.5 % (tolerance 0.5 %) (data obtained from
corresponding Certificate of Analysis)
Thiabendazole (solid substance)/C10H7N3S/Dr. Ehrenstorfer
Value including uncertainty (with units):
Thiabendazole: purity 99.0 % (tolerance 0.5 %) (data obtained from
corresponding Certificate of Analysis)


None

Are all important parameters included in the model
equation?
Yes
No

1
Participate in EU proficiency testing programme
Analyse a CRM (in future, when such CRM becomes available)
141
142
SINGLE LABORATORY VALIDATION OF

MEASUREMENT PROCEDURES
The measurement
procedure
Analyte
The measurand
Unit
Sample preparation procedure is modified AOAC official method 985.22. Analysis

was carried out on an LC-MS system using a self-developed chromatographic
method.
Residues of imazalil and thiabendazole (polar basic pesticides)
Acetone-extractable pesticides in tangerines.
Results are not recovery corrected, thus extractable pesticides are determined, not
total amounts.
mg kg-1 (ppm)

Matrix
Tangerines
Measuring range
imazalil 0.0040.9 mg kg-1

thiabendazole 0.0030.7 mg kg-1

Post-registration control and monitoring of pesticides based on MRLs set by

the EU Directives 93/58/EEC and 00/42/EEC for imazalil and thiabendazole
respectively.
LOD < 0.02 mg kg-1 (imazalil), LOD < 0.05
LOD
mg kg-1 (thiabendazole)
LOQ
Repeatability
Within-lab
reproducibility
Trueness
Recovery between 70110 %
Measurement
uncertainty
Identity/confirmation: retention time (compared with
standard) + MS^2 fragmentation: imazalil (297 201),
thiabendazole (202 175) + additional qualifier ion
comparison if necessary. Guidance document refers to
sufficient confirmation when MS^2 is used and ion ratios in
standard and sample agree within the limits specified in
Table 3 (Yellow sheet, Part II).
Other - state
Mark the customers

requirements and give their
values
143

VALIDATION
144
New in-house method
Full
Partial
At approximate concentration level of 0.05 mg kg-1
Chromatographic separation and mass-spectrometric identification (including MS^2 confirmation of
identity)
The method has been proved via ILC to perform with tangerine, orange and tomato
Confirmation of identity: chromatographic retention time and MS^2 confirmation of identity
6. Measuring range
Linearity
Imazalil: 0.0040.9 mg kg-1; Thiabendazole: 0.0030.7 mg kg-1
Upper limit
Imazalil: 0.9 mg kg-1; Thiabendazole: 0.7 mg kg-1
LOD
Imazalil: 0.004 mg kg-1; Thiabendazole: 0.003 mg kg-1
LOQ
7. Spread precision
Repeatability
Instrumental: standard deviation of the measurement method: 10 % for imazalil and 6 % for
thiabendazole (repeated injection of the same standard solution).
Reproducibility (within Lab)
Full procedure: standard deviation of recovery experiments carried out on three consecutive days
27 % for imazalil, 2 % for thiabendazole (full sample preparation included )
Reproducibility (between Lab)
in ILC the difference between results were 5.6 and 4.4 % for imazalil and thiabendazole respectively
145
8. Robustness
Variation of some of the parameters: during method development two different columns were used
(C182504.6 5, C18150150 2.1), mobile phase composition and velocity were changed in
increments and obtained data analysedd, final extract volumes of 10 and 20 mL were utilized.
9. Quality control
Control charts

R square
Other-state: Confirmation of identity: in accordance with requirements in Section 3.
146

Parameters requested
to be validated
LOD
Calculations
Since the method permits in principle to obtain significantly lower LOD values
than requested by the customer, LOD was estimated in a conservative way by
taking the lowest points on the respective calibration graphs as LOD estimates.
Values obtained:
Imazalil: 0.004 mg kg-1
Thiabendazole: 0.003 mg kg-1
LOQ
Repeatability
Within-lab
reproducibility
Average recovery; for data and equations see first document
Imazalil 104 %
Thiabendazole 73 %
R=
Trueness
wexp
wtheor
100 %
Recovery is found according to the following equation:

R recovery of the method [%]
wexp experimentally measured mass fraction of the pesticide residue in
the sample, in recovery studies the pesticide sis spiked into the sample
homogenate [mg kg-1]
wtheor theoretically calculated mass fraction of the pesticide residues in the
spiked sample [mg kg-1]
Measurement
uncertainty
Other - please
state
147
Parameter

customer
LOD
Value obtained
during validation
The requirement
is fulfilled
Yes/No
Imazalil < 0.02 mg kg-1

Thiabendazole < 0.05 mg kg-1
0.004 mg kg-1
0.003 mg kg-1
Yes
Yes
70110 %
Imazalil 104 %
Thiabendazole 73 %
Yes
Yes
Confirmation based on similarity to

standard (MS^2 spectrum)
MS^2 spectrum in
sample is similar to
standard
Yes
LOQ
Repeatability
Within-lab
reproducibility
Trueness
Measurement
Other

Yes
No
148

Measurand
Extractable pesticide content in fruit/vegetable
Unit
mg kg-1

equation
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Model equation
w=
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Method bias
Matrix effect: matrix effects on ionisation of pesticides (repeatability)
Other: repeatability of extraction of the pesticides
Other: stability of standard solutions, integration
Other: calibration graph linearity
151

Input
quantity
Value
Imazalil
Thiabendazole
wc
2.801
V10
Unit
Remark
7.398
mg kg-1
Mass fraction of residue in extract, calculated based

on calibration
10
10
mL
Volume of final methanol extract
0.791
0.791
g mL-1
Density of methanol
Ve
150
150
mL
Volume of extract after filtration
V50
50
50
mL
Volume of extract taken for further cleaning
49.8003
49.8003
Sample amount taken for extraction
5. Evaluate the standard uncertainty of each input quantity2

Unit
Imazalil
Thiabendazole
uref
0.0375
0.3216
mg kg-1
udev
0.0375
0.2367
mg kg-1
urel_rec
27
urel_meth
10
Remark
systematic uncertainty component evaluated based
on the results of ILC
random component of uncertainty, calculated using
relative uncertainty (repeatability) of recovery and
method
relative standard deviation of recoveries calculated
using addition experiments
relative standard deviation of measuring method
(repeated analysis of the same solution)
w=
w
wF
V
Ve
V
m
wc V10 Ve
V50 m
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152
w(imazalil) =
2.801 10 0.791 150

= 1.335 mg kg -1
50 49.8003
w( thiabendazole) =
7.398 10 0.791 150

= 3.523 mg kg -1
50 49.8003
7. Calculate the combined standard uncertainty (uw ) of the result and specify units
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Using:
Uncertainty
components
Value
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Standard
uncertainty
Unit
usys (imazalil)
0.0530
mg kg-1
urnd (imazalil)
0.3844
mg kg-1
usys (thiabendazole)
0.3993
mg kg-1
urnd(thiabendazole)
0.2228
mg kg-1
CRPPeUFLDOVRIWZDUe
Remark
systematic uncertainty component
evaluated based on the results of ILC
random component of uncertainty,
calculated using relative uncertainty
(repeatability) of recovery and method
systematic uncertainty component
evaluated based on the results of ILC
random component of uncertainty,
calculated using relative uncertainty
(repeatability) of recovery and method
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8. Calculate expanded uncertainty (Uw ) and specify the coverage factor k and the units
Imazalil
uw = 0.053032 + 0.38442 = 0.388 mg kg -1
urnd =
27 % 2 + 10 % 2
1.3350 = 0.3844 mg kg -1
100 %
d = 1.3350 1.2975 = 0.0375 mg kg -1
0.0530
uref =
= 0.0375 mg kg -1
2
udev =
0.03752
= 0.0375 mg kg -1
1
usys = 0.03752 + 0.03752 = 0.05303 mg kg -1
Thiabendazole
uw = 0.39932 + 0.22282 = 0.457 mg kg -1

urnd =
2 %2 + 6 %2
3.860 = 0.2228 mg kg -1
100 %
d = 3.5230 3.2863 = 0.2367 mg kg -1
0.5571
uref =
= 0.3216 mg kg -1
2
udev =
0.2367 2
= 0.2367 mg kg -1
1
usys = 0.32162 + 0.2367 2 = 0.3993 mg kg -1

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154
contributing the most to uw
1
urnd contribution: 98.13 % (imazalil), 23.74 % (thiabendazole)
usys contribution: 1.87 % (imazalil), 76.27 % (thiabendazole)

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Further readings
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% MDJQXVVRQT 1l\NNL + +RYLQG DQG M .U\VeOO Handbook for Calculation of
Measurement Uncertainty in Environmental LaboratoriesQGeGI661
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156
Chapter 5
Determination of Ammonium in Water by Continuous

Flow Analysis (CFA) and Spectrometric Detection
Bertil Magnusson
u
u
u
u
The summary form (blue page)

157
The TrainMiC example summary form
158
Measurand
Mass concentration of ammonium in drinking water in mg L-1
Example number
Ex-07
Author(s) of the example
Bertil Magnusson
Determination of concentration of ammonium in drinking water by

continuous flow analysis (CFA) and spectrometric detection (ISO 11732:
2005)
Customer requirement
Directive 98/83/EC on the quality of water intended for human

consumption
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
II. Attached files
3 - Green
2 - Yellow
1-I
File number, type

and name
Ex-07-1-INH4-waterPhotometry2006-Ver1.ppt
Ex-07-2-YNH4-waterPhotometry2006-Ver1.doc
Ex-07-3-GNH4-waterPhotometry2006-Ver1.doc
File is
attached
Yes No
Content of the file
About the analytical procedure: short

introduction
PART I
Description of the analytical

procedure
PART II

measurement result
PART III

measurement data
PART IV
Measurement uncertainty of the

result relevant equations and
measurement data
PART I

chemistry
PART II

Addendum 1: By spreadsheet
approach
PART III
Remark
Given by the
lecturer
Each participant
receives own
copy and may
keep it

Version
0
1
April 2007
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and

Spectrometric Detection
159
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163
Determination of concentration of ammonium in drinking water
by flow analysis (CFA and FIA) and spectrometric detection.
in the Directive 98/83/EC on the quality intended for human
consumption
PART I ................................................................................................................................ 165

PART II .............................................................................................................................. 168
The customers requirement concerning quality of the measurement result
PART III ............................................................................................................................. 169
measurement data
PART IV ................................................................................................................. 171
data
164
1. Scope
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2. Principle CFA Continuous Flow Analysis
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3. Interferences CFA method

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165
4. Reagents here only calibrant is described

Ammonium stock solution, CN = 1000 mg L-1
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Standard solutions, 10 mg L-1

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Calibration solutions
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Working solutions 0.11.0 mg L-1

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5. Sampling and pre-treatment

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166
6. Procedure
Instrument set-up
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7. Method of calculation
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PART II. The customers requirement concerning quality of the

measurement result
Extract from the Directive 98/83/EC (Draft annex 2005/04/20), on the quality of water
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Parameter
Trueness of parametric value

(Note 1)
Ammonium
10 %
Precision of
parametric value
(Note 2)
10 %
Limit of detection of
parametric value
(Note 3)
10 %
Note 1

TUXeQeVV LV WKe V\VWePDWLF eUURU DQG LV WKe GLIIeUeQFe EeWZeeQ WKe PeDQ
YDOXeRIWKeODUJeQXPEeURIUeSeDWeGPeDVXUePeQWVDQGWKeWUXeYDOXe
Note 2

PUeFLVLRQ LV WKe UDQGRP eUURU DQG LV XVXDOO\ e[SUeVVeG DV WKe VWDQGDUG
GeYLDWLRQ ZLWKLQ DQG EeWZeeQ EDWFK RI WKe VSUeDG RI UeVXOWV DERXW WKe
PeDQ$FFeSWDEOeSUeFLVLRQLVWZLFeWKeUeODWLYeVWDQGDUGGeYLDWLRQ
TKeVeWeUPVDUeIXUWKeUGeQeGLQI62
Note 3:
168
LLPLWRIGeWeFWLRQLVeLWKeU
WKUee WLPeV WKe UeODWLYe ZLWKLQ EDWFK VWDQGDUG GeYLDWLRQ RI D QDWXUDO
VDPSOeFRQWDLQLQJDORZFRQFeQWUDWLRQRIWKeSDUDPeWeURU
Ye WLPeV WKe UeODWLYe ZLWKLQ EDWFK VWDQGDUG GeYLDWLRQ RI D EODQN
VDPSOe

Limit of Detection
Equation
CDOFXODWeGeWeFWLRQOLPLWDVVWDQGDUGGeYLDWLRQVVee'LUeFWLYe(C
Measurement data
$V\QWKeWLFFRQWUROVDPSOeDWDOeYeORIPJLKDVEeeQUXQIRURYeUDSeULRGRI
PRQWKVTKeUeVXOWVLQPJLDUeJLYeQLQWKeWDEOeEeORZ

Internal quality control

TKeVWDQGDUGGeYLDWLRQVREWDLQeGRQWKeVeFRQWUROVDPSOeVDUeeVWLPDWeVRQWKeZLWKLQ
ODERUDWRU\UeSURGXFLELOLW\
Measurement data
ReVXOWVIURPWZRFRQWUROVDPSOeVDUeJLYeQLQWKeWDEOeEeORZ
Unit
QC1
QC2
Mean value
mg L-1
0.114
0.605
mg L-1
0.005
0.021
27
28
Time period
months
Nominal value
mg L-1
0.100
0.600
169
External quality control participating in PT studies
170
Year/Exercise
Nominal value
xref
[Mg l-1]
laboratory result xi
[mg L-1]
Bias
[%]
sR
[%]
Number of
labs
1999/1
81
83
2.4
10
31
1999/2
73
75
2.7
36
2000/1
264
269
1.9
32
2000/2
210
213
1.4
10
35
2001/1
110
112
1.8
36
2001/2
140
144
2.9
11
34

The relevant equations
C = AVDPSOe b/ b fGLO / R
171
172
unitless
unitless
Recovery factor of
the analysis
0.9900
0.9902
AU L
mg-1
Dilution factor
0.0143
0.2560
0.2465
Value
AU
AU
mg L-1
Unit
fdil
b1
b0
Asample
Concentration of
NH4+ in the sample
solution
Absorbance of the
sample solution
Intercept of
calibration line
Slope of calibration
line unit AU
divided by mg N L-1
Quantity
Measurement data
0.0058
0.00
0.0070
0.0021
0.0015
0.0031
Standard
uncertainty
(u)
0.59
0.00
0.71
14
0.58
1.3
Relative standard
uncertainty
(%)
Type of
uncertainty
normal
rectangular
Type of distribution
triangular
TrainMiC Exercises
Determination of concentration of ammonium in drinking
water by continuous flow analysis (CFA) and spectrometric
detection
in the Directive 98/83/EC on the quality of water intended for
human consumption
EXERCISE 1:
EXERCISE 2:
EXERCISE 3:
Addendum I: By spreadsheet solution
173

Analyte
Ammonium
Measurand
Dissolved ammonium in water sample arriving in the laboratory
Units
mg L-1

Measurement
procedure
ISO 11732:2005 using the continuous flow analysis and photometric detection
Type of calibration
standard curve
standard addition
internal standard
Model equation
C AVDPSOeEEfGLOR
C
AVDPSOe
CRQFeQWUDWLRQRI1+LQWKeVDPSOeVROXWLRQ>PJL@
$EVRUEDQFeRIWKeVDPSOeVROXWLRQ>$8@
b
IQWeUFeSWRIFDOLEUDWLRQOLQe>$8@
b
6ORSeRIFDOLEUDWLRQOLQe>$8GLYLGeGE\PJL@
fGLO
'LOXWLRQIDFWRU
ReFRYeU\IDFWRURIWKeDQDO\VLV
TKeFDOLEUDWLRQOLQeeYDOXDWeGE\OLQeDUUeJUeVVLRQLVEDVeGRQYeVWDQGDUGVLQWKeUDQJe
PJL
TKeGLOXWeVWDQGDUGVROXWLRQRIPJLLVSUeSDUeGIURPDVWRFNVROXWLRQRIPJ
LTKLVVWRFNVROXWLRQLVSUeSDUeGIURPDPPRQLXPFKORULGe
174
Recovery factor contributing 30 % to the expanded uncertainty
Absorbance of the sample - here the main source is the drift contributing about 20%
Calibration standard solution purity of ammonium chloride
Calibration volumetric flasks and pipettes
For the analyte
1
Name/ChemicalFormula/Producer:
Ammonium chloride, NH4Cl, Merck pa min 99 %

Absorbance relative measurement. Not direct part of

the traceability chain

Volumetric flasks Class A quality
Volumetric pipettes calibrated by producer and

regularly checked by the laboratory

model equation?
Yes
Within-lab reproducibility, contamination
No

1
Participating in PT rounds
2
3
175

Measurement procedure is based on EN/ISO11732
Analyte
Ammonium
The measurand
Unit
mg L-1

Matrix
Drinking water
Measuring range
up to 1 mg L-1 for undiluted samples

To analyse drinking water according to the EU requirements in the EU directive

LOD

LOD 0.05 mg L-1: - 3s on a natural sample,
5s on a blank: s is repeatability
LOQ
Repeatability
Mark the customers
their values
Within-lab
reproducibility
Trueness
at 0.5 mg L-1, s = 0.025 mg L-1:

at 0.2 mg L-1, s the demand estimated to be
s = 0.010 mg L-1 or 5 %
at 0.5 mg L-1 less than 0.05 mg L-1 or less than
10 % relative
Measurement
uncertainty
Other-state

VALIDATION
176
New in-house method
Full
Partial
6. Measuring range
Linearity
Upper limit
LOD
LOQ
7. Spread precision
Repeatability
8. Robustness
177
9. Quality control
Control charts

R square
178
11. Calculation of parameters requested by the customer 3

Parameters requested
to be validated
Calculations
s = 0.004 mg L-1
LOD
LOD = 5s = 0.02 mg L-1
LOQ
Repeatability
At a level of 0.1 mg L-1 sRw is 4.4 % and at a level of

0.6 mg L-1 sRw is 3.5 %.
Trueness
From PT results the trueneness is estimated to be less than

3 %. The trueness is probably around 2 % - then mean value of
the PT results for levels over 0.08 mg L-1.
The measurement uncertainty at a level of 0.2 mg L-1 is estimated

to be 2.5 %. According to EA guideline this value should be
rounded off to 3 %.3
Comment TKLV YDOXe RI REWDLQeG XVLQJ WKe PRGeO DSSURDFK LV SUREDEO\ DQ
XQGeUeVWLPDWeVLQFeVRPeIDFWRUVDUeQRWWDNeQLQWRDFFRXQWeJFRQWDPLQDWLRQZLWKLQ
ODEUeSURGXFLELOLW\$URXWLQeODERUDWRU\ZRXOGW\SLFDOO\KDYeDQXQFeUWDLQW\RIDW
WKLVOeYeOGXeWRFRQWDPLQDWLRQDQGDQe[SeUWODERUDWRU\PD\W\SLFDOO\KDYeDQXQFeUWDLQW\
RIWR
179
Value obtained
during validation
The requirement
is fulfilled
Yes/No
0.05 mg L-1
0.02 mg L-1
Yes
Within-lab
reproducibility
5 % at a level of 0.2 mg L-1
4%
Yes
Trueness
10 %
2-3 %
Yes
Parameter

customer
LOD
LOQ
Repeatability
Measurement
uncertainty
Other
The analytical procedure is t for the intended use:

Yes
No
180

Measurand
Unit
mg L-1

equation
$PPRQLXP SUeVeQW LQ WKe VDPSOe UeDFWV LQ DONDOLQe VROXWLRQ ZLWK K\SRFKORULWe TKe
FKORUDPLQeVIRUPeGUeDFWVXQGeUFDWDO\VLVRIQLWURSUXVVLGeZLWKVDOLF\ODWeDWDWePSeUDWXUe
RICWRIRUPDEOXeJUeeQLQGRSKeQROG\eZKLFKLVTXDQWLWDWLYeO\PeDVXUeGLQD
RZSKRWRPeWeUDWQP
Model equation
C = AVDPSOe b b fGLO / R
C
AVDPSOe
FRQFeQWUDWLRQRI1+LQWKeVDPSOeVROXWLRQ>PJL@
DEVRUEDQFeRIWKeVDPSOeVROXWLRQ>$8@
b
LQWeUFeSWRIFDOLEUDWLRQOLQe>$8@
b
VORSeRIFDOLEUDWLRQOLQe>$8GLYLGeGE\PJL@
fGLO
GLOXWLRQIDFWRU
UeFRYeU\IDFWRURIWKeDQDO\VLV

Method bias
Matrix effect
Other: measurement of sample
Other: Preparation, measurement of calibration solutions and constructing the calibration graph
Other:
181

Input quantity
Value
Unit
Asample
0.256
AU
b0
0.01734
AU
b1
986.3
AU L mg-1
fdil
unitless
0.99
unitless
Remark

Input
quantity
Standard
uncertainty
Unit
Remark
Asample
1.49 10-3
AU
Takes into account repeatability, drift and rounding
b0
0.00207
AU
b1
0.0070
AU L mg-1
Takes into account reference solution (0.3 % relative

uncertainty, preparation and measurement of calibration
standards and constructing the calibration graph
fdil
unitless
Dilution of sample in this case the sample was not

diluted
0.0058
unitless
A rough estimate of recovery of 99 1 %
6. Calculate the value of the measurand, using the model equation.

C = AVDPSOe b / b fGLO/ R
C=
182
0.256 0.01734
1 0.99 = 0.247 mg L-1
986.3
Using:
6SUeDGVKeeW$SSURDFK
Input
quantity
Value
Standard
uncertainty
Unit
Asample
0.256
1.49 10-3
AU
b0
0.01435
0.00207
AU
b1
0.9902
0.0070
AU L mg-1
fdil
Unitless
0.99
0.01
Unitless
CRPPeUFLDO6RIWZDUe
Remark
From calibration graph note regression without

weights and a slight curvature. A too high
estimate but here we are interested in higher
concentrations.
Sample was not diluted
C =AVDPSOe b b fGLO / R

TKeFRPELQeGVWDQGDUGXQFeUWDLQW\LVPJL
units
U = k u = 2 0.0031 = 0.006 PJL
TKe e[SDQGeG XQFeUWDLQW\ XVLQJ D FRYeUDJe IDFWRU RI LV PJ L 1 RU
UeODWLYe
1
2
3
Recovery factor contributing 20 % to the expanded uncertainty

Absorbance of the sample - here the main source is the drift contributing about 20 % to the expanded
uncertainty
Preparation of standard solution 10 mg L-1 0.13 mg L-1 (k = 2) - main components dilution using a
1mL pipette and purity contribution about 25 %
183
Further readings
(1VWDQGDUGI62
(CCRXQFLO'LUeFWLYe(CRI1RYePEeUTKeTXDOLW\RIZDWeULQWeQGeG

% MDJQXVVRQ T 1l\NNL + +RYLQG DQG M .U\VeOO Handbook for Calculation of
Measurement Uncertainty in Environmental LaboratoriesQGeGI661
1RUGWeVWWeFKQLFDOUeSRUWKWWSZZZQRUGLFLQQRYDWLRQQeWQRUGWeVWOeUWeFSGI
184
Addendum: Measurement uncertainty calculation GumWorkbench

TKeYDOXeVRIXQFeUWDLQW\FRPSRQeQWVRIYROXPeWULFZDUeDQGSKRWRPeWULFeTXLSPeQW
DUe WDNeQ DFFRUGLQJ WR e[SeULeQFe e[SeULPeQWV FDUULeG RXW LQ WKe ODE DQG GDWD IURP
eTXLSPeQW PDQXIDFWXUeUVTKe FDOFXODWLRQV DUe KeUe EDVeG RQ D PDQXDO PeWKRG IRU D
FOeDUeU YLeZ RI WKe FDOFXODWLRQV EXW DQ DXWRPDWeG PeWKRG ZLOO JLYe VLPLODU RU ORZeU
XQFeUWDLQW\
Model equation:
{ The main equation }
C = (Asample - b0) / b1 fdil / R;
{ Nitrogen- Ammonium ion stock solution - 1000 mg N L-1. Prepared from ammonium
chloride.}
Cst_0 = mNH4Cl / V1000 PNH4Cl fNH4Clconv 1000;
{ Ammonium standard solution - 10 mg N/L. Prepared from ammonium stock solution.
The standard solution is further used for preparation of the calibration standard
solutions. }
Cst = Cst_0 V1 / V100;
{ Concentrations of calibration standard solutions 0.1 to 1 mg N L-1.
1 to 10 mL of the standard solution is transferred to 100 mL volumetric asks.
The reagents are added and the solution is made up to the mark. The solution is left to
stand for 60 min and then the absorbance at 655 nm is measured. }
C1 = Cst (V1_st / V1_100);
C2 = Cst (V2_st / V2_100);
C3 = Cst (V3_st / V3_100);
C4 = Cst (V4_st / V4_100);
C5 = Cst (V5_st / V5_100);
fdil = 1;
{in this case the sample was not diluted}
{ Photometric measurements
It is assumed that the uncertainty of all photometric measurements consists of three
components (on the example Asample):
Repeatability uncertainty (included in Asample_rep);
Uncertainty due to drift (Asample_drift)
Uncertainty due to rounding of the reading (Asample_round) (The photometer use din this
example has three decimal places)
The absorbance of blank is not subtracted but all the measurements are made against
blank}
{ Absorbance of sample solution }
Asample = Asample_rep+Asample_drift+Asample_round;
185
{ The regression equations for nding the slope (b1) and intercept (b0) of the calibration
line }
AC = C1 A1 + C2 A2 + C3 A3 +C4 A4 + C5 A5;
AvgC=(C1+C2+C3+C4+C5)/n;
AvgA=(A1+A2+A3+A4+A5)/n;
CC=C1 C1+C2 C2+C3 C3+C4 C4+C5 C5;
b1=(AC-n AvgC AvgA)/(CC-n AvgC AvgC);
b0=AvgA-b1 AvgC
List of quantities:
186
Quantity
Unit
Definition
mg N L-1
Concentration of NH4+ in the sample solution
Asample
AU
Absorbance of the sample solution
b0
AU
Intercept of calibration line
b1
AU L mg-1
Slope of calibration line
fdil
unitless
Dilution factor
unitless
Recovery factor of the analysis

-1
Cst_0
mg N mL
Concentration of NH4+ in calibration stock solution
mNH4Cl
Weight of NH4Cl
V1000
mL
Volume of 1 L volumetric flask
PNH4Cl
unitless
Purity of NH4Cl
fNH4Clconv
unitless
Conversion factor for converting the amount of ammonium chloride (NH4Cl)

to the amount of nitrogen
Cst
mg N L-1
Concentration of NH4+ in the ammonium standard solution
V1
mL
Volume of 1 mL pipette
V100
mL
Volume of 100 mL volumetric flask

-1
C1
mg N L
Concentration of the 1st ammonium calibration standard solution
V1_st
mL
Volume of ammonium standard solution taken for preparing the 1st

ammonium calibration standard solution
V1_100
mL
Volume of the 1st ammonium calibration standard solution

-1
C2
mg N L
Concentration of the 2nd ammonium calibration standard solution
V2_st
mL
Volume of ammonium standard solution taken for preparing the 2nd

V2_100
mL
Volume of the 2nd ammonium calibration standard solution
C3
mg N L-1
Concentration of the 3rd ammonium calibration standard solution
Quantity
Unit
Definition
V3_st
mL
Volume of ammonium standard solution taken for preparing the 3rd

V3_100
mL
Volume of the 3rd ammonium calibration standard solution

-1
C4
mg N L
Concentration of the 4th ammonium calibration standard solution
V4_st
mL
Volume of ammonium standard solution taken for preparing the 4th

V4_100
mL
Volume of the 4th ammonium calibration standard solution
C5
mg N L-1
Concentration of the 5th ammonium calibration standard solution
V5_st
mL
Volume of ammonium standard solution taken for preparing the 5th

V5_100
mL
Volume of the 5th ammonium calibration standard solution
AC
Interim quantity for regression statistics calculation
A1
AU
Absorbance of the 1th ammonium calibration standard solution
A2
AU
Absorbance of the 2nd ammonium calibration standard solution
A3
AU
Absorbance of the 3rd ammonium calibration standard solution
A4
AU
A5
AU
Asample_rep
Asample_drift
Asample_round

-1
AvgC
mg N L
unitless
Number of points on the calibration line
AvgA
AU
CC
R:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXeXQLWOeVV
+DOIZLGWKRIOLPLWVXQLWOeVV
mNH4Cl:
9DOXeJ
+DOIZLGWKRIOLPLWVJ
187
V1000:
9DOXePL
+DOIZLGWKRIOLPLWVPL
PNH4Cl:
9DOXeXQLWOeVV
+DOIZLGWKRIOLPLWVXQLWOeVV
fNH4Clconv:
CRQVWDQW
9DOXe
V1:
9DOXePL
+DOIZLGWKRIOLPLWVPL
V100:
9DOXePL
+DOIZLGWKRIOLPLWVPL
V1_st:
9DOXePL
+DOIZLGWKRIOLPLWVPL
V1_100:
9DOXePL
+DOIZLGWKRIOLPLWVPL
V2_st:
9DOXePL
+DOIZLGWKRIOLPLWVPL
V2_100:
9DOXePL
+DOIZLGWKRIOLPLWVPL
188
V3_st:
9DOXePL
+DOIZLGWKRIOLPLWVPL
V3_100:
9DOXePL
+DOIZLGWKRIOLPLWVPL
V4_st:
9DOXePL
+DOIZLGWKRIOLPLWVPL
V4_100:
9DOXePL
+DOIZLGWKRIOLPLWVPL
V5_st:
9DOXePL
+DOIZLGWKRIOLPLWVPL
V5_100:
9DOXePL
+DOIZLGWKRIOLPLWVPL
Asample_rep:
T\Se$VXPPDUL]eG
MeDQ
6WDQGDUG8QFeUWDLQW\
'eJUeeVRI)UeeGRP
Asample_drift:
T\Se$VXPPDUL]eG
MeDQ
6WDQGDUG8QFeUWDLQW\
'eJUeeVRI)UeeGRP
189
Asample_round:
9DOXe
+DOIZLGWKRIOLPLWV
A1:
9DOXe$8
+DOIZLGWKRIOLPLWV$8
A2:
9DOXe$8
+DOIZLGWKRIOLPLWV$8
A3:
9DOXe$8
+DOIZLGWKRIOLPLWV$8
A4:
9DOXe$8
+DOIZLGWKRIOLPLWV$8
A5:
9DOXe$8
+DOIZLGWKRIOLPLWV$8
n:
CRQVWDQW
9DOXeXQLWOeVV
190
Uncertainty budgets:
C
CRQFeQWUDWLRQRI1+LQWKeVDPSOeVROXWLRQ
Quantity Value
Standard
uncertainty
Distribution
Sensitivity Uncertainty
coefficient contribution
Asample
0.25600 AU
1.48 10-3 AU
b0
0.01435 AU
2.07 10-3 AU
b1
0.99023
AU L mg-1
7.01 10-3
AU L mg-1
fdil
1.0 unitless
0.0 unitless
0.99000 unitless
5.77 10-3
unitless
rectangular
-0.25
-1.4 10-3 mg L-1 21.3 %
Cst_0
995.01 mg mL-1
2.96 mg mL-1
mNH4Cl
3.81900 g
1.15 10-3 g
rectangular
0.065
75 10-6 mg L-1
V1000
1.000000 mL
577 10-6 mL
rectangular
-0.25
-140 10-6 mgL-1 0.2 %
PNH4Cl
0.99500 unitless
2.89 10-3
unitless
rectangular
0.25
720 10-6 mg L-1 5.3 %
fNH4Clconv
0.26185152642501
unitless
Cst
9.9501 mg L-1
0.0649 mg L-1
V1
1.00000 mL
5.77 10-3 mL
rectangular
0.25
1.4 10-3 mg L-1
V100
100.0000 mL
0.0577 mL
rectangular
-2.5 10-3
-140 10-6 mgL-1 0.2 %
C1
0.099501 mg L-1
868 10-6 mg L-1
V1_st
1.00000 mL
5.77 10-3 mL
rectangular
0.035
200 10-6 mg L-1 0.4 %
V1_100
100.0000 mL
0.0577 mL
rectangular
-350 10-6
-20 10-6 mg L-1
C2
0.19900 mg L-1
3.15 10-3 mg L-1
V2_st
2.0000 mL
0.0289 mL
rectangular
0.031
900 10-6 mg L-1 8.4 %
V2_100
100.0000 mL
0.0577 mL
rectangular
-620 10-6
-36 10-6 mg L-1
0.0 %
C3
0.39800 mg L-1
6.31 10-3 mg L-1
V3_st
4.0000 mL
0.0577 mL
rectangular
0.023
1.3 10-3 mg L-1
17.9 %
V3_100
100.0000 mL
0.0577 mL
rectangular
-910 10-6
-53 10-6 mg L-1
0.0 %
Index
0.0 %
20.9 %
0.0 %
191
Standard
uncertainty
Quantity Value
Distribution
Sensitivity Uncertainty
coefficient contribution
Index
C4
0.59701 mg L-1
4.00 10-3 mg L-1
V4_st
6.00000 mL
8.66 10-3 mL
rectangular
0.014
120 10-6 mg L-1 0.2 %
V4_100
100.0000 mL
0.0577 mL
rectangular
-850 10-6
-49 10-6 mg L-1
0.0 %
C5
0.99501 mg L-1
6.67 10-3 mg L-1
V5_st
10.0000 mL
0.0144 mL
rectangular
-2.7 10-3
-39 10-6 mg L-1
0.0 %
V5_100
100.0000 mL
0.0577 mL
rectangular
270 10-6
16 10-6 mg L-1
0.0 %
Asample_rep
0.256000
654 10-6
normal
1.0
670 10-6 mg L-1 4.6 %
Asample_drift
0.0
1.30 10-3
normal
1.0
1.3 10-3 mg L-1
Asample_round 0.0
289 10-6
rectangular
1.0
290 10-6 mg L-1 0.9 %
AC
1.5720 -
0.0108 -
A1
0.108000 AU
577 10-6 AU
rectangular
-0.36
-210 10-6 mgL-1 0.4 %
A2
0.214000 AU
577 10-6 AU
rectangular
-0.32
-180 10-6 mg L-1 0.3 %
A3
0.412000 AU
866 10-6 AU
rectangular
-0.23
-200 10-6 mg L-1 0.4 %
A4
0.60600 AU
1.15 10-3 AU
rectangular
-0.14
-170 10-6 mg L-1 0.3 %
A5
0.99790 AU
1.15 10-3 AU
rectangular
0.027
31 10-6 mg L-1
AvgC
0.45771 mg L-1
3.27 10-3 mg L-1
5.0 unitless
AvgA
0.467580 AU
404 10-6 AU
CC
1.5544 -
0.0211 -
0.24650 mg L-1
3.11 10-3 mg L-1
18.2 %
0.0 %
Results:
192
Quantity
Value
Expanded
uncertainty
Coverage factor
Coverage
0.2465 mg L-1
2.5 % (relative)
2.00
manual
Appendix 1
193
TrainMiC Exercises
Analytical procedure:
EXERCISE 1:
EXERCISE 2:
EXERCISE 3:
195
)LOeQDPeT(MPL$T(:KLWeT9M8$
9eUVLRQ(1
PUeSDUeGE\TUDLQMLC
(GLWRUV1LQeWDMDMFeQPKLOLSTD\ORU
IVVXeGMDUFK
)RUXVeDWWKeTUDLQMLCFRXUVeVRQO\
196

Analyte
Measurand
Units

Measurement
procedure
Type of calibration
standard curve
Standard addition
internal standard
Model equation
197
judgement should be based on your previous experience only
1
2
3
4
5
For the analyte
1

1
(k = 2) see also data yellow sheet

Are all important parameters included in the model
equation?
Yes

1
2
3
198
No
199

Analyte
The measurand
Unit

Matrix
Measuring range

Intended use of the results:
LOD
LOQ
Mark the customers
their values
Repeatability
Trueness
Other-state

VALIDATION
200
New in-house method
Full
Partial
6. Measuring range
Linearity
Upper limit
LOD
LOQ
7. Spread precision
Repeatability
8. Robustness
201
9. Quality control
Control charts
Participation in proficiency testing schemes

R squared
202

validated
Calculations
LOD
LOQ
Repeatability
Trueness
Parameter

customer
(the same as stated in question3)
Value obtained
during validation
The requirement
is fulfilled
Yes/No
LOD
LOQ
Repeatability
Within-lab
reproducibility
Trueness
Measurement
Other

Yes
No
203

EXERCISE
Measurand
Unit

equation
Model equation:

Method bias
Matrix effect
Other:
Other:
Other:
204

Input quantity
Value
Unit
Remark

Input quantity
Standard
uncertainty
Unit
Remark

Using:
Input
quantity
Value
Standard
uncertainty
6SUeDGVKeeWDSSURDFK
Unit
CRPPeUFLDOVRIWZDUe
Remark
units
205
1
2
3
206
Addendum I: Measurement uncertainty calculation:

Addendum II: Measurement uncertainty calculation

GumWorkbench
207
Appendix 2
209
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European Commission Joint Research Centre Institute for Reference Materials

and Measurements
EUR 22791/2 EN Practical examples on traceability, measurement uncertainty
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Producing reliable measurements in analytical chemistry can be rather demanding.

PRACTICAL EXAMPLES ON TRACEABILITY, MEASUREMENT UNCERTAINTY AND VALIDATION IN CHEMISTRY

The mission of the JRC-IRMM is to promote a common and reliable European

More information on the European Union is available on the Internet (http://europa.eu).

CHAPTER 4....................................................................................................................... 121

CHAPTER 5....................................................................................................................... 157

APPENDIX 1 ..................................................................................................................... 193

Practical examples on traceability, measurement uncertainty and validation in chemistry

How to use the Book

How does a standardised TrainMiC example look like?

How to use the Book

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Figure 1. Harmonised TrainMiC example

What is a recommended approach of conducting a TrainMiC

Practical examples on traceability, measurement uncertainty and validation in chemistry

About the structure of this handbook

Figure 2. A process of conducting a completeTrainMiC example

How to use the Book

About the Authors

Practical examples on traceability, measurement uncertainty and validation in chemistry

About the Authors

Practical examples on traceability, measurement uncertainty and validation in chemistry

About the Authors

Practical examples on traceability, measurement uncertainty and validation in chemistry

QXDOLW\CRQWUROIRU(QYLURQPHQWDOLDERUDWRULHV UHSRUW +HLVDOVRZRUNLQJZLWK

Analysis of Gold Alloys by Flame Atomic

TrainMiC example summary form (blue page)

Practical examples on traceability, measurement uncertainty and validation in chemistry

TrainMiC example summary form

I. General information about the example

Mass fraction of Au in gold alloys ()

Authors of the example

Veselin Kmetov, Emilia Vassileva

Determination of gold in jewellery gold alloys by flame atomic

Analysis of Gold Alloys by Flame Atomic Absorption Spectrometry

II. Attached files

File number, type

About the analytical procedure: short introduction

Content of the file

Description of the analytical procedure

Establishing traceability in analytical

Single laboratory validation of

Building an uncertainty budget

Addendum 1: By spreadsheet approach

Addendum 2: By dedicated software

III. History of the example

Uploaded on the webhotel

Short description of the change

Practical examples on traceability, measurement uncertainty and validation in chemistry

A short introduction to the analytical procedure

Analysis of Gold Alloys by Flame Atomic Absorption Spectrometry

Practical examples on traceability, measurement uncertainty and validation in chemistry

Analysis of Gold Alloys by Flame Atomic Absorption Spectrometry

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Practical examples on traceability, measurement uncertainty and validation in chemistry

All input needed to do the three exercises yellow pages

Analysis of Gold Alloys by Flame Atomic Absorption Spectrometry

PART I. Description of the analytical procedure

Practical examples on traceability, measurement uncertainty and validation in chemistry

Analysis of Gold Alloys by Flame Atomic Absorption Spectrometry

Description of the analytical procedure

Practical examples on traceability, measurement uncertainty and validation in chemistry

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