Practical Examples Traceability, Uncertainty and Validation in Chemistry Vol 1

The mission of the JRC is to provide customer-driven scientific and technical support for the
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PRACTICAL EXAMPLES ON TRACEABILITY, MEASUREMENT UNCERTAINTY AND VALIDATION IN CHEMISTRY

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,
Producing reliable measurements in analytical chemistry can be rather demanding.
Some would say an uphill struggle. Comparable to mountain walking. Hard work, but then
Measurement Uncertainty
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
and Validation
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
in Chemistry
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. Volume 1
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.
Edited by
We hope it succeeds in doing so. Nineta Majcen, Philip Taylor
Nineta Majcen Authors:

Philip Taylor Ljudmila Benedik
Steluta Duta Urška Repinc
Koit Herodes Philip Taylor
Monika Inkret Emilia Vassileva
Veselin Kmetov
Allan Künnapas
Ivo Leito
Bertil Magnusson
ISBN 978-92-79-12021-3 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 Ivo Leito
Steluta Duta Bertil Magnusson
Koit Herodes Urška Repinc
Monika Inkret Philip Taylor
Veselin Kmetov Emilia Vassileva
Allan Künnapas
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: [email protected]
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 (*):

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(*) 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.
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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 α-Spectrometry
Ljudmila Benedik, Urška Repinc, Monika Inkret
CHAPTER 4....................................................................................................................... 121

Determination of Polar Pesticides by Liquid Chromatography Mass Spectrometry
Allan Künnapas, 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
3
Practical examples on traceability, measurement uncertainty and validation in chemistry
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About the Authors
Introduction
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Chapter 1
Analysis of Gold Alloys by Flame Atomic
Absorption Spectrometry
Veselin Kmetov, Emilia Vassileva
u TrainMiC example summary form (‘blue page’)

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

Analytical procedure
absorption spectrometry
Customer’s requirement U = 9 ‰ (k = 3)
18
II. Attached files

File is
File number, type
Content of the file attached Remark
and name
Yes No
Ex-06-1-I-Au-
Given by the
1-I
alloys-FAAS-2006- About the analytical procedure: short introduction 9 lecturer

Ver1.ppt
PART I Description of the analytical procedure 9

Each
The customer’s requirements participant
PART II concerning the quality of the 9 receives own
2 - Yellow
Ex-06-2-Y-Au- measurement result copy and

alloys-FAAS-2006- Validation of the measurement may keep it
Ver1.doc PART III procedure – relevant equations and 9
measurement data
Measurement uncertainty of the result
PART IV – relevant equations and measurement 9
data
Establishing traceability in analytical
PART I
chemistry
9
Single laboratory validation of

9
3 - Green
EX-06-3-G-Au- PART II
measurement procedures
alloys-FAAS-2006-
Ver1.doc Building an uncertainty budget 9
PART III Addendum 1: By spreadsheet approach 9
Addendum 2: By dedicated software 9
III. History of the example

Version Uploaded on the webhotel Short description of the change
0 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
Description of the analytical procedure
PART II .................................................................................................................................33
The customer’s 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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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
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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] 242.8 Ql- aspiration rate 6.4 mL min-1 checked by BDW
Au spectral slit [nm] 0.7 Injection time 5 s; Injection volume ≈ 0.530 μL
Au hollow cathode lamp current [mA] 10 Washing time 10 s; Total replicate time 15 s
Air/C2H2 units 50/18 Smoothing Savitzky-Golay 24 points

Observation high [mm] 6 Ensemble summation N signal profiles
Working range μg g-1 37−43 Pseudo plateau 3 s

Deuterium BG corrector OFF 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
m_ pureAu × Au_ purity

C_ Au 999.9 = × 104
G _100
C_ Au 999.9 FRQFHQWUDWLRQRILQLWLDOVWDQGDUGVROXWLRQPDGHXSIURPSXUHJROG>μJJ@
m_ pureAu PDVVZHLJKHGRISXUHJROG>J@
PDVVRIWKHVROXWLRQLQWKHYROXPHWULFÀDVNPDGHXSWRJZLWK
GB
1+CO>J@
Au− purity WKHSXULW\RIJROGVWDWHGLQWKHFHUWL¿FDWH>@
FRQYHUVLRQ IDFWRU IURP WR ȝJ J ȡ § HTXDOLVHG IRU VWDQGDUG DQG

VDPSOHVLQ1+CO
Concentration of calibration standard solutions
G_0.37 G_0.43
C _ St1 = C Au _999.9 × C _ St 2 = C Au _999.9 ×
G _100 G _100
C _ St1 CRQFHQWUDWLRQRI$XZRUNLQJVWDQGDUGVROXWLRQV>ȝJJ@
C _ St 2 CBStIRUORZȝJJDQGCBStIRUKLJKȝJJ
C Au _999.9 CRQFHQWUDWLRQRI$XVWDQGDUGVROXWLRQ$X>ȝJJ@SUHSDUHGIURP
SXUHJROG
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JUHVSHFWLYHO\
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DGGLQJ1+COLQSRO\SURS\OHQHYLDOV>J@
30
Bracketing calibration
C− st1 ( A_ St 2 − A _ X ) + C− St 2 ( A− x − A− St1 )
Cx =
A− St 2 − A− St1
Cx CRQFHQWUDWLRQRI$XLQWKHDQDO\VHGVROXWLRQ>ȝJJ@
CRQFHQWUDWLRQ RI WKH ORZHU FDOLEUDWLRQ VWDQGDUG VROXWLRQ XVHG IRU
C− St1 EUDFNHWLQJFDOLEUDWLRQ>ȝJJ@
CRQFHQWUDWLRQ RI WKH KLJKHU FDOLEUDWLRQ VWDQGDUG VROXWLRQ XVHG IRU
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A_ X
$EVRUEDQFHPHDVXUHGIRUWKHDQDO\VHGVDPSOHVROXWLRQ
Calculation of Au mass fraction (W_‰) in analysed sample

1 V_ 50 1 Gvials _12
WBÅ= × × × Cx
1000 m_ 0.1 R GP _ 0, 4
WBÅ ¿QDOFRQFHQWUDWLRQRI$XLQWHVWHGMHZHOOHU\JROGDOOR\ZZ>Å@
YROXPHRIWKHVROXWLRQLQWKHYROXPHWULFÀDVN>PL@
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m_ 0.1
PDVVRIDQDO\VHGDOOR\VDPSOH>J@
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GP _ 0.4 PDVVRI$XVDPSOHVROXWLRQWDNHQIURPVB>J@
R FRUUHFWLRQIRUUHFRYHU\
Combined model equation for calculation of Au content (‰)
WBÅ = × × ×
( )
1 ⎛ V _ 50 Gvials _ 12 ⎞ CAu_999.9 GP _0.37 ( A_ St 2 − A _ X ) + GP _0.43 ( A− X − A− St1 ) 1
×
1000 ⎜⎝ m _ 0.1 GP _ 0.4 ⎟⎠ G_10 A− St 2 − A− St1 R
31
Calculation of signal standard uncertainty estimated as standard deviation

u_ A _ one _ set
u_ A =
N
FDOFXODWHG VWDQGDUG XQFHUWDLQW\ IURP WKH SODWHDX SDUW V RI

u_ A
WKHDEVRUEDQFHVLJQDODIWHUHQVHPEOHDYHUDJLQJRINVHWVRIVDPSOLQJ
6WBVDPSOHB6W
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u_ A _ one _ set
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B6W
N QXPEHURIVHWVSHUIRUPHGDQGVXPPDWHGDVHQVHPEOH
32
PART II. The customer’s requirements concerning quality of the

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

equations and measurement data
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SHUIRUPHG
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Recovery:
CXSHOODWLRQPHWKRGÅ
$'I)$$6Å
Repeatability:
Å
Å
Å
Å
Å
Å
34
PART IV. Measurement uncertainty of the result – relevant

CDOFXODWH FRPELQHG DQG H[SDQGHG XQFHUWDLQW\ k IURP WKH IROORZLQJ

PHDVXUHPHQWGDWD
Input Standard
Value Unit Remark
quantity uncertainty
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 g 0.0002 Mass of analysed alloy sample
Gvials _12 12.0030 g 0.0008 Mass of sample solution prepared in vials
GP _ 0.4 Mass of Au sample solution taken from V_50

0.4015 g 0.0009
flask
m_ pureAu 0.1004 g 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 Masses of the stock Au standard solution

0.3701
g 0.0006 transferred for the preparation of calibration
G p _0.43 0.4302
solutions C_St1 and C_St2
G_10 10.0321 g 0.0008 Mass of calibration standard solutions
A− St1 0.5203 0.0010 Absorbance measured for calibration

AU
A_ St 2 0.6041 0.0011 standard solutions
Absorbance measured for the analysed

AX 0.5488 AU 0.0011
sample solution
R 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:
Building an uncertainty budget
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 curve standard addition internal standard
Model equation
1. Standard solutions
1.1. Stock standard solution - prepared from pure gold

m− pureAu × Au_ purity
C Au _999.9 = × 104
G _100
1.2. Calibration standard solutions

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

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

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

1 ⎛ V_ 50 Gvials _ 12 ⎞ m− pureAu × Au purity
WBÅ = × × × 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 ) )× 1
A− St 2 − A− St1 R
V _ 50 YROXPHRIDQDO\VHGVROXWLRQ>PL@
V _100 YROXPHRIVWRFNVWDQGDUGVROXWLRQ>PL@
m_ 0.1 PDVVRIDQDO\VHGDOOR\VDPSOH>J@
Gvials _12 PDVVRIVDPSOHVROXWLRQGLOXWHGLQYLDOV>J@
GP _ 0.4 PDVVRI$XVDPSOHVROXWLRQWDNHQIURPVBÀDVN>J@
m_ pureAu
PDVVZHLJKHGRISXUHJROG>J@
Au_ purity
WKHSXULW\RIJROGVWDWHGLQWKHFHUWL¿FDWH>@
PDVVHV RI WKH VWRFN $X VWDQGDUG VROXWLRQ WUDQVIHUUHG IRU WKH
G p _0.37 or G p _0.43 SUHSDUDWLRQRIFDOLEUDWLRQVROXWLRQV6WDQG6W>J@
G_100
PDVVRIFDOLEUDWLRQVWDQGDUGVROXWLRQV>J@
A− St1 DQG A_ St 2
DEVRUEDQFHPHDVXUHGIRUFDOLEUDWLRQVWDQGDUGVROXWLRQVDQG
AX DEVRUEDQFHPHDVXUHGIRUWKHDQDO\VHGVDPSOHVROXWLRQ
R UHFRYHU\
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.
1 Recovery – 28.5 % to the expanded uncertainty
2 Absorption of analysed gold sample − contributing 19.8 % to the expanded uncertainty
3 Mass of analysed gold sample − contributing 11.8 % to the expanded uncertainty
38
Mass of stock solution taken for the preparation of first standard solution − contributing 12.1 % to the
4
expanded uncertainty
5 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

Pure Gold − certified by Non-Ferrous Metallurgical
1 Name/Chemical Formula/Producer:
Plant Plovdiv − Bulgaria
For the other input quantities

Quantity/Equipment/Calibration:
1 e.g. mass/balance/calibrated by NMI, U = xx Balance – calibrated by NMI
(k = 2), see also data yellow sheet
2 Quantity/Equipment/Calibration: Volumetric flask − class A quality
Absorbance − relative measurement. Not direct part of
3 Quantity/Equipment/Calibration:
the traceability chain.
5. Estimating uncertainty associated with the measurement
Are all important parameters included in the

Yes No
measurement equation?
Other important parameters are: Within-lab reproducibility
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
Gold in jewellery alloys containing gold 14 ± 0.5 carats after aqua
The measurand
regia dissolution
Unit ‰
2. Specify the Scope

Matrix Gold in 5 % NH4Cl
Measuring range 37-43 μg 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 customer’s requirements
Within-lab reproducibility
and give their values
Measurement uncertainty 9‰
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
Calculations
validated
LOD
LOQ
Repeatability 2.4 ‰
Within-lab reproducibilty
Trueness
Measurement uncertainty 8.3 ‰ (k = 3)
Other - please state
1.0002 ± 0.0025
Recovery
12. Does the analytical procedure fulfil the requirement(s) for the intended use?
Value requested by the Value obtained The requirement
Parameter customer during is fulfilled
(the same as stated in question 3) validation Yes/No
LOD
LOQ
Repeatability
Within-lab
reproducibility
Trueness
Measurement
9 ‰ (k = 3) 8.3 ‰ (k = 3) yes
uncertainty
Other
The analytical procedure is fit for the intended use:

Yes No
For measurement uncertainty and traceability refer to the corresponding report-

sheets
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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DV$JCO$JCOLVGLVVROYHGE\DGGLQJRIJ1+COWRWKHFRROHGVROXWLRQDQGYROXPH
LVPDGHXSWRWKHPDUNPLZLWK%':DWC
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FRQLFDOYLDODGGLQJ1+COLQRUGHUWRNHHSWKHVROXWLRQKRPRJHQHRXVZLWK¿QDO
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
m pureAu × Au purity G_0.43
C Au 999.9 = × 104 C _ St 2 = C Au _999.9 ×
G _100 G _100
2. Concentration of calibration standard solutions

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

1 V_ 50 1 Gvials _ 12
WBÅ = × × × Cx
1000 m_ 0.1 R GP _ 0.4
45
5. Calculation of signal standard uncertainty

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

WBÅ = × × ×
(
1 ⎛ V _ 50 Gvials _ 12 ⎞ CAu_999.9 GP _0.37 ( A_ St 2 − A _ X ) + GP _0.43 ( A− X − A− St1 ) 1
×
)
1000 ⎜⎝ m _ 0.1 GP _ 0.4 ⎟⎠ G_100 A− St 2 − A− St1 R
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

Input quantity Value Unit Remark
V _ 50 50 mL Volume of analysed solution
V _100 100 mL Volume of stock standard solution
m_ 0.1 0.1001 g Mass of analysed alloy sample
Gvials _12 12.0030 g Mass of sample solution prepared in vials
GP _ 0.4 0.4015 g Mass of Au sample solution taken from V_50 flask
m− pureAu 0.1004 g Mass weighed of pure gold
Au_ purity 99.99 % The purity of gold stated in the certificate
Masses of the stock Au standard solution

G p _0.37 ; G p _0.43 0.3701; 0.4302 g transferred for the preparation of calibration
46
G_100 10.0321 AU Mass of calibration standard solutions

Absorbance measured for calibration standard
A− St1 ; A_ St 2 0.5203; 0.6041 AU
solutions
Absorbance measured for the analysed sample
AX 0.5488 AU
solution
R 1.002 - Recovery
5. Evaluate the standard uncertainty of each input quantity

Standard
Input quantity Unit Remark
uncertainty
V _ 50 0.0379 mL Volume of analysed solution
V _100 0.0697 mL Volume of stock standard solution
m_ 0.1 0.0002 g Mass of analysed alloy sample
Gvials _12 0.0008 g Mass of sample solution prepared in vials
GP _ 0.4 0.0009 g Mass of Au sample solution taken from V_50 flask
m− pureAu 0.0002 g Mass weighed of pure gold
Au_ purity 0.0058 % The purity of gold stated in the certificate
Masses of the stock Au standard solution

G p _0.37 ; G p _0.43 0.0006; 0.0006 g transferred for the preparation of calibration
G_10 0.0008 g Mass of calibration standard solutions

Absorbance measured for calibration standard
A− St1 ; A_ St 2 0.0010; 0.0011 AU
solutions
Absorbance measured for the analysed sample
AX 0.0011 AU
solution
R 0.0025 Recovery
6. Calculate the value of the measurand, using the model equation

Å
7. Calculate the combined standard uncertainty (uc) of the result and specify units
Using: MDWKHPDWLFDOVROXWLRQ 6SUHDGVKHHWDSSURDFK CRPPHUFLDOVRIWZDUH
47
Input Standard
Value 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
Åk
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
2 Absorption of analysed gold sample − contributing 26.1 % to the expanded uncertainty
3 Mass of analysed gold sample − contributing 14.9 % to the expanded uncertainty
10. Prepare your uncertainty budget report

Åk
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k ZKLFKJLYHVDOHYHORIFRQ¿GHQFHRIDSSUR[LPDWHO\
48
Further readings
I62-HZHOOHU\±)LQHQHVVRISUHFLRXVPHWDODOOR\V
CI%-2PUHFLRXVPHWDOVFRPPLVVLRQThe Precious Metals Book
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SODWLQXPDQGSDOODGLXPMHZHOOHU\DOOR\V'LIIHUHQFHPHWKRGXVLQJLQGXFWLYHO\FRXSOHG
SODVPDRSWLFDOHPLVVLRQVSHFWURVFRS\ICP2(6
RMDXUL(+XHUWDDQGMGHOD*XDUGLD)ODPHDWRPLFDEVRUSWLRQDQDO\VLVRIJROG
LQMHZHOU\VDPSOHVFresenius J. Anal. Chem.−
MMRRLPDQ'-.LQQHEHUJL:6LPSVRQPCHWWRXDQGPRDPRQL+LJKSXULW\
SUHFLRXVPHWDOVTM6$QQXDOMHHWLQJ−
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Protect. Metals−
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D FRUUHODWLRQEDVHG FDOLEUDWLRQ PHWKRG Spectrochim. Acta B Atom. Spectrosc.
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Chapter 2
Determination of Calcium in Serum by
Spectrophotometry
Steluta Duta, Philip Taylor

51
Measurand Concentration of calcium in human serum (mg dL-1)
Authors of the example Steluta Duta, Philip Taylor
Analytical procedure Standard WHO procedure
Customer’s requirement Standard WHO procedure
52
II. Attached files

File is
File number, type
and name
Yes No
Ex-10-1-I-
Ca-serum- Given by the
1-I
Photometry-
About the analytical procedure: short introduction 9 lecturer
2006-Ver1.ppt

Each
The customer’s requirements concerning participant
Ex-10-2-Y-
PART II
the quality of the measurement result
9 receives own
2 - Yellow
Ca-serum- copy and

Photometry- PART Validation of the measurement procedure – may keep it
2006-Ver1.doc III relevant equations and measurement data
9
PART Measurement uncertainty of the result –

IV relevant equations and measurement data
9

PART I
chemistry
9
Ex-10-3-G- Single laboratory validation of

9
3 - Green
PART II
Ca-serum- measurement procedures
Photometry-
2006-Ver1.doc
Bulding an uncertainty budget 9
PART
III
Addendum 1: By spreadsheet approach 9

0 April 2007
1
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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Blank S5 S7.5 S10 S12.5 Serum QC

Distilled water (mL) 0.1 - - - - - -
Standard (mL) - 0.1 0.1 0.1 0.1 - -
Serum/QC (mL) - - - - - 0.1 0.1
58
Colour reagent (mL) 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Mix well
Buffer solution (mL) 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Mix well
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59

measurement result according to WHO*
Clinical interpretation:1
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Within-laboratory reproducibility (between day precision)
Model equation
CRHI¿FLHQWRIYDULDWLRQC9
5
∑ (c
1
i , obs − cQC ) 2
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CV = × 100
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n QXPEHURIUHSURGXFLEOHPHDVXUHPHQWV
Measurement data
Mean value ±
Value ± standard deviation
Input quantity standard deviation Unit
(3 replicates)
1st day: 9.280 ± 0.021

nd
ci,obs 2 day: 8.990 ± 0.057
rd
3 day: 9.210 ± 0.105 9.16 ± 0.05 mg dL-1
(i = 1−5) day
3 replicates/day 4th day: 9.230 ± 0.086
5th day: 9.110 ± 0.120
9.38 ± 0.38
cQC 8.24−10.52 mg dL-1
n 5 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
m 625.0 0.2 mg
MCa 40.078 0.002 g mol-1
P 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 ⎟
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IV.3 Calculation of calcium concentration in serum sample

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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

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
Measurement
procedure. The absorbance of calcium calibration solutions and serum sample are
procedure
measured by visible spectrophotometry at 540 nm. From the calibration data the
concentration of calcium in human serum is calculated.
Model equation: calcium concentration in serum

⎛V ⎞
( )
cCa = ⎡⎣( m × M Ca × P ) × 100 / V500 × M CaCO3 ⎤⎦ × (Vi / V100 ) × ⎡⎣( Ax − Ablank ) / ( A−10 − Ablank )⎤⎦ × ⎜ f V ⎟
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65
1 Matrix effect - recovery
2 Instrumental signal (absorbance)
3 Concentration of standard solutions - purity of CaCO3
4 Volume of the glassware (pipettes, volumetric flasks)
5 Mass
4. List the reference standards needed and state the information regarding
For the analyte

1 Name/Chemical Formula/Producer: CaCO3 purity, Merck, min. 99.99 %
2 Name/Chemical Formula/Producer: CaCO3 molar masses/IUPAC

Absorbance/(Spectro)photometer/Calibrated against
1 e.g. mass/balance/calibrated by NMI, U = xx
traceable optical standard (i.e. PTB)
Volume/Laboratory glassware (pipettes, volumetric
2 Quantity/Equipment/Calibration: flasks/calibrated by manufacturer (i.e. Hirschmann
Laborgerate )
Mass/Analytical balance/calibrated by manufacturer
against traceable mass standards

Are all important parameters included
Yes No
in the model equation?
Other important parameters are: Matrix effect
66

1 Via traceable calibration data
2 Via traceable volumetric measurements
3 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
The measurement procedure
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 1.0−12.0 mg dL-1

Calcium concentration in serum result is intended to be used for clinical
Intended use of the results
interpretation
Parameters to be validated Value requested by the customer
LOD
LOQ
Repeatability
Mark the customer’s
requirements and give 8 % as CV, by WHO procedure
Within-lab reproducibility
their values 2 % as CV, the actual state-of-art
Trueness
Measurement
uncertainty
Other-state
68

VALIDATION
69
Further information: ROCHE-Control serum type Precipath U
6. Measuring range
Linearity
Upper limit
LOD
LOQ
Repeatability
8. Robustness
70
9. Quality control
Control charts

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

Calculations
validated
LOD
LOQ
Repeatability
5
∑ (c
1
i , obs − cQC ) 2
n ( n − 1)
CV = × 100 = 1.27 %
cQC
Trueness
Value requested by The requirement

Value obtained
Parameter the customer is fulfilled
during validation
(the same as stated in question 3) Yes/No
LOD
LOQ
Repeatability
Within-lab 8 % as CV, by WHO procedure
1.27 % YES
reproducibility 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
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73

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

m 625.0 mg
MCa 40.078 g mol-1
P 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

Standard
uncertainty
m 0.2 mg
MCa 0.002 g mol-1
P 0.0058 mass fraction
V500 0.15 mL
MCaCO3 0.0024 g mol-1
74
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 ⎞
( )
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Standard
uncertainty
m 625.0 0.2 mg
MCa 40.078 0.002 g mol-1
P 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 mL
V100 100.000 0.058 mL
Ax 0.323 0.004 no units
A-10 0.338 0.002 no units
Ablank 0.052 0.004 no units
Vf 0.100 0.002 mL
Vint 0.100 0.002 mL
ucCD PJPRO
75
units
U(cCa) = k u (cCa) = 0.606 [mg dL-1], k = 2
1 Volume serum measurements
2 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

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6WDQGDUG RSHUDWLRQ SURFHGXUH IRU COLQLFDO FKHPLVWU\ 'HWHUPLQDWLRQ RI FDOFLXP E\
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77
Addendum I: Measurement uncertainty calculation:

Preparation of the standard solution
78
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79
Calibration
Calculation of calcium concentration in serum sample

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80
Chapter 3
Determination of Radium in Water
by a-Spectrometry
Ljudmila Benedik, Urška Repinc, Monika Inkret

81
Measurand Activity concentration of Ra-226 in water (Bq L-1) (by α-spectrometry)
Authors of the example Ljudmila Benedik, Urška Repinc, Monika Inkret
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) 1−2, 133−137
Directive 98/83/EC on the quality of water intended for human

Customer’s requirement
consumption
82
II. Attached files

File is
File number, type and
name
Yes No
Given
EX-08-1-I-Ra226-water- About the analytical procedure: short
9
1-I
by the
AS-2006-Ver1.ppt introduction
lecturer
Description of the analytical
PART I
procedure
9
Each
The customer’s requirements participant
PART II concerning the quality of the 9 receives
2 - Yellow
measurement result own copy

EX-08-2-Y-Ra226-water-
Validation of the measurement and may
AS-2006-Ver1.doc
keep it
PART III procedure – relevant equations 9
and measurement data
Measurement uncertainty of the
PART IV result – relevant equations and 9
measurement data
Establishing traceability in
PART I
analytical chemistry
9

PART II 9
3 - Green
measurement procedures
EX-08-3-G-Ra226-water-
AS-2006-Ver1.doc Building an uncertainty budget 9
Addendum 1: By spreadsheet
PART III approach
9
Addendum 2: By dedicated
software
9

0 April 2007
1
83
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84
Determination Radiumby in
Flame by α-Spectrometry
Atomic
Water Absorption Spectrometry
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Determination Radiumby in
Flame by α-Spectrometry
Atomic
Water Absorption Spectrometry
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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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89
Figure 4. Experimental protocol for determination Ra-226 in water
3. Apparatus
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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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9. Calculation
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PBa-133sample tBa-133Std × mBa-133Std
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9.2 Alpha spectrometer efficiency determination
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94
9.3 Activity concentration of Ra-226 in the sample (Bq L-1)

PRa-226
A Ra-226 =
tRa-226 × eα det × Vsample × Rchem
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95

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 arti¿cial radionuclide Reference concentrations for other radionuclides can be
calculated using the dose coef¿cients 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

Note 1
Ra-226 0.04 Bq L-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
2.71 + 4.65 Bkg
LLD =
tBkg × ε α det × Rchem × Vsample
Measurement data
Input quantity Unit Value

Rchem radiochemical yield (recovery) - 0.803
εα 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 s
Vsample volume of the sample L
97

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Equations
u ( ARa-226 ) ⎛ u (PRa-226 ) ⎞ ⎛ u ( eα det ) ⎞
2 2 2 2
⎛ u (Vsample ) ⎞ ⎛ u (Rchem ) ⎞
= ⎜ ⎟ +⎜ ⎟ + ⎜ ⎟ +⎜
ARa-226 ⎝ PRa-226 ⎠ ⎝ eα det ⎠ ⎝ Vsample ⎠ ⎝ Rchem ⎟⎠
( )⎞⎟ ( )⎞⎟
2 2
u ( Rchem ) ⎛ u PBa-133sample ⎛ u mBa-133sample
2 2
⎛ u (PBa-133Std ) ⎞ ⎛ u (mBa-133Std ) ⎞
= ⎜ ⎟ + ⎜ ⎟ + ⎜ +⎜
Rchem ⎝ PBa-133Std ⎠ ⎝ mBa-133Std ⎠ ⎜⎝ PBa-133sample ⎟⎠ ⎜⎝ mBa-133sample ⎟⎠
u ( eαdet )
2 2 2 2
⎛ u (PRa-226Std ) ⎞ ⎛ u (mRa-226SS ) ⎞ ⎛ u (ARa-226SS ) ⎞ ⎛ u ( RRa-226Std ) ⎞
= ⎜ ⎟ + ⎜ +⎜ +⎜
eαdet ⎝ Ra-226Std ⎠
P ⎝ mRa-226SS ⎟⎠ ⎝ A Ra-226SS
⎟⎠ ⎝ R ⎟⎠
Ra-226Std
u (ARa-226 ) = k × (ARa-226 )
98
Measurement data
Standard Type of
Unit Value Type of distribution
Input quantity uncertainty uncertainty
(u) normal rectangular triangular
Vsample volume of the sample L 1.0 0.002 B X
mBa-133 sample mass of added Ba-133 in the sample g 0.301 0.001 B X
mBa-133Std mass of added Ba-133 in barium
g 0.112 0.001 B X
standard disc
mRa-226 SS mass of added Ra-226 in standard
g 0.010 0.001 B X
solution
ARa-226 SS activity concentration of Ra-226 in
Bq g-1 2729 - B X
standard solution
tRa-226 time of measurement s 300 000 - - -
tBa-133 sample time of the sample measurement (s) s 3000 - - -

tBa-133Std time of measurement of Ba-133 in
s 3000 - - -
barium standard disc
PRa-226 peak area of Ra-226 - 7516 87 A X
PBa-133 sample peak area of Ba-133 in the sample - 10 914 104 A X
PBa-133 Std peak area of Ba-133 in barium
- 5090 71 A X
standard disc
PRa-226 Std peak area of Ra-226 in standard disc - 12 785 113 A X
Rchem radiochemical yield (recovery) - - - A X
εα det efficiency of alpha detector - - - A X
RRa-226Std radium standard disc recovery - - - A X
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
alpha-spectrometrical sources
procedure
Lozano et al., Journal of Radioanalytical and Nuclear Chemistry
Type of calibration mixed standard source standard addition internal standard
Model equation
TKHDFWLYLW\FRQFHQWUDWLRQRIRDLQVDPSOH%TLLVFDOFXODWHGE\
PRa-226
A Ra-226 =
tRa-226 × eα det × Vsample × Rchem
ARD DFWLYLW\FRQFHQWUDWLRQRIRDLQWKHVDPSOH>%TL@
PRD SHDNDUHDRIRD
V YROXPHRIWKHVDPSOH>L@
Rchem = ×
RHFRYHU\REWDLQHGE\JDPPDVSHFWURPHWU\LVFDOFXODWHGDVIROORZV

P%DVDPSOH SHDNDUHDRI%DLQWKHVDPSOH
P%D6WGD SHDNDUHDRI%DLQEDULXPVWDQGDUGGLVF
101
t%D6WG WLPHRIPHDVXUHPHQWRI%DVWDQGDUGGLVF>V@
$OSKDVSHFWURPHWHUHI¿FLHQF\LVFDOFXODWHGDVIROORZV
PRa-226Std
İĮGHW =
PRD6WG SHDNDUHDRIRDRIVWDQGDUGGLVF
tRD6WG WLPHRIPHDVXUHPHQWRIRDVWDQGDUGGLVF>V@
mRD66 PDVVRIDGGHGRDVWDQGDUGVROXWLRQ>J@
ARD66 RDDFWLYLW\FRQFHQWUDWLRQLQVWDQGDUGVROXWLRQ>%TJ@
1 Uncertainty of concentration of reference solutions
2 Uncertainty of volumes
3 Uncertainty of weighing
4 Uncertainty of measurement, using alpha and gamma detectors
For the analyte

1 Name/Chemical Formula/Producer: Standard Radionuclide Source, Analytics, SRS 67978-121
Ba-133 standard solution, Czech Metrological Institute,
Cert. No: 931-OL-137/99
2 Name/Chemical Formula/Producer: Ra-226 standard solution, NIST SRM 4967
102

Quantity/Equipment/Calibration: Graduated and mixing cylinders, volumetric flask/with
1 e.g. mass/balance/calibrated by NMI, U = xx established traceability
(k = 2) see also data yellow sheet BLAUBRAND® tolerance
Mass/calibrated balance/with established traceability
Sartorius

Yes No
model equation?
Uncertainty of measured background of detector,
Other important parameters are: uncertainty of measured blank reagents (minor
contributions)

1 Analysis of matrix CRM
2 Participation in a proficiency testing scheme
3 -
103


The measurement alpha-spectrometric sources
procedure J.C. Lozano, F. Fernandez and J.M.G. Gomez
Journal of Radioanalytical and Nuclear Chemistry 223 (1997) 1−2, 133−137.
Analyte Ra-226
The measurand Activity concentration of Ra-226 in drinking water
Unit Bq L-1

Matrix Drinking water
Measuring range 0.01–10 Bq L-1

Compliance to the requirements in the revised water directive 98/83/EC on
Intended use of the results
the quality of water intended for human consumption
LOD 0.04 Bq L-1
LOQ
Mark the customer’s Repeatability
requirements and give
their values Within-lab reproducibility
Trueness
Other-state

VALIDATION
104
spiking of samples with pure substances and calculation of recovery
6. Measuring range
Linearity
Upper limit
LOD
LOQ
Repeatability
105
8. Robustness
9. Quality control
Control charts

R square
106

Parameters requested to
Calculations
be validated
2.71 + 4.65 14.26092744
LOD LLD = = 0.000245 Bq L-1
420 730 × 0.2453 × 0.803 × 1
LOQ
Repeatability
Trueness
Value requested by the The requirement
Value obtained
Parameter customer is fulfilled
during validation
LOD 0.04 Bq L-1 0.00025 Bq L-1 YES
LOQ
Repeatability
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\
PRa-226
A Ra-226 =
tRa-226 × α det × Vsample × Rchem
ARD $FWLYLW\FRQFHQWUDWLRQRIRDLQWKHVDPSOH>%TL@
PRD SHDNDUHDRIRD
V YROXPHRIWKHVDPSOH>L@
108
RHFRYHU\PHDVXUHGE\JDPPDVSHFWURPHWU\LVFDOFXODWHGDVIROORZV
Rchem = ×

P%DVDPSOH PHDNDUHDRI%DLQWKHVDPSOH
P%D6WG SHDNDUHDRI%DLQEDULXPVWDQGDUGGLVF
t%D6WG WLPHRIPHDVXUHPHQWRI%DLQEDULXPVWDQGDUGGLVF>V@
$OSKDVSHFWURPHWHUHI¿FLHQF\GHWHUPLQDWLRQLVFDOFXODWHGDVIROORZV
PRa-226Std
İĮGHW =
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

PRa-226 7516 -
tRa-226 300 000 s
εαdet 0.2453 -
Vsample 1.0 L
Rchem 0.803 -

Standard
uncertainty
PRa-226 87 -
tRa-226 0 s Constant
εαdet 0.01392 -
Vsample 0.0020 L
Rchem 0.0142 -

PRa-226 1
A Ra-226 = ×
tRa − 226 × eα det × Vsample Rchem
7516 1
A Ra-226 = × = 0.127 Bq L-1
300 000 × 0.2453 × 1 0.803
7. Calculate the combined standard uncertainty (uc ) of the result and specify units
Using: MDWKHPDWLFDOVROXWLRQ 6SUHDGVKHHW$SSURDFK CRPPHUFLDO6RIWZDUH

Standard
uncertainty
PRa-226 7516 87 -
tRa-226 300 000 0 s
εαdet 0.2453 0.01392 -
110
Vsample 1.0 0.0020 L

Rchem 0.803 0.0142 -
u ( ARa-226 ) ⎛ u (PRa-226 ) ⎞ ⎛ u ( eαdet ) ⎞

2 2 2 2
⎛ u (Vsample ) ⎞ ⎛ u (Rchem ) ⎞
= ⎜ ⎟ +⎜ ⎟ + ⎜ ⎟ +⎜
ARa-226 ⎝ PRa-226 ⎠ ⎝ eαdet ⎠ ⎝ Vsample ⎠ ⎝ Rchem ⎟⎠
u ( ARa-226 ) 2
⎛ 87 ⎞ ⎛ 0.01392 ⎞
2
⎛ 0.0020 ⎞
2
⎛ 0.0142 ⎞
2
= ⎜ + + ⎜ +⎜ = 0.00806
ARa-226 ⎝ 7516 ⎟⎠ ⎜⎝ 0.2453 ⎟⎠ ⎝ 1 ⎟⎠ ⎝ 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
2 Peak area of Ba-133 in the standard disc
3 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
IRUKXPDQFRQVXPSWLRQOf¿c. 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\ Of¿c. J. Eur. Commun. L

(8R$T2M (XURSHDQ CRPPLVVLRQ RHFRPPHQGDWLRQ (8R$T2M

Of¿c. 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
LQFOXGLQJWKH¿UVWDGGHQGXP:+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
Addendum I: Measurement uncertainty calculation, spreadsheet approach (Excel)


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Addendum II: Measurement uncertainty calculation –

GumWorkbench
Model equation:
ARD= PRDtRD×εαGHW× VVDPSOH×RFKHP
RFKHP P%DVDPSOHW%DVDPSOH×m%DVDPSOH×t%D6WG×m%D6WGP%D6WG
εαGHW= PRD6WGtRD6WG×mRD66× ARD66×RRD6WG
List of quantities:
Quantity Unit Definition
-1
ARa-266 Bq L Activity of Ra-266 in sample
PRa-266 Area of Ra-266
tRa-266 s Time of measurement
eαdet Efficiency for alfa detector
Vsample L Volume of the sample
Rchem Radiochemical yield (recovery)
PBa-133sample Area of Ba-133 in sample
tBa-133sample s Time of measurement of the sample
mBa-133sample g Mass of Ba-133 in the sample
tBa-133Std s Time of measurement of Ba-133 standard disc
mBa-133Std g 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 s Time of measurement of the standard disc
mRa-226SS g 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
Standard Sensitivity Uncertainty

Quantity Value Distribution Index
Uncertainty Coefficient Contribution
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 %
PBa-133sample 10 914 104 normal -12 × 10 -6
-1.2 × 10 Bq L
-3 -1
2.3 %
tBa-133sample 3000.0 s
mBa-133sample 0.301200 g 577 × 10-6 g rectangular 0.42 240 × 10-6 Bq L-1 0.0 %
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 0.12719 Bq L -1
8.04 × 10 Bq L
-3 -1

119
εαdet: Ef¿ciency of alfa detector

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 90.1 %
ARa-226SS 2729.0 10.7 normal -90 × 10 -6
-960 × 10 -6
0.4 %
RRa-226Std 0.9344 0.0150 normal -0.26 -3.9 × 10-3
7.2 %
eαdet 0.2453 0.0146
Rchem: Radiochemical yield (recovery)

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 %
PBa-133Std 5090.0 71.0 normal -160 × 10 -6
-0.011 61.7 %
Rchem 0.8030 0.0143
Result:
Expanded
Quantity Value Coverage factor Coverage
Uncertainty
ARa-266 0.127 Bq L-1 0.016 Bq L-1 2.00 95 %
120
Chapter 4
Determination of Polar Pesticides by Liquid
Chromatography Mass Spectrometry
Allan Künnapas, Koit Herodes, Ivo Leito
u TrainMiC example summary form (’blue page’)

u A short introduction to the analytical procedure (’slides’)
u All input needed to do the three exercises (’yellow pages’)
u The solved exercises (’green pages’)
121

Concentration of imazalil and thiabendazole in tangerines by liquid
Measurand
chromatography-mass spectrometry
Authors of the example Allan Künnapas, Koit Herodes, Ivo Leito

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
Customer’s requirement in the EU Directives 93/58/EEC and 00/42/EEC on pesticide residues
analysis
122
II. Attached files
File is
File number,
type and name
Yes No
Ex-04-1-I-
Pesticides- Given by the
1-I
Food-LCMS-
About the analytical procedure: short introduction 9 leacturer
2006-Ver1.ppt

Each
The customer’s requirements concerning participant
Ex-04-2-Y- PART II 9 receives own
2 - Yellow
the quality of the measurement result

Pesticides- copy and may
Validation of the measurement keep it
Food-LCMS-
2006-Ver1.doc
PART III procedure – relevant equations and 9
measurement data
Measurement uncertainty of the result
PART IV – relevant equations and measurement 9
data
PART I
chemistry
9
Ex-04-3-G- Single laboratory validation of

9
3 - Green
PART II
Pesticides- measurement procedures
Food-LCMS-
2006-Ver1.doc
Bulding an uncertainty budget 9
PART III Addendum 1: By spreadsheet approach 9

0 April 2007 -
1
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 customer’s 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
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4. Reagents
1000 mg kg-1 individual pesticide standard solutions
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131
6. Calculation
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132
PART II. The customer’s requirement concerning quality of the

measurement result
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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
Relative intensity EI-GC-MS CI-GC-MS, GC-MSn, LC-MS, LC-MSn

(% of base peak) (relative) (relative)
>50 % ±10 % ±20 %
>20−50 % ±15 % ±25 %
>10−20 % ±20 % ±30 %
≤ 10 % ±50 % ±50 %
134

Equations
wexp
R= × 100 %
wtheor
n∑ x 2 − ( ∑ x)
2
STDEV =
n(n − 1)
AVERAGE =
∑x
n
STDEV
RSD = ×100 %
AVERAGE
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135
Measurement data
Thiaben-
Imazalil Thiabendazole Imazalil
dazole
wexp wtheor R wexp wtheor R
Peak area Peak area
(mg kg-1) (mg kg-1) (%) (mg kg-1) (mg kg-1) (%)
0.06427 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
uw = usys
2
+ urnd
2
2
urel_rec + urel_meth
2
urnd = ×w
100 %
d = w − wref
s
uref =
n1
d2
udev =
n
usys = uref
2
+ udev
2
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137
Measurement data
Imazalil Thiabendazole Comments
The relative standard deviation of recovery
urel_rec 27 % 2% calculated from parallel measurement results (two
measurements per day on three consecutive days)
The relative standard deviation of results obtained
urel_meth 10 % 6% for the same solution from repeated injections of
the same solution
w 1.3350 mg kg-1 3.5230 mg kg-1
consensus value of interlaboratory comparison
wref 1.2975 mg kg-1 3.2863 mg kg-1
measurement
s 0.0530 mg kg-1 0.5571 mg kg-1
nl 2 3
n 1 1
138
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)

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
Measurement
to almost dryness and the sample is dissolved in 10−20 mL of methanol. Sample is
procedure
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
wc × V10 × ρ × Ve
w=
V50 × m
w PDVVIUDFWLRQRIe[WUDFWDEOeSeVWLFLGeLQVDPSOePJRISeVWLFLGeSeUNJRI
VDPSOe>PJNJ@
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140
1 Mass fraction of extractable pesticide in analysed extract (wc, mg kg-1)
2 The full volume of acetone extract (Ve, mL)
3 The volume of final extract in methanol (V10, mL)
4 The volume of acetone extract to be purified (V50, mL)
5 The density of methanol (ρ, g mL-1)
6 The mass of homogenized sample (m, g)
For the analyte

Imazalil (solid substance)/C14H14Cl2N2O/Dr. Ehrenstorfer
Name/ChemicalFormula/ Value including uncertainty (with units):
1
Producer: Imazalil: purity 97.5 % (tolerance ±0.5 %) (data obtained from
corresponding Certificate of Analysis)
Thiabendazole (solid substance)/C10H7N3S/Dr. Ehrenstorfer
Name/ChemicalFormula/ Value including uncertainty (with units):
2
Producer: Thiabendazole: purity 99.0 % (tolerance ±0.5 %) (data obtained from
corresponding Certificate of Analysis)

1 e.g. mass/balance/calibrated by NMI, U = xx None

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

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

MEASUREMENT PROCEDURES

Sample preparation procedure is modified AOAC official method 985.22. Analysis
The measurement
was carried out on an LC-MS system using a self-developed chromatographic
procedure
method.
Analyte Residues of imazalil and thiabendazole (polar basic pesticides)
Acetone-extractable pesticides in tangerines.
The measurand Results are not recovery corrected, thus extractable pesticides are determined, not
total amounts.
Unit mg kg-1 (ppm)

Matrix Tangerines
imazalil 0.004–0.9 mg kg-1
Measuring range
thiabendazole 0.003–0.7 mg kg-1

Post-registration control and monitoring of pesticides based on MRLs set by
Intended use of the results 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 70–110 %
requirements and give their
values Measurement
uncertainty
Identity/confirmation: retention time (compared with
standard) + MS^2 fragmentation: imazalil (297 → 201),
Other - state
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).
143

VALIDATION
144
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: 0.004–0.9 mg kg-1; Thiabendazole: 0.003–0.7 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
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
(C18 250 ¥ 4.6 5μ, C18 150 ¥ 150 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
Calculations
to be validated
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.
LOD
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 %
wexp
R= × 100 %
wtheor
Trueness 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
Value obtained
during validation
Imazalil < 0.02 mg kg-1 0.004 mg kg-1 Yes
LOD
Thiabendazole < 0.05 mg kg-1 0.003 mg kg-1 Yes
LOQ
Repeatability
Within-lab
reproducibility
Imazalil 104 % Yes
Trueness 70–110 %
Thiabendazole 73 % Yes
Measurement
MS^2 spectrum in
Confirmation based on similarity to
Other sample is similar to Yes
standard (MS^2 spectrum)
standard

Yes No
148

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

equation
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Model equation
wc × V10 × ρ × Ve
w=
V50 × m
w PDVVIUDFWLRQRISeVWLFLGeLQVDPSOe>PJNJ@
wF PDVVIUDFWLRQRISeVWLFLGeLQDQDO\VeGe[WUDFW>PJNJ@
149
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uw = udev 2 + uref 2
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150
2
urel_rec + urel_meth
2
urnd = ×w
100 %
d = w − wref
s
uref =
n1
d2
udev =
n
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w SeVWLFLGe PDVV IUDFWLRQ LQ D UeIeUeQFe VDPSOe DV GeWeUPLQeG E\ WKe
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>PJNJ@
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n QXPEeURIFRPSOeWeGILCVn LQRXUFDVe
uGeY XQFeUWDLQW\PDQLIeVWeGE\WKeGeYLDWLRQRIWKeODERUDWRU\¶VUeVXOWIURPWKe
UeIeUeQFeYDOXe>PJNJ@

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 Value
Unit Remark
quantity Imazalil Thiabendazole
Mass fraction of residue in extract, calculated based
wc 2.801 7.398 mg kg-1
on calibration
V10 10 10 mL Volume of final methanol extract
ρ 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
m 49.8003 49.8003 g Sample amount taken for extraction
5. Evaluate the standard uncertainty of each input quantity2

Standard uncertainty
Unit Remark
Imazalil Thiabendazole
systematic uncertainty component evaluated based
uref 0.0375 0.3216 mg kg-1
on the results of ILC
random component of uncertainty, calculated using
udev 0.0375 0.2367 mg kg-1 relative uncertainty (repeatability) of recovery and
method
relative standard deviation of recoveries calculated
urel_rec 27 2 %
using addition experiments
relative standard deviation of measuring method
urel_meth 10 6 %
(repeated analysis of the same solution)

wc × V10 × ρ × Ve
w=
V50 × m
w PDVVIUDFWLRQRISeVWLFLGeLQVDPSOe>PJNJ@
wF PDVVIUDFWLRQRISeVWLFLGeLQDQDO\VeGe[WUDFW>PJNJ@

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152
2.801 × 10 × 0.791 × 150

w(imazalil) = = 1.335 mg kg -1
50 × 49.8003
7.398 × 10 × 0.791 × 150
w( thiabendazole) = = 3.523 mg kg -1
50 × 49.8003
7. Calculate the combined standard uncertainty (uw ) of the result and specify units
Using: MDWKePDWLFDOVROXWLRQ 6SUeDGVKeeWDSSURDFK CRPPeUFLDOVRIWZDUe
Uncertainty Standard
Value Unit Remark
components uncertainty
systematic uncertainty component
usys (imazalil) - 0.0530 mg kg-1
evaluated based on the results of ILC
random component of uncertainty,
urnd (imazalil) - 0.3844 mg kg-1 calculated using relative uncertainty
(repeatability) of recovery and method
systematic uncertainty component
usys (thiabendazole) - 0.3993 mg kg-1
evaluated based on the results of ILC
random component of uncertainty,
urnd(thiabendazole) - 0.2228 mg kg-1 calculated using relative uncertainty
(repeatability) of recovery and method
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2
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2
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d = w − wref uUeOBUeF UeODWLYeXQFeUWDLQW\RIUeFRYeU\>@
s uUeOBPeWK UeODWLYeXQFeUWDLQW\RIDQDO\VLVPeWKRG>@
uref = w SeVWLFLGePDVVIUDFWLRQLQVDPSOe>PJNJ@
n1 d GLIIeUeQFeLQPDVVIUDFWLRQEeWZeeQRXU
ODERUDWRU\DQGUeIeUeQFeYDOXe>PJNJ@
d2
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n VDPSOe>PJNJ@
2
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+ udev s WKeVWDQGDUGGeYLDWLRQIRUUeIeUeQFeYDOXe
>PJNJ@
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ILC
n QXPEeURIFRPSOeWeGILCV
153
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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

27 % 2 + 10 % 2
urnd = × 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
0.03752
udev = = 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

2 %2 + 6 %2
urnd = × 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
0.2367 2
udev = = 0.2367 mg kg -1
1
usys = 0.32162 + 0.2367 2 = 0.3993 mg kg -1
ULPD]DOLO ¥uZLPD]DOLO ¥PJNJ PJNJQRUPk
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contributing the most to uw
1 urnd contribution: 98.13 % (imazalil), 23.74 % (thiabendazole)
2 usys contribution: 1.87 % (imazalil), 76.27 % (thiabendazole)

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Further readings
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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 The summary form (‘blue page’)

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

Analytical procedure continuous flow analysis (CFA) and spectrometric detection (ISO 11732:
2005)
Directive 98/83/EC on the quality of water intended for human
Customer requirement
consumption
158
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
II. Attached files

File is
File number, type
and name
Yes No
Ex-07-1-I-
NH4-water- About the analytical procedure: short Given by the
1-I
Photometry- introduction
9 lecturer
2006-Ver1.ppt
Description of the analytical
PART I
procedure
9
The customer’s requirements Each participant
PART II concerning the quality of the 9 receives own
Ex-07-2-Y- measurement result
2 - Yellow
copy and may

NH4-water- Validation of the measurement keep it
Photometry- PART III procedure – relevant equations and 9
2006-Ver1.doc measurement data
Measurement uncertainty of the

PART IV result – relevant equations and 9
measurement data

PART I
chemistry
9

Ex-07-3-G- PART II 9
3 - Green
NH4-water- measurement procedures

Photometry- Bulding an uncertainty budget 9
2006-Ver1.doc
Addendum 1: By spreadsheet
PART III
approach


0 April 2007 -
1
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 customer’s 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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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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5. Sampling and pre-treatment

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6. Procedure
Instrument set-up
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7. Method of calculation
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PART II. The customer’s 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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Precision of Limit of detection of

Parameter Trueness of parametric value
parametric value parametric value
(Note 1)
(Note 2) (Note 3)
Ammonium 10 % 10 % 10 %
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GeYLDWLRQ ZLWKLQ DQG EeWZeeQ EDWFK RI WKe VSUeDG RI UeVXOWV DERXW WKe
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Note 3: LLPLWRIGeWeFWLRQLVeLWKeU
² WKUee WLPeV WKe UeODWLYe ZLWKLQ EDWFK VWDQGDUG GeYLDWLRQ RI D QDWXUDO
VDPSOeFRQWDLQLQJDORZFRQFeQWUDWLRQRIWKeSDUDPeWeURU
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168

Limit of Detection
Equation
CDOFXODWeGeWeFWLRQOLPLWDVVWDQGDUGGeYLDWLRQV±Vee'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
s mg L-1 0.005 0.021
n - 27 28
Time period months 7 7
Nominal value mg L-1 0.100 0.600
169
External quality control – participating in PT studies
Nominal value
laboratory result xi Bias sR Number of
Year/Exercise xref
[mg L-1] [%] [%] labs
[Mg l-1]
1999/1 81 83 2.4 10 31
1999/2 73 75 2.7 7 36
2000/1 264 269 1.9 8 32
2000/2 210 213 1.4 10 35
2001/1 110 112 1.8 7 36
2001/2 140 144 2.9 11 34
170

The relevant equations
C = AVDPSOe – b/ b ¥fGLO / R
171
172
Measurement data
Standard Relative standard Type of
Quantity Unit Value Type of distribution
uncertainty uncertainty uncertainty
(u) (%) normal rectangular triangular
Concentration of
C NH4+ in the sample mg L-1 0.2465 0.0031 1.3 x
solution
Absorbance of the
Asample AU 0.2560 0.0015 0.58 x
sample solution
Intercept of
b0 AU 0.0143 0.0021 14 x
calibration line
Slope of calibration
AU L
b1 line – unit AU 0.9902 0.0070 0.71 x
mg-1
divided by mg N L-1
fdil Dilution factor unitless 1 0.00 0.00
Recovery factor of
R unitless 0.9900 0.0058 0.59 x
the analysis
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
ISO 11732:2005 using the continuous flow analysis and photometric detection
procedure
Model equation
C AVDPSOe±EE¥fGLOR
C CRQFeQWUDWLRQRI1+LQWKeVDPSOeVROXWLRQ>PJL@
AVDPSOe $EVRUEDQFeRIWKeVDPSOeVROXWLRQ>$8@
b IQWeUFeSWRIFDOLEUDWLRQOLQe>$8@
b 6ORSeRIFDOLEUDWLRQOLQe>$8GLYLGeGE\PJL@
fGLO 'LOXWLRQIDFWRU
R ReFRYeU\IDFWRURIWKeDQDO\VLV
TKeFDOLEUDWLRQOLQeeYDOXDWeGE\OLQeDUUeJUeVVLRQLVEDVeGRQ¿YeVWDQGDUGVLQWKeUDQJe
−PJL
TKeGLOXWeVWDQGDUGVROXWLRQRIPJLLVSUeSDUeGIURPDVWRFNVROXWLRQRIPJ
LTKLVVWRFNVROXWLRQLVSUeSDUeGIURPDPPRQLXPFKORULGe
1 Recovery factor – contributing 30 % to the expanded uncertainty
2 Absorbance of the sample - here the main source is the drift contributing about 20%
3 Calibration – standard solution – purity of ammonium chloride
4 Calibration – volumetric flasks and pipettes
174
For the analyte
1 Name/ChemicalFormula/Producer: Ammonium chloride, NH4Cl, Merck pa min 99 %
2 Name/ChemicalFormula/Producer:

Absorbance – relative measurement. Not direct part of
the traceability chain
2 Quantity/Equipment/Calibration: Volumetric flasks – Class A quality
Volumetric pipettes – calibrated by producer and

regularly checked by the laboratory

Yes No
model equation?
Other important parameters are: Within-lab reproducibility, contamination

1 Participating in PT rounds
2
3
175


The measurement procedure Measurement procedure is based on EN/ISO11732
Analyte Ammonium
The measurand Dissolved ammonium in water sample arriving in the laboratory
Unit mg L-1

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

Intended use of the results To analyse drinking water according to the EU requirements in the EU directive
LOD 0.05 mg L-1: - 3s on a natural sample,
LOD
5s on a blank: s is repeatability
LOQ
Repeatability
at 0.5 mg L-1, s = 0.025 mg L-1:
requirements and give Within-lab
at 0.2 mg L-1, s the demand estimated to be
their values reproducibility
s = 0.010 mg L-1 or 5 %
at 0.5 mg L-1 less than 0.05 mg L-1 or less than
Trueness
10 % relative
Measurement
uncertainty
Other-state

VALIDATION
176
6. Measuring range
Linearity
Upper limit
LOD
LOQ
Repeatability
8. Robustness
177
9. Quality control
Control charts

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

Parameters requested
Calculations
to be validated
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 %.
From PT results the trueneness is estimated to be less than

Trueness 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
Measurement uncertainty 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
LOD 0.05 mg L-1 0.02 mg L-1 Yes
LOQ
Repeatability
Within-lab
5 % at a level of 0.2 mg L-1 4% Yes
reproducibility
Trueness 10 % 2-3 % Yes
Measurement
uncertainty
Other
The analytical procedure is ¿t for the intended use:
Yes No
180

Measurand Dissolved ammonium in water sample arriving in the laboratory
Unit mg L-1

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

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

Asample 0.256 AU
b0 0.01734 AU
b1 986.3 AU L mg-1
fdil 1 unitless
R 0.99 unitless

Input Standard
Unit Remark
Asample 1.49 ¥ 10-3 AU Takes into account repeatability, drift and rounding
b0 0.00207 AU
Takes into account reference solution (0.3 % relative
b1 0.0070 AU L mg-1 uncertainty, preparation and measurement of calibration
standards and constructing the calibration graph
Dilution of sample – in this case the sample was not
fdil 0 unitless
diluted
R 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
0.256 − 0.01734
C= × 1 × 0.99 = 0.247 mg L-1
986.3
182
Using: MDWKePDWLFDOVROXWLRQ 6SUeDGVKeeW$SSURDFK CRPPeUFLDO6RIWZDUe
Input Standard
Value Unit Remark
Asample 0.256 1.49 ¥ 10-3 AU
From calibration graph – note regression without
weights and a slight curvature. A too high
b0 0.01435 0.00207 AU
estimate but here we are interested in higher
concentrations.
b1 0.9902 0.0070 AU L mg-1
fdil 1 0 Unitless Sample was not diluted
R 0.99 0.01 Unitless
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 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
2
uncertainty
Preparation of standard solution 10 mg L-1 ± 0.13 mg L-1 (k = 2) - main components dilution using a
3
1 mL 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
1RUGWeVWWeFKQLFDOUeSRUWKWWSZZZQRUGLFLQQRYDWLRQQeWQRUGWeVW¿OeUWeFSGI
184
Addendum: Measurement uncertainty calculation -

GumWorkbench
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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 Àasks.
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 }
ΣAC = C1 ¥ A1 + C2 ¥ A2 + C3 ¥ A3 +C4 ¥ A4 + C5 ¥ A5;
AvgC=(C1+C2+C3+C4+C5)/n;
AvgA=(A1+A2+A3+A4+A5)/n;
ΣCC=C1 ¥ C1+C2 ¥ C2+C3 ¥ C3+C4 ¥ C4+C5 ¥ C5;
b1=(ΣAC-n ¥ AvgC ¥ AvgA)/(ΣCC-n ¥ AvgC ¥ AvgC);
b0=AvgA-b1 ¥ AvgC
List of quantities:
C 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
R unitless Recovery factor of the analysis
-1
Cst_0 mg N mL Concentration of NH4+ in calibration stock solution
mNH4Cl g Weight of NH4Cl
V1000 mL Volume of 1 L volumetric flask
PNH4Cl unitless Purity of NH4Cl
Conversion factor for converting the amount of ammonium chloride (NH4Cl)
fNH4Clconv unitless
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
Volume of ammonium standard solution taken for preparing the 1st
V1_st mL
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
Volume of ammonium standard solution taken for preparing the 2nd
V2_st mL
V2_100 mL Volume of the 2nd ammonium calibration standard solution
C3 mg N L-1 Concentration of the 3rd ammonium calibration standard solution
186
Volume of ammonium standard solution taken for preparing the 3rd

V3_st mL
V3_100 mL Volume of the 3rd ammonium calibration standard solution
-1
C4 mg N L Concentration of the 4th ammonium calibration standard solution
Volume of ammonium standard solution taken for preparing the 4th
V4_st mL
V4_100 mL Volume of the 4th ammonium calibration standard solution
C5 mg N L-1 Concentration of the 5th ammonium calibration standard solution
Volume of ammonium standard solution taken for preparing the 5th
V5_st mL
V5_100 mL Volume of the 5th ammonium calibration standard solution
Asample_rep
Asample_drift
Asample_round
ΣAC - 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
-1
AvgC mg N L Interim quantity for regression statistics calculation
n unitless Number of points on the calibration line
AvgA AU Interim quantity for regression statistics calculation
ΣCC - Interim quantity for regression statistics calculation
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

uncertainty coefficient contribution
Asample 0.25600 AU 1.48 ¥ 10-3 AU
b0 0.01435 AU 2.07 ¥ 10-3 AU

0.99023 7.01 ¥ 10-3
b1
AU L mg-1 AU L mg-1
fdil 1.0 unitless 0.0 unitless
5.77 ¥ 10-3
R 0.99000 unitless rectangular -0.25 -1.4 ¥ 10-3 mg L-1 21.3 %
unitless
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 0.0 %
V1000 1.000000 mL 577 ¥ 10-6 mL rectangular -0.25 -140 ¥ 10-6 mg L-1 0.2 %
2.89 ¥ 10-3
PNH4Cl 0.99500 unitless rectangular 0.25 720 ¥ 10-6 mg L-1 5.3 %
unitless
0.26185152642501
fNH4Clconv
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 20.9 %
V100 100.0000 mL 0.0577 mL rectangular -2.5 ¥ 10-3 -140 ¥ 10-6 mg L-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 0.0 %
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 %
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 %
191

uncertainty coefficient contribution
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 %
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 18.2 %
Asample_round 0.0 289 ¥ 10-6 rectangular 1.0 290 ¥ 10-6 mg L-1 0.9 %
ΣAC 1.5720 - 0.0108 -
A1 0.108000 AU 577 ¥ 10-6 AU rectangular -0.36 -210 ¥ 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 0.0 %
AvgC 0.45771 mg L-1 3.27 ¥ 10-3 mg L-1
n 5.0 unitless
AvgA 0.467580 AU 404 ¥ 10-6 AU
ΣCC 1.5544 - 0.0211 -
C 0.24650 mg L-1 3.11 ¥ 10-3 mg L-1
Results:
Expanded
Quantity Value Coverage factor Coverage
uncertainty
C 0.2465 mg L-1 2.5 % (relative) 2.00 manual
192
Appendix 1
TrainMiC® Exercises (‘white pages’)
193
TrainMiC Exercises (‘white pages’)
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


(k = 2) see also data yellow sheet

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

1
2
3
198
199


The measurement procedure
Analyte
The measurand
Unit

Matrix
Measuring range

Intended use of the results:
LOD
LOQ
Mark the customer’s Repeatability
requirements and give
their values Within-lab reproducibility
Trueness
Other-state

VALIDATION
200
6. Measuring range
Linearity
Upper limit
LOD
LOQ
Repeatability
8. Robustness
201
9. Quality control
Control charts
Participation in proficiency testing schemes

R squared
202

Calculations
validated
LOD
LOQ
Repeatability
Trueness
Value obtained
during validation
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


Standard
uncertainty

Å
Using: MDWKePDWLFDOVROXWLRQ 6SUeDGVKeeWDSSURDFK CRPPeUFLDOVRIWZDUe
Input Standard
Value Unit 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

and validation in chemistry Vol. 1
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Abstract
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The mission of the JRC is to provide customer-driven scientific and technical support for the

PRACTICAL EXAMPLES ON TRACEABILITY, MEASUREMENT UNCERTAINTY AND VALIDATION IN CHEMISTRY

Nineta Majcen Authors:

ISBN 978-92-79-12021-3 EUR22791/2 EN - 2010

Freephone number (*):

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.

© European Union, 2010

Reproduction is authorised provided the source is acknowledged

HOW TO USE THE BOOK ...................................................................................................6

ABOUT THE AUTHORS .....................................................................................................11

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

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

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

APPENDIX 2 ..................................................................................................................... 209

If you will tell it to me, I will forget

How does a standardised TrainMiC® example look like?

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Figure 1. Harmonised TrainMiC® example

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What is a recommended approach of conducting a TrainMiC®

About the structure of this handbook

Nineta Majcen and Philip Taylor

Figure 2. A process of conducting a completeTrainMiC® example

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u TrainMiC example summary form (‘blue page’)

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I. General information about the example

Measurand Mass fraction of Au in gold alloys (‰)

Example number Ex-06

Authors of the example Veselin Kmetov, Emilia Vassileva

Determination of gold in jewellery gold alloys by flame atomic

II. Attached files

alloys-FAAS-2006- About the analytical procedure: short introduction 9 lecturer

PART I Description of the analytical procedure 9

Ex-06-2-Y-Au- measurement result copy and

Single laboratory validation of

III. History of the example

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 III ................................................................................................................................34

PART I. Description of the analytical procedure

Description of the analytical procedure

Sample preparation procedure

Atomic absorption measurement

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

FAAS parameters Values ASDI parameters

Air/C2H2 units 50/18 Smoothing Savitzky-Golay 24 points

Working range μg g-1 37−43 Pseudo plateau 3 s

Readings – points [s] 50 Total time for one set 66 s

Concentration of initial standard solution made up from pure gold

m_ pureAu × Au_ purity

Concentration of calibration standard solutions

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Calculation of Au mass fraction (W_‰) in analysed sample

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