Professional Documents
Culture Documents
Some would say an uphill struggle. Comparable to mountain walking. Hard work, but then
the satisfaction of reaching the top is absolutely great. And so is the view.
As with all human endeavour, it always helps to know what you are doing, thus theoretical
knowledge forms the basis. Likewise in analytical chemistry. Understanding the measurement
science, the metrology, is important. That is why in the international standard ISO/IEC-17025
General requirements for the competence of testing and calibration laboratories section five deals
with technical requirements such as traceability, validation and uncertainty. The European Life
Long Learning Programme TrainMiC, created in 2001, produced material for teaching the
theory.
As excellence in theory does not necessarily mean mastering practice, a need for developing
practical examples later arose. This is what you can find in this book, which is intended as a first
of a series of such compilations.
Inspired by the NORDTEST Trollbook, we also decided to have a mascot. For each volume,
a different one, which would be taken from the treasure of European fairy tales and legends.
For this first volume, the fairy tale character of Kekec (pronounced as Kekets) was chosen. Kekec
is a brave, clever and cheerful shepherd boy who lives in Slovenian mountains. He always brings
good to the people that surround him and he helps those that are in trouble. And in that sense,
that is what is the intention of this book.
We hope it succeeds in doing so.
Nineta Majcen
Philip Taylor
ISBN 978-92-79-12021-3
/$1(1&
The mission of the JRC is to provide customer-driven scientific and technical support for the
conception, development, implementation and monitoring of EU policies. As a service of the
European Commission, the JRC functions as a reference centre of science and technology for
the Union. Close to the policy-making process, it serves the common interest of the Member
States, while being independent of special interests, whether private or national.
Practical Examples on
Traceability,
Measurement Uncertainty
and Validation
in Chemistry
Volume 1
Edited by
Nineta Majcen, Philip Taylor
Authors:
Ljudmila Benedik
Steluta Duta
Koit Herodes
Monika Inkret
Veselin Kmetov
Allan Knnapas
Ivo Leito
Bertil Magnusson
Urka Repinc
Philip Taylor
Emilia Vassileva
EUR22791/2 EN - 2010
Practical Examples on
Traceability,
Measurement Uncertainty
and Validation
in Chemistry
Volume 1
Second edition
Edited by
Nineta Majcen, Philip Taylor
Authors:
Ljudmila Benedik
Steluta Duta
Koit Herodes
Monika Inkret
Veselin Kmetov
Allan Knnapas
Ivo Leito
Bertil Magnusson
Urka Repinc
Philip Taylor
Emilia Vassileva
European Commission
Joint Research Centre
Institute for Reference Materials and Measurements
Contact information
Address: Retieseweg 111, B-2440 Geel, Belgium
E-mail: philip.taylor@ec.europa.eu
Tel.: +32 (0)14 571 605
Fax: +32 (0)14 571 863
http://irmm.jrc.ec.europa.eu/
http://www.jrc.ec.europa.eu/
Legal Notice
Neither the European Commission nor any person acting on behalf of the Commission
is responsible for the use which might be made of this publication.
(XURSH'LUHFWLVDVHUYLFHWRKHOS\RXQGDQVZHUV
WR\RXUTXHVWLRQVDERXWWKH(XURSHDQ8QLRQ
Freephone number (*):
00 800 6 7 8 9 10 11
(*) Certain mobile telephone operators do not allow access to 00 800 numbers or these calls may be billed.
JRC 59026
EUR 22791/2 EN
ISBN 978-92-79-12021-3
ISSN 1018-5593
doi: 10.2787/10402
European Union, 2010
Reproduction is authorised provided the source is acknowledged
Printed in
TABLE OF CONTENTS
INTRODUCTION ..................................................................................................................5
HOW TO USE THE BOOK ...................................................................................................6
ABOUT THE AUTHORS .....................................................................................................11
CHAPTER 1..........................................................................................................................17
Analysis of Gold Alloys by Flame Atomic Absorption Spectrometry
Veselin Kmetov, Emilia Vassileva
CHAPTER 2..........................................................................................................................51
Determination of Calcium in Serum by Spectrophotometry
Steluta Duta, Philip Taylor
CHAPTER 3..........................................................................................................................81
Determination of Radium in Water by -Spectrometry
Ljudmila Benedik, Urka Repinc, Monika Inkret
Abbreviations
CRM
CHUWLHGUHIHUHQFHPDWHULDOV
RM
RHIHUHQFHPDWHULDOV
QC
QXDOLW\FRQWURO
PT
PURFLHQF\WHVWLQJ
ILC
IQWHUODERUDWRU\FRPSDULVRQV
Introduction
If you will tell it to me, I will forget
If you will show it to me, I will forget
If you involve me, I will remember.
Xun Zi
Chinese philosopher
310-237 BC
CKHPLFDO DQG ELRDQDO\WLFDO PHDVXUHPHQWV DUH RPQLSUHVHQW DQG RIWHQ YHU\ LPSRUWDQW
LQRXUVRFLHW\-XVWWKLQNRIWKHTXDOLW\RIWKHIRRGZHHDWWKHDLUZHEUHDWKHWKHUROH
RIWKHVHPHDVXUHPHQWVLQKHDOWKFDUHLQWUDGHDQGLQUHVHDUFKIQDOOWKHVHFDVHVSHRSOH
VWULYHWRJHWUHOLDEOHGDWDTKHUHLVDQLQWHUQDWLRQDOVWDQGDUGIRUDVVXULQJWKHTXDOLW\RI
PHDVXUHPHQWGDWDQDPHO\(1I62I(CIWFRQWDLQVSDUWLFXODUPDQDJHPHQWDVZHOO
DVWHFKQLFDOUHTXLUHPHQWVTKHVHWHFKQLFDOUHTXLUHPHQWVDUHOLQNHGWRWKHVFLHQFHEHKLQG
WKHPHDVXUHPHQWVPHDQLQJWKDWPHWURORJLFDOLVVXHVVXFKDVWUDFHDELOLW\XQFHUWDLQW\DQG
YDOLGDWLRQDUHDWWKHKHDUWRIWKLV
TKLVERRNZLOOKHOS\RXPRYLQJIURPWKHWKHRU\RI(1I62I(CWRWKHSUDFWLFH
E\ VKDULQJ SUDFWLFDO H[DPSOHV LQ D GHWDLOHG ZD\ RHDGLQJ WKH ERRN PLJKW JLYH \RX
LQVSLUDWLRQRQKRZWRGHPRQVWUDWHWKHWUDFHDELOLW\RI\RXUUHVXOWVWRDWHFKQLFDODVVHVVRU
LQDQDFFUHGLWDWLRQDXGLW2U\RXFDQPD\EHXVHWKLVPDWHULDOWRH[SODLQWRVWXGHQWVZKDW
LVDQDSSURSULDWHZD\WRWDFNOHYDOLGDWLRQRIDFHUWDLQPHDVXUHPHQWSURFHGXUH"PHUKDSV
\RXZLOOQGLQWKHERRNWKHFRQUPDWLRQRI\RXUDSSURDFKRIXQFHUWDLQW\HVWLPDWLRQ"
IQ VKRUW WKLV ERRN LV LQWHQGHG IRU DQDO\WLFDO FKHPLVWV SHUIRUPLQJ PHDVXUHPHQWV LQ
ODERUDWRULHVRUIRUWKRVHUHVSRQVLEOHIRUVXFKPHDVXUHPHQWVTKRVHOHFWXULQJDQDO\WLFDO
FKHPLVWU\PLJKWDOVRQGLWXVHIXODVZHOODVWKHVWXGHQWVWKHPVHOYHV
TKHERRNLVDSURGXFWRIWKHTUDLQMLCSURJUDPPH>ZZZWUDLQPLFRUJ@TKLVSURJUDPPH
ZDVFRQFHLYHGLQE\WKHIQVWLWXWHIRURHIHUHQFHMDWHULDOVDQGMHDVXUHPHQWVRI
WKH(XURSHDQCRPPLVVLRQ-RLQWRHVHDUFKCHQWUHWRDGGUHVVDQHHGDULVLQJZLWKWKRVH
FRXQWULHV ZDQWLQJ WR HQWHU WKH (8 DW WKDW WLPH RDWKHU WKDQ DSSURDFKLQJ WKLV WUDLQLQJ
LQ DQ DQHFGRWDO ZD\ DQG RUJDQL]LQJ DG KRF HYHQWV D SURJUDPPH ZDV VHW XS FDOOHG
TUDLQMLCWRFUHDWHKDUPRQLVHGWUDLQLQJPDWHULDODVZHOODVWRGLVVHPLQDWHNQRZOHGJH
LQWKHYDULRXVFRXQWULHVYLDDQHWZRUNRIDXWKRULVHGTUDLQMLCWUDLQHUV$IWHUZDUGVWKH
TUDLQMLCSURJUDPPHZDVVSUHDGDOVRLQWKHUHVWRIWKH(8DQG(XURSHVODUJHVWLLIH
LRQJLHDUQLQJSURJUDPPHLQWKLVDUHDZDVFUHDWHG8SWRQRZQDWLRQDOTUDLQMLC
WHDPVKDYHEHHQVHWXSDQGPRUHWKDQSHRSOHKDYHEHHQWUDLQHGDOODFURVV(XURSH
%\VKDULQJWKHUHVRXUFHVLQDSUHGHQHGPDQQHUDWWKH(XURSHDQOHYHODEHWWHUWUDLQLQJ
WRWKHQDWLRQDOFRPPXQLWLHVFDQEHSURYLGHGWKDQLIWKH\ZRXOGRQO\UHO\RQWKHPVHOYHV
I DFLOLWDWHH[FKDQJHRIWUDLQLQJPDWHULDOWKDWKDVEHHQSUHSDUHGDQGFROOHFWHGE\
WKHYDULRXVWUDLQHUV
IDFLOLWDWHH[FKDQJHRIIHHGEDFNIURPWKHSDUWLFLSDQWVDVZHOODVIURPWKHWUDLQHUV
LPSURYHWHDFKLQJLPSDFWRIWKHFRXUVH
TKHUHIRUHDVWUXFWXUHIRUDTUDLQMLCH[DPSOHKDVEHHQGHYHORSHGDQGVRPHJXLGHOLQHV
RQKRZWRFRQGXFWDW\SLFDOTUDLQMLCH[DPSOHVHVVLRQKDYHEHHQGUDIWHG$VWKLVLV
FUXFLDOIRUSURSHUXQGHUVWDQGLQJDQGFRQGXFWLQJRIWKHTUDLQMLCH[DPSOHVHVVLRQVD
GHWDLOHGGHVFULSWLRQLVJLYHQEHORZ
6WUXFWXUHRID7UDLQ0L& H[DPSOH
6XPPDU\
ILFKH
,QWURGXFWRU\
VOLGHV
*HQHUDOLQIRUPDWLRQ
DERXWWKHH[DPSOH
$ERXWWKHDQDO\WLFDO
SURFHGXUH
&KHFNOLVWRQZKDW
H[DFWO\LVLQFOXGHGIRU
WKHSDUWLFXODU
H[DPSOH
'DWD VKHHW
([HUFLVHV
Traceability
&XVWRPHUV
UHTXLUHPHQWV
5HOHYDQW
HTXDWLRQVDQG
PHDVXUHPHQW GDWD
Validation
Measurement
uncertainty
6ROXWLRQV
Traceability
Validation
Measurement
uncertainty
IQSUDFWLFHWKLVPHDQVWKDWDTUDLQMLCH[DPSOHVHVVLRQDWDFHUWDLQTUDLQMLCHYHQW
FDQEHFRQGXFWHGLQRQHRIWKHIROORZLQJIRUPV
2QHH[DPSOHDOOWKUHHH[HUFLVHV
2QHH[DPSOHRQHRUWZRH[HUFLVHVRQO\
MRUHWKDQRQHH[DPSOHDOOH[HUFLVHVIRUHDFK
MRUHWKDQRQHH[DPSOHRQHRUWZRH[HUFLVHVRQO\
2QHH[DPSOHMHDVXUHPHQWXQFHUWDLQW\H[HUFLVHFRPSDULQJGLIIHUHQWWRROVIRU
LWVHYDOXDWLRQ
:KHQ GHFLGLQJ RQ ZKLFK IRUPDW WR FKRRVH LW LV HVVHQWLDO QRW WR IRUJHW DERXW WKH WLPH
FRQVWUDLQWVRIDFHUWDLQWUDLQLQJHYHQWDVLWLVFUXFLDOWKDWWKHWUDLQHHVKDYHHQRXJKWLPH
WRGRWKHH[HUFLVHVDVZHOODVWRGHGLFDWHHQRXJKWLPHWRDSURSHUO\OHGGLVFXVVLRQDIWHU
FRPSOHWLQJWKHH[HUFLVHV%DVHGRQRXUH[SHULHQFHZHVXJJHVWWRGHGLFDWHDERXWPLQXWHV
IRUHDFKRIWKHH[HUFLVHVJURXSZRUNDQGDERXWPLQXWHVIRUDIROORZXSGLVFXVVLRQTKH
JURXSVVKRXOGQRWEHELJJHUWKDQYHSDUWLFLSDQWVDQGHDFKJURXSVKRXOGLQWKHEHJLQQLQJ
RIHDFKH[HUFLVHnominate a rapporteur ZKRDIWHUZDUGVUHSRUWVRQWKHUHVXOWVDQGRQWKH
TXHVWLRQVDQGWKHGLVFXVVLRQWKHJURXSKDGGXULQJWKHH[HUFLVH1RPLQDWLQJDUDSSRUWHXU
LPSURYHVWKHUHSRUWLQJVLJQLFDQWO\VRLWLVKLJO\UHFRPPHQGHGWRJLYHHDFKJURXSDFDUG
UDSSRUWHXUDWWKHVWDUWIWLVRIDYLWDOLPSRUWDQFHWKDWWKHWUDLQHHVDUHSURSHUO\EULHIHG
EHIRUHVWDUWLQJZLWKWKHH[DPSOHVHVVLRQTKHVOLGHVZKLFKFDQEHXVHGIRUWKLVSXUSRVH
DUHLQ$SSHQGL[DQGDG\QDPLFSURFHVVRIFRQGXFWLQJDTUDLQMLCH[DPSOHVHVVLRQLV
VFKHPDWLFDOO\VKRZQLQ)LJXUH
Acknowledgment
TKHMHWURORJ\IQVWLWXWHRIWKHRHSXEOLFRI6ORYHQLDLVJUDWHIXOO\DFNQRZOHGJHGIRULWVFRQWULEXWLRQWRWKH
JUDSKLFLOOXVWUDWLRQVLQWKLVERRN
Nineta Majcen
1LQHWDMDMFHQVWDUWHGDVDUHVHDUFKHUDWWKH8QLYHUVLW\RILMXEOMDQD6ORYHQLDZKHUH
VKHREWDLQHGKHUPK'RQYDOLGDWLRQRIQHZO\GHYHORSHGPHWKRGVDQGFKHPRPHWULFV6KH
KDVFRQWLQXHGKHUDQDO\WLFDOZRUNLQWKHTXDOLW\FRQWUROODERUDWRULHVLQLQGXVWU\EHIRUH
VWHSSLQJLQWRPHWURORJ\DFWLYLWLHVDWWKHQDWLRQDODQG(XURSHDQOHYHOIQPHWURORJ\VKH
KDVEHHQPDLQO\LQYROYHGLQWRSLFVUHODWHGWRPHWURORJ\LQFKHPLVWU\DQGLQLVVXHVUHODWHG
WRPHDVXUHPHQWLQIUDVWUXFWXUH6KHLVDOVRFORVHO\FROODERUDWLQJZLWKDFFUHGLWDWLRQERGLHV
DQGVKHLVOHFWXULQJDWWKH8QLYHUVLW\RIMDULERU
6KHLVWKH6ORYHQLDQTUDLQMLCWHDPOHDGHUPHPEHURIWKHTUDLQMLCMDQDJHPHQW
%RDUGDQGLVFKDLULQJWKHTUDLQMLC(GLWRULDO%RDUG6KHLVFXUUHQWO\ZRUNLQJDWWKH
MHWURORJ\LQVWLWXWHRIWKHRHSXEOLFRI6ORYHQLD
Chapter 1
Veselin Kmetov
+HREWDLQHGKLVPDVWHUGHJUHHLQFKHPLVWU\DWWKH8QLYHUVLW\RIPORYGLY%XOJDULDDQG
WKHUHKHWRRNWKHSRVLWLRQRIDUHVHDUFKFKHPLVWDWWKHCHQWHURI$QDO\WLFDOCKHPLVWU\
DQG$SSOLHG6SHFWURVFRS\+HPRYHGWRDVVLVWDQWSURIHVVRUSRVLWLRQLQWKH'HSDUWPHQW
RI$QDO\WLFDOCKHPLVWU\ZKHUHKHUHFHLYHGKLVPK'GHJUHH+HEHFRPHDKHDGRIWKH
UHVHDUFK JURXS RI DWRPLF VSHFWURPHWU\ WKDW DFFRPSOLVKHG D QXPEHU RI UHVHDUFK DQG
DSSOLHGSURMHFWVLQWKHHOGRIWKHLQVWUXPHQWDODQDO\VLVZLWKDWRPLFVSHFWURPHWU\PHWKRGV
11
$$6 ICP2(6 DQG ICPM6 IRU WUDFH HOHPHQWV GHWHUPLQDWLRQ LQ HQYLURQPHQWDO
FOLQLFDO DQG LQGXVWULDO PDWHULDOV TKH JURXS PDLQWDLQV H[FHOOHQW FROODERUDWLRQ ZLWK D
UHVHDUFKWHDPIURPWKH8QLYHUVLW\RI$OLFDQWH6SDLQ
+LVUHVHDUFKLQWHUHVWVDUHVDPSOHSUHSDUDWLRQXVHRIPLFURZDYHUDGLDWLRQDQDO\VLV
RI KHDY\ PDWULFHV E\ GLVFUHWH VDPSOH LQWURGXFWLRQ RZ LQMHFWLRQ HOHFWURWKHUPDO
YDSRULVDWLRQPHWURORJ\LQFKHPLVWU\GDWDDFTXLVLWLRQDQGWUHDWPHQWPHWKRGRORJ\RI
WHDFKLQJ
$WWKHPRPHQWKHLVOHFWXULQJIQVWUXPHQWDODQDO\VLV6WDWLVWLFVDQGPHWURORJ\
DQGCRPSXWHUQXDOLPHWU\
+H MRLQHG WKH TUDLQMLC SURJUDP LQ DV D PHPEHU RI %XOJDULDQ WHDP RI
DXWKRULVHGTUDLQMLCWUDLQHUV
Emilia Vassileva
(PLOLD 9DVVLOHYD LV D UHVHDUFK VFLHQWLVW DQG LQRUJDQLF FKHPLVWU\ JURXS OHDGHU LQ WKH
81I$($(QYLURQPHQWDOLDERUDWRULHVLQMRQDFR6KHUHFHLYHGKHUPDVWHUGHJUHHDW
WKH8QLYHUVLW\RI*HQHYD6ZLW]HUODQGDQGKHUPK'GHJUHHDWWKH8QLYHUVLW\RI6RD
%XOJDULDZKHUHVKHVWDUWHGDVDVVLVWDQWSURIHVVRU+HUPDLQUHVHDUFKLQWHUHVWVDUHLQWKH
DUHDRIWUDFHDQGXOWUDWUDFHLVRWRSHDQGHOHPHQWDODQDO\VLVXVLQJICPMDVV6SHFWURPHWU\
DQGRWKHUDGYDQFHGLQVWUXPHQWDOWHFKQLTXHV6KH LV DXWKRUDQGFRDXWKRURI DERXW
VFLHQWLF SDSHUV DQG UHSRUWV IQ WKH FRQWH[W RI PHWURORJ\ LQ FKHPLVWU\ VKH KDV EHHQ
ZRUNLQJIRUVHYHQ\HDUVDWWKHDWIQVWLWXWHIRURHIHUHQFHMDWHULDOVDQGMHDVXUHPHQWV
ZKHUHVKHZDVLQYROYHGLQUHIHUHQFHLVRWRSHPHDVXUHPHQWVIRUFHUWLFDWLRQSXUSRVHV
IPSRUWDQWSDUWRIKHUSUHVHQWDFWLYLWLHVLVWKHWUDLQLQJIRU81MHPEHU6WDWHVDQDO\WLFDO
ODERUDWRULHVLQQ$QC
6KHLVTUDLQMLCFRRUGLQDWRUPHPEHURIWKHTUDLQMLC(GLWRULDODQGMDQDJHPHQW
%RDUGVDQG1DWLRQDOTUDLQMLCWHDPOHDGHUIRU%XOJDULD
Chapter 2
Steluta Duta
6WHOXWD 'XWD ZRUNV DW 1DWLRQDO IQVWLWXWH RI MHWURORJ\ RRPDQLDQ %XUHDX RI LHJDO
MHWURORJ\ LQ %XFKDUHVW RRPDQLD I1M%RML LQ WKH HOG RI 6SHFWURPHWU\ DQG
RHIHUHQFH MDWHULDOV +HU PK' RQ CKHPLFDO MHWURORJ\ WRSLF ZDV GHIHQGHG DW WKH
PROLWHFKQLFIQVWLWXWH%XFKDUHWLQRRPDQLD6KHLVLQYROYHGLQGHYHORSPHQWFRRUGLQDWLRQ
RI I1M%RML UHVHDUFK SURJUDPPHV DQG KHU SHUVRQDO UHVHDUFK LQWHUHVWV DUH UHODWHG
WR WKH GHYHORSPHQW RI SULPDU\UHIHUHQFH PHDVXUHPHQW PHWKRGV PDLQO\ 899I6IR
)$$6(T$$6ICPM6DQGPHDVXUHPHQWVWDQGDUGVLQWKHHOGRISK\VLFRFKHPLFDO
TXDQWLWLHV 6KH LV DFWLYH LQ LQWHUQDWLRQDO UHVHDUFK QHWZRUNV DQG LQ WKH GLVVHPLQDWLRQ
RI NQRZOHGJH RQ LVVXHV UHODWHG WR PHWURORJ\ LQ FKHPLVWU\ XQFHUWDLQW\ WUDFHDELOLW\
YDOLGDWLRQCRMVHWF
6KHLVDPHPEHURIWKHTUDLQMLCMDQDJHPHQW%RDUGDQG1DWLRQDOTUDLQMLC
WHDPOHDGHUIRURRPDQLD
12
Philip Taylor
VHHDERYH
Chapter 3
Ljudmila Benedik
LMXGPLOD %HQHGLN VWDUWHG KHU SURIHVVLRQDO FDUHHU LQ WKH HOG RI UDGLRFKHPLVWU\ LQ
ZKHQVKHMRLQHGWKH'HSDUWPHQWIRU1XFOHDUCKHPLVWU\DW-RHI6WHIDQIQVWLWXWH
LMXEOMDQD 6ORYHQLD 6KH QLVKHG PK' VWXG\ LQ DW )DFXOW\ IRU CKHPLVWU\ DQG
CKHPLFDOTHFKQRORJ\8QLYHUVLW\RILMXEOMDQDZLWKWKHVLV'HYHORSPHQWRIPHWKRGVIRU
GHWHUPLQDWLRQ RI ORZOHYHO XUDQLXP DQG WKRULXP E\ UDGLRFKHPLFDO QHXWURQ DFWLYDWLRQ
DQDO\VLV
+HU VFLHQWLF UHVHDUFK ZRUN ZDV PDLQO\ GHYRWHG WR UHVHDUFK LQ WKH HOG RI
GHWHUPLQDWLRQRIWUDFHHOHPHQWVE\QHXWURQDFWLYDWLRQDQDO\VLVDVZHOODVGHWHUPLQDWLRQ
RI QDWXUDO DQG PDQPDGH UDGLRQXFOLGHV XVLQJ DOSKD EHWD DQG JDPPD VSHFWURPHWU\
DQG OLTXLG VFLQWLOODWLRQ WHFKQLTXH 6KH SXEOLVKHG UHVXOWV RI KHU UHVHDUFK ZRUN LQ RYHU
VFLHQWLF SDSHUV DQG SUHVHQWHG LW DW QXPHURXV LQWHUQDWLRQDO FRQIHUHQFHV 6KH ZDV
LQYROYHGLQYDULRXVSURMHFWVFRQQHFWHGWRPHDVXUHPHQWRIHQYLURQPHQWDOUDGLRDFWLYLW\
6KHZDVDFWLQJDVDPHQWRUIRUXQGHUJUDGXDWHDQGSRVWJUDGXDWHVWXGHQWV
6KH KDV EHHQ ZRUNLQJ DW IQVWLWXWH IRU RHIHUHQFH MDWHULDOV DQG MHDVXUHPHQWV
RI WKH -RLQW RHVHDUFK CHQWUH RI WKH (XURSHDQ CRPPLVVLRQ ZKHUH VKH ZDV LQYROYHG
DPRQJVWRYHULQWKHSURMHFW186IM(P1XFOHDU6LJQDWXUHIQWHUODERUDWRU\MHDVXUHPHQW
PURJUDPPHDQGLQSURMHFWUHODWHGWR(8GULQNLQJZDWHUGLUHFWLYH
$W WKH SUHVHQW VKH ZRUNV DV D VHQLRU UHVHDUFK DVVRFLDWH DW WKH 'HSDUWPHQW RI
(QYLURQPHQWDO6FLHQFHV-RHI6WHIDQIQVWLWXWH
6KHLVDPHPEHURI6ORYHQLDQTUDLQMLCWHDP
Urka Repinc
8UND RHSLQF VWDUWHG KHU SURIHVVLRQDO FDUHHU DV UDGLRFKHPLVW DW WKH 'HSDUWPHQW RI
(QYLURQPHQWDO 6FLHQFHV -RHI 6WHIDQ IQVWLWXWH LMXEOMDQD 6ORYHQLD LQ +HU
GLSORPDZRUNZDVGHYRWHGWRGHWHUPLQDWLRQRIRDE\OLTXLGVFLQWLOODWLRQFRXQWLQJ
6KHFRQWLQXHGWKHZRUNRQGHYHORSLQJQHZPHWKRGVEDVHGRQDOSKDEHWDVSHFWURPHWU\RU
UDGLRFKHPLFDOQHXWURQDFWLYDWLRQDQDO\VLVIQVKHQLVKHGKHUPK'ZKLFKFRQVLVWV
RIGHYHORSHGSURFHGXUHVIRUGHWHUPLQDWLRQRIYDQDGLXPXUDQLXPPDQJDQHVHDQGFREDOW
YLDLQGXFHGWKHLUVKRUWOLYHGQXFOLGHV98MQDQGPCRUHVSHFWLYHO\+HU
UHVHDUFK ZRUN ZDV QRW IRFXVHG RQO\ RQ D VLQJOH HOHPHQW GHWHUPLQDWLRQ EXW LPSURYHG
SURFHGXUHVIRUWKHLUVLPXOWDQHRXVGHWHUPLQDWLRQ
IQ)HEUXDU\VKHMRLQHGWKHIQVWLWXWHIRUTUDQVXUDQLXP(OHPHQWVRIWKH-RLQW
RHVHDUFKCHQWUHRIWKH(XURSHDQCRPPLVVLRQ.DUOVUXKH*HUPDQ\DVDSRVWGRFIHOORZ
13
Monika Inkret
MRQLNDIQNUHWVWDUWHGKHUFDUHHUDWWKHMHWURORJ\IQVWLWXWHRIWKHRHSXEOLFRI6ORYHQLD
LQLDERUDWRU\IRUPUHFLRXVMHWDOV
)RUVL[\HDUVVKHKDVEHHQZRUNLQJDIWHUZDUGVDWWKHIQVWLWXWHIRURHIHUHQFHMDWHULDOV
DQGMHDVXUHPHQWVRIWKH-RLQWRHVHDUFKCHQWUHRIWKH(XURSHDQCRPPLVVLRQTKHUHVKH
ZDVZRUNLQJRQWKH$YRJDGURSURMHFWIRUWKHUHGHWHUPLQDWLRQRIWKH$YRJDGURFRQVWDQW
+HUPDLQUHVHDUFKWRSLFZDVVLOLFRQLVRWRSHUDWLRPHDVXUHPHQWVDQGVLOLFRQPRODUPDVV
GHWHUPLQDWLRQ XVLQJ GLIIHUHQW PDVV VSHFWURPHWULF WHFKQLTXHV WKHUPDO LRQL]DWLRQ DQG
HOHFWURQLPSDFW
$IWHU GHIHQGLQJ KHU GRFWRUDO GLVVHUWDWLRQ LQ MDUFK DW WKH 8QLYHUVLW\ RI
LMXEOMDQD PDVV VSHFWURPHWU\ DQG PHWURORJ\ EHLQJ WKH FHQWUDO WRSLF VKH ZRUNHG DV
D SRVWGRF DW 8QLYHUVLW\ RI 6LQJDSRUH )DFXOW\ RI 6FLHQFH LQ WKH LDERUDWRU\ IRU WUDFH
PHWDOVGHWHUPLQDWLRQLQIRRGDQGELRORJLFDOVDPSOHV
6LQFHMD\VKHKDVEHHQZRUNLQJLQCLQNDUQDCHOMHCHOMH6ORYHQLDLQR '
8QLWZLWKWKHUHVHDUFKIRFXVHGRQSURGXFWLRQRIQDQRWLWDQLXPGLR[LGHZKLWHSLJPHQW
CXUUHQWO\ VKH LV HPSOR\HG DW .UND 1RYR PHVWR ZKHUH VKH LV GHDOLQJ ZLWK WKH
TXDOLW\LVVXHVUHODWHGWRSKDUPDFHXWLFDOV
6KHLVDPHPEHURI6ORYHQLDQTUDLQMLCWHDP
Chapter 4
Allan Knnapas
$OODQ.QQDSDVUHFHLYHGKLVM6FLQDW8QLYHUVLW\RITDUWX(VWRQLDIQMDVWHUV
WKHVLV KH VWXGLHG WKH LPSOHPHQWDWLRQ RI QX(CK(R6 PHWKRG LQ LCM6 LQ )LQQLVK
CXVWRPV LDE (VSRR )LQODQG TKH H[DPSOH 'HWHUPLQDWLRQ RI PRODU PHVWLFLGHV E\
LLTXLGCKURPDWRJUDSK\MDVV6SHFWURPHWU\ZDVFRPSLOHGLQFRQMXQFWLRQZLWKKLV%6F
ZRUNLQYROYLQJWKHGHYHORSLQJDSHVWLFLGHUHVLGXHVDQDO\WLFDOPHWKRG
+HLVFXUUHQWO\DGRFWRUDOVWXGHQWDW8QLYHUVLW\RITDUWXDQGLQKLVGRFWRUDOWKHVLV
KH ZLOO VWXG\ LVRWRSH GLOXWLRQ PDWUL[ HIIHFW DQG VXSSUHVVLRQ LQ LCM6 DQDO\VLV +H
KDVEHHQLQYROYHGLQSURMHFWVFRQFHUQLQJIXUWKHUZLGHQLQJSHVWLFLGHUHVLGXHVDQDO\WLFDO
PHWKRGLPSOHPHQWLQJQX(CK(R6LQJRYHUQPHQWDOODERUDWRULHVDQDO\VLVRIDQWLELRWLFV
LQVHZDJHVOXGJH+LVUHVHDUFKLQWHUHVWVLQFOXGHFKURPDWRJUDSKLFVHSDUDWLRQPHWKRGV
HVSHFLDOO\ LC DQG LCM6 PDVV VSHFWURPHWU\ UHVLGXHV DQDO\WLFDO PHWKRGV I'M6
PHWKRGGHYHORSPHQWVDPSOHSUHSDUDWLRQ
Koit Herodes
.RLW +HURGHV UHFHLYHG KLV PK' LQ DW 8QLYHUVLW\ RI TDUWX (VWRQLD +H KDV
LQYHVWLJDWHG ELQDU\ SURSHUWLHV RI VROYHQW PL[WXUHV E\ PHDQV RI LRQLF HTXLOLEULD DW
8QLYHUVLW\ RI %DUFHORQD 6SDLQ DQG (T SDUDPHWHUV $W 8QLYHUVLW\ RI )UHLEXUJ
*HUPDQ\KHDFTXLUHGVNLOOVRIV\QWKHVL]LQJSKRVSKD]HQHVXSHUEDVHVLQVWULFWO\QRQ
DTXHRXVFRQGLWLRQV
14
+HLVFXUUHQWO\ZRUNLQJDVDVVRFLDWHSURIHVVRURIDQDO\WLFDOFKHPLVWU\DW8QLYHUVLW\
RITDUWXTRJHWKHUZLWKKLVVWXGHQWVKHLVGHYHORSLQJDQGYDOLGDWLQJVDPSOHSUHSDUDWLRQ
DQGOLTXLGFKURPDWRJUDSKLFLCM6DQDO\VLVPHWKRGVIRUVPDOOPROHFXOHVLQGLIIHUHQW
PDWULFHV HJ SHVWLFLGH UHVLGXHV LQ IRRG SKDUPDFHXWLFDO UHVLGXHV LQ VHZDJH VOXGJH
DPLQR DFLGV LQ KRQH\ SKDUPDFHXWLFDOV LQ ELRORJLFDO XLGV HWF MRUH IXQGDPHQWDO
UHVHDUFKWRSLFVLQFOXGHHOHFWURVSUD\LRQL]DWLRQSURFHVVDQGHIFLHQF\VWXGLHVDQGQRYHO
EXIIHUFRPSRXQGVIRULCM6
$W8QLYHUVLW\RITDUWXKHLVKHDGRI8QLYHUVLW\THVWLQJCHQWUHDXQLWWKDWSURYLGHV
DQDO\WLFDOVHUYLFHVWRLQGXVWU\DQGRWKHUODERUDWRULHV
Ivo Leito
PURIIYRLHLWRUHFHLYHGKLVPK'LQDW8QLYHUVLW\RITDUWX(VWRQLD+HKDVZRUNHG
DWVHYHUDOXQLYHUVLWLHVDQGUHVHDUFKLQVWLWXWHVLQ)UDQFH6SDLQ-DSDQDQG%HOJLXPDQG
LV FXUUHQWO\ ZRUNLQJ DV SURIHVVRU RI DQDO\WLFDO FKHPLVWU\ DW 8QLYHUVLW\ RI TDUWX +LV
UHVHDUFK LQWHUHVWV LQFOXGH H[SHULPHQWDO DQG WKHRUHWLFDO VWXGLHV RI DFLGEDVH HTXLOLEULD
DQGVROYHQWHIIHFWVLQQRQDTXHRXVVROYHQWVDQGLQWKHJDVSKDVHPHWURORJ\LQFKHPLVWU\
PHDVXUHPHQW XQFHUWDLQW\ LQ FKHPLVWU\ DQDO\WLFDO FKHPLVWU\ LQVWUXPHQWDO DQDO\WLFDO
PHWKRGV IR VSHFWURVFRS\ *CM6 LCM6 6(M ('6 HWF DSSOLHG WR DQDO\VLV RI
PDWHULDOVDQGREMHFWVRIFXOWXUDOKHULWDJHDQGPHWKRGLFDODVSHFWVRIWHDFKLQJDQDO\WLFDO
FKHPLVWU\ DQG PHWURORJ\ LQ FKHPLVWU\ KWWSWHUDFKHPXWHHaLYRR'KWPO 1XPEHU
RI LQWHUQDWLRQDO VFLHQWLF SXEOLFDWLRQV DOO LQ MRXUQDOV LQGH[HG E\ I6I +H KDV
VXSHUYLVHG PK' VWXGHQWV PRUH WKDQ M6F DQG PRUH WKDQ %6F VWXGHQWV +H LV
FXUUHQWO\VXSHUYLVLQJPK'VWXGHQWVM6FVWXGHQWVDQG%6FVWXGHQW+HKDVVHWXS
DQGLVWKHSURJUDPGLUHFWRURIWKHLQWHUQDWLRQDOMDVWHUCXUULFXOXP$SSOLHGMHDVXUHPHQW
6FLHQFH KWWSZZZXWHHDPV DQG LV WKH FRRUGLQDWRU RI WKH (XURPDVWHU FRQVRUWLXP
MHDVXUHPHQW6FLHQFHLQCKHPLVWU\KWWSZZZPVFHXURPDVWHUHX
Chapter 5
Bertil Magnusson
%HUWLOMDJQXVVRQVWDUWHGDVDPDULQHFKHPLVWORRNLQJIRUWUDFHVRIPHWDOVLQWKHRFHDQV
ULYHUVODNHVDQGUDLQLQWKHV$IWHUPK'KHMRLQHGDFKHPLFDOFRPSDQ\(NDCKHPLFDOV
ZLWKLQ$.=212%(LDQGZRUNHGWKHUHDVDVSHFLDOLVWLQDQDO\WLFDOFKHPLVWU\PDLQO\
ZLWKVSHFWURVFRS\;R);R'DQGICPDQGZHWFKHPLVWU\
IQKHMRLQHGWKH6PTHFKQLFDORHVHDUFKIQVWLWXWHRI6ZHGHQDQGLVFXUUHQWO\
ZRUNLQJ ZLWK TXDOLW\ LQ PHDVXUHPHQWV MHWURORJ\ LQ CKHPLVWU\ D UHVHDUFK DUHD RQ
LQWHUQDWLRQDOFRPSDUDELOLW\DQGWUDFHDELOLW\RIFKHPLFDOPHDVXUHPHQWUHVXOWV$PDMRU
SDUW LV WHDFKLQJ DQG ZULWLQJ JXLGHOLQHV DQG UHVHDUFK SDSHUV UHJDUGLQJ PHDVXUHPHQW
TXDOLW\IPSRUWDQWSDUWRIKLVZRUNLVHGXFDWLRQIRUDQDO\WLFDOODERUDWRULHVLQQ$QC
IQ 1RUGLF FRRSHUDWLRQ KH KDV ZULWWHQ D +DQGERRN RQ MHDVXUHPHQW 8QFHUWDLQW\ IRU
(QYLURQPHQWDOLDERUDWRULHV1RUGWHVWWHFKQLFDOUHSRUWDQGD+DQGERRNIRUIQWHUQDO
15
16
Chapter 1
18
Measurand
Example number
Ex-06
Analytical procedure
Customers requirement
U = 9 (k = 3)
2 - Yellow
1-I
PART I
PART II
Ex-06-2-Y-Aualloys-FAAS-2006Ver1.doc
PART III
3 - Green
PART IV
EX-06-3-G-Aualloys-FAAS-2006Ver1.doc
File is
attached
Yes No
Each
participant
receives own
copy and
may keep it
9
9
PART II
Given by the
lecturer
PART I
PART III
Remark
April 2007
1
2
19
$QDO\VLVRI*ROG$OOR\VE\)$$6
6FRSHRIWKHSUHVHQWDWLRQ
7KHDQDO\WLFDOSURFHGXUHDQGWKHFXVWRPHUVUHTXLUHPHQWV
$ERXWWKHFKHPLVWU\ DQGWKHPHDVXUHPHQWPHWKRG
0RGHOHTXDWLRQ
7KHDQDO\WLFDOSURFHGXUHDQGWKH
FXVWRPHUVUHTXLUHPHQWV
20
7KHWUDGLWLRQDOLQWHUQDWLRQDOO\UHFRJQLVHGPHWKRGLVEDVHGRQFXSHOODWLRQILUH
DVVD\,62 6WDQGDUG
7KHILQHQHVVRISUHFLRXVPHWDODOOR\VDUHVSHFLILHGLQ,62
DFFRUGLQJWRWKHSXULW\RIJROGDVDQGDQG
NDUDWVUHVSHFWLYHO\2QHNDUDWLVHTXDOWR
7KH$XDQDO\VLVKDVWRNHHSWKHH[SDQGHGXQFHUWDLQW\N OHVVWKDQ
21
0RGHOHTXDWLRQ
*ROGFRQWHQWLQMHZHOOHU\JROGDOOR\V
: B R
22
9B *YLDOV B
u
u
u &[ u
PB *3 B
5
6RPHPRUHHTXDWLRQV
&DOFXODWLRQRIVLJQDOVWDQGDUGXQFHUWDLQW\
5HFRYHU\FRUUHFWLRQ
: B
: B UHI B
X B $ B RQH B VHW
XB $
%UDFNHWLQJFDOLEUDWLRQ
7KHVHOHFWHGFDOLEUDWLRQUDQJHFRUUHVSRQGVWR
WKH UDQJH NW UHFDOFXODWHG IRU
DQDO\]HGDOOR\
,W LV SURYHG WKDW WKH 61 UDWLRQ LV PLQLPXP
DQG WKH FDOLEUDWLRQ LQWHUYDO EHORQJV WR WKH
OLQHDUUDQJH
&[
$ 6W $ 6W
\ [
5
$EVRUEDQFH
$XPJNJ
23
Analytical procedure
Determination of gold in jewellery gold alloys by Flame Atomic
Absorption Spectrometry
PART I ...................................................................................................................................25
Description of the analytical procedure
PART II .................................................................................................................................33
The customers requirements concerning the quality of the measurement result
PART III ................................................................................................................................34
Validation of the measurement procedure relevant equations and
measurement data
PART IV ................................................................................................................................35
Measurement uncertainty of the result relevant equations and measurement
data
24
Task description
TKHQHQHVVRIMHZHOOHU\JROGDOOR\VGHSHQGVIURPWKH$XFRQWHQGLQWKHXVHGPDWHULDO
WKDWPXVWEHVWULFWO\PDUNHGTKLVPDUNLVJLYHQE\WKHMLQLVWU\RI)LQDQFHVDIWHUWHVWLQJ
LQDFFUHGLWHGIRUWKHVFRSHODERUDWRULHVTKHVHWRIPDUNVRISUHFLRXVPHWDODOOR\VDUH
VSHFLHGLQISO 9202:1991DQGDUHQRPLQDWHGDFFRUGLQJWRWKHSXULW\IRUJROGmm
DVDQGZKLFKFRUUHVSRQGWRDQGFDUDWVUHVSHFWLYHO\
2QH FDUDW LV HTXDO WR IQ D FRPPRQ SUDFWLFH FDUDWV JROG
DOOR\VDUHXVHGIRUMHZHOOHU\WKHUHIRUHVXFKVDPSOHVDUHPRUHRIWHQDVXEMHFWRIDQDO\VHV
IPSRUWDQWFRQFOXVLRQVDQGGHFLVLRQVOLQNHGWRWKHFXVWRPHULQWHUHVWSURWHFWLRQVSKHUH
GHULYHIURPPHDVXUHPHQWUHVXOWVWKDWKDYHWREHEDVHGRQUHOLDEOHGDWDRIJRRGTXDOLW\
HJ VXIFLHQWO\ VPDOO XQFHUWDLQW\ TKH OHJLVODWLRQ UHTXLUH WKH DFWXDO QHQHVV RI
MHZHOOHU\ DOOR\V VKDOO QRW EH OHVV E\ PRUH WKDQ WKUHH RQHWKRXVDQGWK SDUWV WKDQ WKH
QHQHVV LQGLFDWHGE\ WKH PDUN VWDPSHGTKHUHIRUH WKH WHVWLQJ PHWKRG VKRXOG EH DEOH
WR SURYLGH UHVXOWV ZLWK KLJK DFFXUDF\ DQG ORZ XQFHUWDLQW\ OHVV than k RI
DQDO\WLFDO PHDVXUHPHQWV TKH FDOFXODWHG H[SDQGHG XQFHUWDLQW\ IRU $X PDVV IUDFWLRQ
VKRXOGEHOHVVWKDQk
TKHWUDGLWLRQDODQGLQWHUQDWLRQDOO\UHFRJQLVHGPHWKRGIRUJROGDOOR\DQDO\VLVLVEDVHG
RQWKHFXSHOODWLRQUHDVVD\I626WDQGDUG. RHFHQWO\RWKHUDOWHUQDWLYHPHWKRGV
EDVHGRQDWRPLFVSHFWURPHWU\KDYHEHHQVXJJHVWHG
1.
ISO/TC 174. rev.N71. Gouda 1992 Determination of gold in gold jewelry
allows ICP solution spectrometric method using yttrium as internal
standard
2.
CNR-PRO Art Project (1998) Tecniche spettrometriche alternative alla
copellazione per il saggio delle leghe dioro
Scope
TKLVH[DPSOHGHVFULEHVDODERUDWRU\GHYHORSHGPHWKRGIRUGHWHUPLQDWLRQRIJROGDIWHUaqua
regiaVROXELOLVDWLRQDQGPHDVXUHPHQWVE\DPHDWRPLFDEVRUSWLRQVSHFWURPHWU\)$$6
TKHUDQJHRIDSSOLFDWLRQLVMHZHOOHU\DOOR\VFRQWDLQLQJJROGFDUDWV
TKHSURFHGXUHLVRSWLPLVHGWRWIRUSXUSRVHE\PHDQVRIDV\VWHPIRUDLUVHJPHQWHG
GLVFUHWHLQWURGXFWLRQ$6'IWKDWDOORZVVLJQDOVWREHDFFXPXODWHGZLWKRXWGULIW([WHUQDO
SURFHGXUHIRUSVHXGRVWHDG\VWDWHVLJQDOVPRRWKLQJDQGHQVHPEOHVXPPDWLRQLVXVHGIRU
EHWWHULQJWKHUHSHDWDELOLW\RIWKHLQVWUXPHQWDOSHUIRUPDQFH
TKHH[SHULPHQWDOSURWRFROLVVKRZQLQWKH)LJXUH
25
Figure 3. Flow chart of the analytical procedure for determination of gold in gold
alloys
26
Reagents
(MHUFNFODVVSDYY+12IUHVKO\SUHSDUHGaqua regia1+COVDOW
PXUH$XFHUWLHGIURP1RQ)HUURXVMHWDOOXUJLFDOPODQWPORYGLY
Apparatus
)ODPH$WRPLF$EVRUSWLRQ6SHFWURPHWHUHTXLSSHGZLWKKROORZFDWKRGHODPSIRU
JROG
'LVFUHWHVDPSOHLQWURGXFWLRQV\VWHP$6'I
%DODQFHd JFHUWLHG%'6(1
+RWSODWH
PLSHWWHYDULDEOHLJUDYLPHWULFDOO\FKHFNHGFHUWLHGd LQ
LUDQJH
9ROXPHWULFDVNPLODERUDWRU\JODVVZDUHFODVV$FHUWLHGd PLIRU
C
9ROXPHWULFDVNPLODERUDWRU\JODVVZDUHFODVV$FHUWLHGd PLIRU
C
PRO\SURS\OHQHYLDOVJ$6'IDXWRVDPSOHUNLW
Calibration
6WRFNVWDQGDUGVROXWLRQZDVPDGHLQODERUDWRU\E\GLVVROXWLRQRIJ$XZLWKSXULW\
ZLWKPLaqua regiaDQGOOHGXSWRJZLWK1+COTZRFDOLEUDWLRQ
27
VWDQGDUGVDUHREWDLQHGLQSRO\SURS\OHQHYLDOVDIWHUIXUWKHUGLOXWLRQRIJDQGJ
IURPVWRFNVWDQGDUGVROXWLRQZLWKSURFHGXUDOEODQNVROXWLRQWRJJUDYLPHWULFDOO\
FRQWUROOHG
TKHVHOHFWHGFDOLEUDWLRQUDQJHUHFDOFXODWHGIRUDQDO\VHGDOOR\FRUUHVSRQGVWRWKHUDQJH
FDUDWV
TKHFDOLEUDWLRQVWDQGDUGVDUHVXEMHFWWRWKHVDPHVDPSOHSUHSDUDWLRQSURFHGXUHDVWKH
DQDO\VHGVDPSOHTKHH[DFWPDWFKLQJRIVDPSOHDQGVROXWLRQXVHGIRUFDOLEUDWLRQDOORZV
WRDYRLGWKHLQXHQFHRIPDWUL[HIIHFWRQREWDLQHGVLJQDOV
28
Values
ASDI parameters
242.8
0.7
10
Air/C2H2 units
Observation high [mm]
50/18
6
3743
OFF
Pseudo plateau 3 s
Sampling mode (St1 _ sample _ St2 ) N
50
29
Calculations
Concentration of initial standard solution made up from pure gold
C_ Au 999.9 =
104
C_ Au 999.9
FRQFHQWUDWLRQRILQLWLDOVWDQGDUGVROXWLRQPDGHXSIURPSXUHJROG>JJ@
m_ pureAu
PDVVZHLJKHGRISXUHJROG>J@
GB
PDVVRIWKHVROXWLRQLQWKHYROXPHWULFDVNPDGHXSWRJZLWK
1+CO>J@
Au purity
WKHSXULW\RIJROGVWDWHGLQWKHFHUWLFDWH>@
G _100
C _ St 2 = C Au _999.9
G_0.43
G _100
C _ St1
C _ St 2
CRQFHQWUDWLRQRI$XZRUNLQJVWDQGDUGVROXWLRQV>JJ@
CBStIRUORZJJDQGCBStIRUKLJKJJ
C Au _999.9
CRQFHQWUDWLRQRI$XVWDQGDUGVROXWLRQ$X>JJ@SUHSDUHGIURP
SXUHJROG
G_0.37
G_0.43
G_100
30
G_0.37
MDVVHVRIWKHLQLWLDO$XVWDQGDUGVROXWLRQWUDQVIHUUHGIRUWKHSUHSDUDWLRQ
RIFDOLEUDWLRQVROXWLRQVCBStJJRUCBStJJ>J@JRU
JUHVSHFWLYHO\
MDVV RI JUDYLPHWULFDOO\ FRQWUROOHG FDOLEUDWLRQ VWDQGDUG VROXWLRQV DIWHU
DGGLQJ1+COLQSRO\SURS\OHQHYLDOV>J@
Bracketing calibration
Cx =
C st1 ( A_ St 2 A _ X ) + C St 2 ( A x A St1 )
A St 2 A St1
CRQFHQWUDWLRQRI$XLQWKHDQDO\VHGVROXWLRQ>JJ@
Cx
C St 2
A St1
$EVRUEDQFHPHDVXUHGIRUWKHORZHUFDOLEUDWLRQVWDQGDUGVROXWLRQCB6W
A_ St 2
$EVRUEDQFHPHDVXUHGIRUWKHKLJKHUFDOLEUDWLRQVWDQGDUGVROXWLRQCB6W
C St1
$EVRUEDQFHPHDVXUHGIRUWKHDQDO\VHGVDPSOHVROXWLRQ
A_ X
1 V_ 50 1 Gvials _12
Cx
1000 m_ 0.1 R GP _ 0, 4
WB
QDOFRQFHQWUDWLRQRI$XLQWHVWHGMHZHOOHU\JROGDOOR\ZZ>@
YROXPHRIWKHVROXWLRQLQWKHYROXPHWULFDVN>PL@
V_ 50
PDVVRIDQDO\VHGDOOR\VDPSOH>J@
m_ 0.1
Gvials _12
ZHLJKWRIQDOVDPSOHVROXWLRQSUHSDUHGLQYLDOV>J@
GP _ 0.4
PDVVRI$XVDPSOHVROXWLRQWDNHQIURPVB>J@
FRUUHFWLRQIRUUHFRYHU\
A St 2 A St1
R
G_10
1000 m _ 0.1 GP _ 0.4
31
u_ A _ one _ set
N
u_ A
u_ A _ one _ set
32
33
34
Value
Unit
Standard
uncertainty
Remark
V_ 50
50
mL
0.0379
V_100
100
mL
0.0697
m_0.1
0.1001
0.0002
Gvials _12
12.0030
0.0008
GP _ 0.4
0.4015
0.0009
m_ pureAu
0.1004
0.0002
Au_ purity
99.99
0.0058
G p _0.37
G p _0.43
0.3701
0.4302
0.0006
G_10
10.0321
0.0008
A St1
A_ St 2
0.5203
0.6041
AU
0.0010
0.0011
AX
0.5488
AU
0.0011
1.002
0.0025
Recovery
35
TrainMiC Exercises
Analytical procedure
Determination of gold in jewellery gold alloys by flame atomic
absorption spectrometry
EXERCISE 1:
Establishing traceability in analytical chemistry
EXERCISE 2:
Single laboratory validation of measurement procedures
Part I: General issues
Part II: Parameters to be validated
Part III: Some calculations and conclusions
EXERCISE 3:
Building an uncertainty budget
Addendum I: By spreadsheet approach
Addendum II: By dedicated software
36
Gold
Measurand
Units
(g/1000 g)
standard addition
standard curve
internal standard
Model equation
1. Standard solutions
1.1. Stock standard solution - prepared from pure gold
C Au _999.9 =
104
G p_0.37
G_ 100
C _ St 2 = C Au _999.9
G p_0.43
G_ 100
2. Bracketing calibration
Cx =
C St1 ( A_ St 2 A_ X ) + C St 2 ( A x A St1 )
A St 2 A St1
1 V_ 50 Gvials _12
1
Cx
1000 m_ 0.1
GP _ 0.4
R
u_ A _ one _ set
N
37
5. Calculation of recovery
R=
Wobserved
Wref
104
(G
P _0.37
( A_ St 2 A _ X ) + GP _0.43 ( A X A St1 )
A St 2 A St1
) 1
V _ 50
YROXPHRIDQDO\VHGVROXWLRQ>PL@
V _100
YROXPHRIVWRFNVWDQGDUGVROXWLRQ>PL@
m_ 0.1
PDVVRIDQDO\VHGDOOR\VDPSOH>J@
Gvials _12
PDVVRIVDPSOHVROXWLRQGLOXWHGLQYLDOV>J@
GP _ 0.4
PDVVRI$XVDPSOHVROXWLRQWDNHQIURPVBDVN>J@
m_ pureAu
Au_ purity
G p _0.37 or G p _0.43
G_100
PDVVZHLJKHGRISXUHJROG>J@
WKHSXULW\RIJROGVWDWHGLQWKHFHUWLFDWH>@
PDVVHV RI WKH VWRFN $X VWDQGDUG VROXWLRQ WUDQVIHUUHG IRU WKH
SUHSDUDWLRQRIFDOLEUDWLRQVROXWLRQV6WDQG6W>J@
PDVVRIFDOLEUDWLRQVWDQGDUGVROXWLRQV>J@
A St1 DQG A_ St 2
AX
DEVRUEDQFHPHDVXUHGIRUFDOLEUDWLRQVWDQGDUGVROXWLRQVDQG
UHFRYHU\
DEVRUEDQFHPHDVXUHGIRUWKHDQDO\VHGVDPSOHVROXWLRQ
3. List the input quantities according to their influence on the uncertainty of the
result of the measurement (first the most important ones). At this point, your
judgement should be based on your previous experience only.
38
Mass of stock solution taken for the preparation of first standard solution contributing 12.1 % to the
expanded uncertainty
4. List the reference standards needed and give also the information regarding
traceability of the reference value
For the analyte
1
Name/Chemical Formula/Producer:
Name/Chemical Formula/Producer:
Quantity/Equipment/Calibration:
e.g. mass/balance/calibrated by NMI, U = xx
(k = 2), see also data yellow sheet
Quantity/Equipment/Calibration:
Quantity/Equipment/Calibration:
Yes
Within-lab reproducibility
No
39
40
Analyte
Gold
The measurand
Unit
Gold in 5 % NH4Cl
Measuring range
37-43 g g-1
Within-lab reproducibility
Measurement uncertainty
Trueness
Other-state
Full
Partial
Confirmation/Verification
41
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
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
43
Calculations
LOD
LOQ
Repeatability
2.4
Within-lab reproducibilty
Trueness
Measurement uncertainty
8.3 (k = 3)
1.0002 0.0025
12. Does the analytical procedure fulfil the requirement(s) for the intended use?
Parameter
Value obtained
during
validation
The requirement
is fulfilled
Yes/No
9 (k = 3)
8.3 (k = 3)
yes
LOD
LOQ
Repeatability
Within-lab
reproducibility
Trueness
Measurement
uncertainty
Other
No
44
Unit
(g/1000 g)
Model equation:
1. Concentration of initial standard solution made up from pure gold
C Au 999.9 =
m pureAu Au purity
G _100
104
C _ St 2 = C Au _999.9
G_0.43
G _100
G_0.37
G _100
3. Bracketing calibration
Cx =
C St1 ( A_ St 2 A_ X ) + C St 2 ( A x A St1 )
A St 2 A St1
1 V_ 50 1 Gvials _ 12
Cx
1000 m_ 0.1 R GP _ 0.4
45
u_ A _ one _ set
N
6. Calculation of recovery
R=
Wobserved
Wref
A St 2 A St1
R
G_100
1000 m _ 0.1 GP _ 0.4
46
Input quantity
Value
Unit
Remark
V _ 50
50
mL
V _100
100
mL
m_ 0.1
0.1001
Gvials _12
12.0030
GP _ 0.4
0.4015
m pureAu
0.1004
Au_ purity
99.99
G p _0.37 ; G p _0.43
0.3701; 0.4302
G_100
10.0321
AU
A St1 ; A_ St 2
0.5203; 0.6041
AU
AX
0.5488
AU
1.002
Standard
uncertainty
Unit
Remark
V _ 50
0.0379
mL
V _100
0.0697
mL
m_ 0.1
0.0002
Gvials _12
0.0008
GP _ 0.4
0.0009
m pureAu
0.0002
Au_ purity
0.0058
G p _0.37 ; G p _0.43
0.0006; 0.0006
G_10
0.0008
A St1 ; A_ St 2
0.0010; 0.0011
AU
AX
0.0011
AU
0.0025
7. Calculate the combined standard uncertainty (uc) of the result and specify units
Using:
MDWKHPDWLFDOVROXWLRQ
6SUHDGVKHHWDSSURDFK
CRPPHUFLDOVRIWZDUH
47
Input
quantity
Value
Standard
uncertainty
Unit
Remark
W_
583.5
2.8
8. Calculate expanded uncertainty (Uc) and specify the coverage factor k and the
units
k
9. Analyse the uncertainty contribution and specify the main three input quantities
contributing the most to Uc
1
48
Further readings
I62-HZHOOHU\)LQHQHVVRISUHFLRXVPHWDODOOR\V
CI%-2PUHFLRXVPHWDOVFRPPLVVLRQThe Precious Metals Book
I62'HWHUPLQDWLRQRIJROGLQJROGMHZHOOHU\DOOR\VCXSHOODWLRQPHWKRG
UHDVVD\
I62 -HZHOOHU\ 'HWHUPLQDWLRQ RI SUHFLRXV PHWDOV LQ R JROG
SODWLQXPDQGSDOODGLXPMHZHOOHU\DOOR\V'LIIHUHQFHPHWKRGXVLQJLQGXFWLYHO\FRXSOHG
SODVPDRSWLFDOHPLVVLRQVSHFWURVFRS\ICP2(6
RMDXUL(+XHUWDDQGMGHOD*XDUGLD)ODPHDWRPLFDEVRUSWLRQDQDO\VLVRIJROG
LQMHZHOU\VDPSOHVFresenius J. Anal. Chem.
MMRRLPDQ'-.LQQHEHUJL:6LPSVRQPCHWWRXDQGPRDPRQL+LJKSXULW\
SUHFLRXVPHWDOVTM6$QQXDOMHHWLQJ
I(UXVDOLPVKLNDQG6MRLVHHY(OHFWURFKHPLFDODQGFRUURVLRQSURSHUWLHVRIJROGDQG
LWVDOOR\V9I-HZHOU\JROGDOOR\VRISXULW\VWDQGDUGLQK\GURFKORULFDFLGVROXWLRQV
Protect. Metals
* *DOEiFV 1 -HGOLQV]NL * CVHK = *DOEiFV DQG L T~UL$FFXUDWH TXDQWLWDWLYH
DQDO\VLV RI JROG DOOR\V XVLQJ PXOWLSXOVH ODVHU LQGXFHG EUHDNGRZQ VSHFWURVFRS\ DQG
D FRUUHODWLRQEDVHG FDOLEUDWLRQ PHWKRG Spectrochim. Acta B Atom. Spectrosc.
$ MDUXFFR C MDUFROOL DQG R MDJDULQL ICP2(6 DQDO\VLV RI JROG DOOR\V XVLQJ
\WWULXPRULQGLXPDVLQWHUQDOVWDQGDUGAtom. Spectrosc.
9 6WHIDQRYD 9 .PHWRY DQG L )XWHNRY$LU VHJPHQWHG GLVFUHWH LQWURGXFWLRQ LQ
LQGXFWLYHO\ FRXSOHG SODVPD PDVV VSHFWURPHWU\ J. Anal. Atom. Spectrom.
9.PHWRY'+ULVWR]RY96WHIDQRYD6THQHYDQGL)XWHNRYCRPSXWHUDXWRPDWHG
V\VWHP IRU PLFURVDPSOLQJ LQ )$$6 VRIWZDUH IRU VLJQDO DFTXLVLWLRQ DQG WUHDWPHQW
8QLYHUVLW\RIPORYGLYP+LOHQGDUVNLScientic Works-Chem.
9.PHWRY96WHIDQRYD'*HRUJLHYDDQGL)XWHNRY$QDO\VLVRIMHZHOOHU\JROG
DOOR\V E\ PLFURVDPSOLQJ RI FRPSOH[ VROXWLRQV LQWR )$$6 DQG ICPM6 LQ Forth
National Conference of Chemistry Soa6HSWHPEHUP
-.UDJWHQCDOFXODWLQJVWDQGDUGGHYLDWLRQVDQGFRQGHQFHLQWHUYDOVZLWKDXQLYHUVDOO\
DSSOLFDEOHVSUHDGVKHHWWHFKQLTXHAnalyst
49
50
$/3 0$+$,2
6 7
%""
.,-/
) 2 2
/
3
/
+
+
(
8
!*1!-4
,.323 ,2
*'0(!*")'4.! 0.*'0/%*)
#*' +%!(..
!%#$/*"1%'.
..*"0.*'0/%*)
*)!)/-/%*)/*"./*&./) - .*'0/%*)
!%#$/*""'.&
..*"./*&.*'0/%*)0.! "*-+-!+-/%*)*"/
..*"./*&.*'0/%*)0.! "*-+-!+-/%*)*"/
.*-).!*"$%#$/
.*-).!*"/$!.(+'!
-*-)!*"/$!'*2/
&-/
)
$13*2
+
+
+
4' *1
.
3
.
.
2
6
2
0")
#
#
#
#
8#
#
#
#
)0(
,'21
(
1%'.
+
0
+
+
/
3
/
3 "
.
&
0&$2
4' *1
.
4' *1
*3$1
3
3
3 "
.
.
2
6
.
.
2
6
2
2
Chapter 2
52
Measurand
Example number
Ex-10
Analytical procedure
Customers requirement
3 - Green
2 - Yellow
1-I
Ex-10-2-YCa-serumPhotometry2006-Ver1.doc
Ex-10-3-GCa-serumPhotometry2006-Ver1.doc
File is
attached
Yes No
PART I
PART II
PART
III
PART
IV
PART I
PART II
PART
III
Remark
Given by the
lecturer
Each
participant
receives own
copy and
may keep it
April 2007
53
'HWHUPLQDWLRQ RI FDOFLXPLQVHUXP
E\ VSHFWURSKRWRPHWU\
6FRSHRIWKHSUHVHQWDWLRQ
7KHDQDO\WLFDOSURFHGXUHDQGWKHFXVWRPHUVUHTXLUHPHQWV
$ERXWWKHFKHPLVWU\ DQGWKHPHDVXUHPHQWDVSHFWV
0RGHOHTXDWLRQDQGPRUHDERXWWUDFHDELOLW\YDOLGDWLRQDQG
XQFHUWDLQW\H[HUFLVHV
7KHDQDO\WLFDOSURFHGXUHDQGWKH
FXVWRPHUVUHTXLUHPHQWV
$QDO\WLFDOSURFHGXUH
*XLGHOLQHRQ6WDQGDUG2SHUDWLQJ3URFHGXUHIRU&OLQLFDO&KHPLVWU\
&DOFLXP2&UHVROSKWDOHLQ FRPSOH[RQH PHWKRG6WDQGDUG0HWKRGV
KWWSZZKRVHDRUJ
&XVWRPHUVUHTXLUHPHQWV
$QDO\WLFDOUHSURGXFLELOLW\&9:+2DFWXDO
VWDWHRIDUW
,QWHQGHGXVHFOLQLFDOLQWHUSUHWDWLRQ
54
Analysis of GoldofAlloys
Determination
Calcium
by Flame
in Serum
Atomic
by Spectrophotometry
Absorption Spectrometry
([SHULPHQWDOSURWRFRO
SUHSDUHEXIIHUUHDJHQWVS+ DQG
FRORXUUHDJHQWV
SUHSDUH&DVWRFN VROXWLRQ FDOLEUDQWV
6DPSOH VHUXPQRVDPSOHWUHDWPHQW
0,;ZDWHUVWGFRORXU UHDJ VDPSOH
LQFXEDWHDW&IRUPLQ
&DOLEUDWLRQFKHFNOLQHDULW\
EODQNWR]HUR
LQWHUSRODWLRQ 2QHSRLQWFDOLEUDWLRQ
FKHFN4& EHWZHHQGD\VSUHFLVLRQ
55
Analytical procedure
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
Description of the analytical procedure
PART II .................................................................................................................................60
The customers requirements concerning the quality of the measurement result
PART III ................................................................................................................................61
Validation of the measurement procedure relevant equations and
measurement data
PART IV ................................................................................................................................62
Measurement uncertainty of the result relevant equations and measurement
data
56
Laboratory task
COLQLFDO ODERUDWRU\ KDV WR GHWHUPLQH FDOFLXP FRQFHQWUDWLRQ LQ KXPDQ VHUXP VDPSOH
DULYLQJLQWKHLUODERUDWRU\IWLVWKHFDVHZKHQRQO\WKHDQDOLWLFDOSDUWLVFRQVLGHUHGWKH
ODERUDWRU\KDVQRWUHVSRQVLELOLW\KRZVDPSOHLVWDNHQSUHSDUHGWUDQVSRUWHG
TKH ODERUDWRU\ VKRXOG HYDOXDWH WKH DQDO\WLFDO SURFHGXUH UHOLDELOLW\ ZLWKLQ ODERUDWRU\
UHSURGXFLELOLW\TKHUHSRUWHGUHVXOWVVKRXOGFRPSO\ZLWKWKHFOLQLFDOLQWHUSUHWDWLRQWKH
H[SHFWHGQRUPDOUDQJHRIFDOFLXPFRQFHQWUDWLRQLQVHUXPLVPJGL
Analytical procedure
Serum sample preparation and storage
1RVHUXPSUHSDUDWLRQLVSHUIRUPHGE\WKHODERUDWRU\LQFKDUJHZLWKWKHDQDO\WLFDOZRUN
6HUXP VDPSOH DULYHV LQ WKH ODERUDWRU\ DIWHU VHSDUDWLRQ IURP WKH EORRG FHOOV GXULQJ
WKHSUHDQDO\WLFDOVWHSSHUIRUPHGE\DQRWKHUGHSDUWPHQW+DHPRO\VHGDQGKHSDULQLVHG
VDPSOHVDUHXQVXLWDEOHIRUWKLVPHWKRG
CDOFLXPLQVHUXPLVVWDEOHIRUKDWURRPWHPSHUDWXUHCRQHZHHNDWC
DQGIRUDORQJHUSHULRGXSWRPRQWKVDWC
Reagents
$MP%XIIHUS+
IQPLRI$MPUHDJHQWDGGPLRIGLVWLOOHGZDWHUDQGPL[$GMXVWWKHS+WR
ZLWK+CO1DQGPDNHXSWRPLZLWKGLVWLOOHGZDWHU6WRUHLQWKHUHIULJHUDWRULQD
EURZQFRORXUHGJODVVERWWOH6WDEOHIRUWKUHHZHHNV
57
CRORXUUHDJHQWV
$GG PL FRQFHQWUDWHG +CO WR D PL YROXPHWULF DVN FRQWDLQLQJ DERXW PL
RIGLVWLOOHGZDWHUTUDQVIHUPJ2FUHVROSKWKDOHLQFRPSOH[RQHSRZHULQWRLWPL[WR
GLVVROYHTKHQDGGPJRIK\GUR[\TXLQROLQHGLVVROYHDQGWKDQPDNHXSWR
PLZLWKGLVWLOOHGZDWHU6WRUHLQDEURZQFRORXUHGJODVVERWWOHDWURRPWHPSHUDWXUH
C6WDEOHIRUDERXWRQHPRQWK
CDOFLXPVWDQGDUGVROXWLRQV
Stock calcium standard solution
CDOFLXPFDUERQDWHLVGULHGDWCIRUK$OORZWRFRROLQDGHVLFDWRU'LVVROYH
PJRIGULHGFDOFLXPFDUERQDWHLQPLRIGLVWLOOHGZDWHUWDNHQLQDPLYROXPHWULF
DVNDQGDGGPL+COFRQFML[WRGLVVROYHDQGPDNHXSWRPLZLWKGLVWLOOHG
ZDWHU6WRUHLQEURZQERWWOHDWURRPWHPSHUDWXUHC6WDEOHIRUPRQWKVTKH
FDOFLXPFRQFHQWUDWLRQLQWKLVVROXWLRQLVPJGL
Calibration calcium standard solutions
TKH FDOLEUDWLRQ FDOFLXP VWDQGDUG VROXWLRQV DUH SUHSDUHG E\ GLOXWLRQ RI VWRFN FDOFLXP
VWDQGDUGVROXWLRQLQWRIRXUPLYROXPHWULFDVNVWUDQVIHUDQGPLRI
VWRFNFDOFLXPVWDQGDUGVROXWLRQDQGGLOXWHHDFKWRPLZLWKEHQ]RLFDFLGTKHZRUNLQJ
VWDQGDUGVFRQWDLQ666DQG6PJGLFDOFLXPUHVSHFWLYHO\
6WRUHLQEURZQERWWOHVDWURRPWHPSHUDWXUHC6WDEOHIRUPRQWKV
Instrumentation
$SKRWRPHWHURUVSHFWURSKRWRPHWHULVXVHGLQWKHYLVLEOHUDQJHLQWH[WLWLVFDOOHGVSHFWUR
SKRWRPHWHUTKH LQVWUXPHQWDO SHUIRUPDQFHV VSHFWUDO UDQJH QP DEVRUEDQFH
DFFXUDF\DW$TKHLQVWUXPHQWKDVWKHDEVRUEDQFHVFDOHDVDFRQFHTXHQFHIRU
FRQFHQWUDWLRQPHDVXUHPHQWVWKHFDOLEUDWLRQJUDSKVKRXOGEHHVWDEOLVKHGE\ODERUDWRU\
LWVHOI
Experimental protocol
TKHH[SHULPHQWDOVWHSVRIWKHPHDVXUHPHQWSURFHGXUHDUHGHVFULEHGLQWKHWDEOHEHOORZ
DGHQHGYROXPHVRIFDOLEUDWLRQVROXWLRQVDQGVHUXPVDPSOHPLDUHPL[HGZLWK
PLRIFRORXUUHDJHQWML[HGWKDQZLWKPLRIEXIIHUVROXWLRQ
58
Blank
S5
S7.5
S10
S12.5
Serum
QC
0.1
Standard (mL)
0.1
0.1
0.1
0.1
Serum/QC (mL)
0.1
0.1
2.0
2.0
2.0
2.0
Mix
well
2.0
2.0
Mix
well
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Calculation of result
TKHIROORZLQJHTXDWLRQLVLQGLFDWHGLQ:+2SURFHGXUH
cCa = ( Ax A10 ) 10 >PJGL@
ZKHUHcCDFRQFHQWDWLRQRIFDOFLXPLQVHUXPVDPSOH
AxDEVRUEDQFHRIVHUXPVDPSOH
ADEVRUEDQFHRIWKHFDOLEUDWLRQVROXWLRQPJGL
Analytical reliability
IQFOXGH RQH LQWHUQDO TXDOLW\ FRQWURO VDPSOH QC LQ HYHU\ EDWFK RI VDPSOHV DQDO\VHG
HDFKGD\LUUHVSHFWLYHRIWKHQXPEHURIVDPSOHVLQDEDWFK6LQFHFDOFLXPLVDQDO\VHG
VLQJOH EDWFK LQ D GD\ LQ DQ LQWHUPHGLDWH ODERUDWRU\ LW ZLOO QRW EH SRVVLEOH WR DQDO\VH
VHYHUDOQCVDPSOHVDQGFDOFXODWHZLWKLQGD\SUHFLVLRQ+RZHYHUHYHQLIRQO\DVLQJOH
QCVDPSOHLVDQDO\VHGLQDGD\WKLVYDOXHFDQEHSRROHGZLWKWKHSUHFHGLQJRU
YDOXHVREWDLQHGLQWKHSUHYLRXVGD\VDQGEHWZHHQGD\SUHFLVLRQFDQEHFDOFXODWHGDQG
H[SUHVVDVC9(QVXUHWKDWWKLVLVZHOOZLWKLQWKHDFFHSWDEOHOLPLWLHDFWXDO
SHUIRUPDQFHHYHQ
$WOHDVWRQFHDZHHNDQDO\VHDQRWKHUQCVHUXPIURPHLWKHUDORZRUKLJKQCSRRO
59
:RUOG+HDOWK2UJDQL]DWLRQ
60
(c
i , obs
CV =
cQC
n ( n 1)
100
cQC
CV
FRHIFLHQWDVYDULDWLRQ>@
cREV
cQC
WDUJHWFDOFLXPFRQFHQWUDWLRQLQQCVHUXP>PJGL@
QXPEHURIUHSURGXFLEOHPHDVXUHPHQWV
Measurement data
Input quantity
ci,obs
(i = 15) day
3 replicates/day
8.990 0.057
rd
3 day:
9.210 0.105
4th day:
9.230 0.086
5th day:
9.110 0.120
cQC
8.2410.52
Unit
9.16 0.05
mg dL-1
9.280 0.021
nd
2 day:
Mean value
standard deviation
9.38 0.38
mg dL-1
no units
CV =
61
cVWRFN
FRQFHQWUDWLRQRIFDOFLXPVWRFNVROXWLRQ>PJGL@
PDVVRICDC2>PJ@
MCD
PRODUPDVVRIFDOFLXP>JPRO@
SXULW\RICDC2>PDVVIUDFWLRQ@
V
QDOYROXPHRIFDOFLXPVWRFNVROXWLRQ>PL@
MCDC2
PRODUPDVVRICDC2>JPRO@
MHDVXUHPHQWGDWD
Input quantity
Value
Standard uncertainty
Unit
625.0
0.2
mg
MCa
40.078
0.002
g mol-1
0.9999
0.0058
mass fraction
V500
500.00
0.15
mL
MCaCO3
100.0869
0.0024
g mol-1
cVWRFN
CRQFHQWUDWLRQRIFDOFLXPVWRFNVROXWLRQ>PJGL@
Vi
V
9ROXPHRIFDOLEUDWLRQVROXWLRQ>PL@
+HUH\RXPD\DOVRZDQWWRLQFOXGHWKHUHOHYDQWFHUWLFDWHV
62
MHDVXUHPHQWGDWD
Input quantity
Value
Standard uncertainty
Unit
cstock
50.05
0.02
mg dL-1
Vi
20.000
0.043
mL
V100
100.000
0.058
mL
cx
c
Ax
A
AEODQN
CRQFHQWUDWLRQRIVHUXPVDPSOHIURPFDOLEUDWLRQGDWD>PJGL@
CRQFHQWUDWLRQRIFDOFLXPFDOLEUDWLRQVROXWLRQPJGL>PJGL@
$EVRUEDQFHFRUUHVSRQGLQJWRVHUXPVDPSOH
$EVRUEDQFHFRUUHVSRQGLQJWRFDOLEUDWLRQVROXWLRQPJGL
$EVRUEDQFHFRUUHVSRQGLQJWREODQNVROXWLRQ
MHDVXUHPHQWGDWD
Input quantity
Value
Standard uncertainty
Unit
c_10
10.000
0.023
mg dL-1
Ax
0.323
0.004
no units
A-10
0.338
0.002
no units
Ablank
0.052
0.004
no units
c
cCa = cx f V x
int
VI
VLQW
FDOFLXPFRQFHQWUDWLRQLQVHUXPVDPSOH>PJGL@
FRQFHQWUDWLRQRIVHUXPVDPSOHIURPFDOLEUDWLRQGDWD>PJGL@
YROXPHRIVHUXPVDPSOHXQGHULQYHVWLJDWLRQ>PL@
LQWDNHYROXPHIURPVHUXPVDPSOH>PL@
MHDVXUHPHQWGDWD
Input quantity
Value
Standard uncertainty
Unit
cx
9.486
0.303
mg dL-1
Vf
0.100
0.002
mL
Vint
0.100
0.002
mL
63
TrainMiC Exercises
Analytical procedure
Determination of calcium concentration in human serum by
molecular absorbtion (spectro)photometry
The quality of results should comply with WHO procedure
requirements
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
64
Calcium
Measurand
Units
mg dL-1
Type of calibration
standard curve
standard addition
internal standard
int
cCD
M
WRWDOFDOFLXPFRQFHQWUDWLRQLQVHUXPVDPSOH>PJGL@
PDVVRICDC2>PJ@
MCD
PRODUPDVVRIFDOFLXP>JPRO@
SXULW\RICDC2>PDVVIUDFWLRQ@
V
QDOYROXPHRIFDOFLXPVWRFNVWDQGDUGVROXWLRQ>PL@
MCDC2
PRODUPDVVRICDC2>JPRO@
Vi
V
QDOYROXPHRIFDOLEUDWLRQVROXWLRQ>PL@
Ax
DEVRUEDQFHFRUUHVSRQGLQJWRVHUXPVDPSOH
A
DEVRUEDQFHFRUUHVSRQGLQJWRFDOLEUDWLRQVROXWLRQPJGL
AEODQN
DEVRUEDQFHFRUUHVSRQGLQJWREODQN
VI
YROXPHRIVHUXPVDPSOHXQGHULQYHVWLJDWLRQ>PL@
VLQW
LQWDNHYROXPHIURPVHUXPVDPSOH>PL@
65
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
Mass
4. List the reference standards needed and state the information regarding
traceability of the reference value
For the analyte
1
Name/Chemical Formula/Producer:
Name/Chemical Formula/Producer:
Quantity/Equipment/Calibration:
e.g. mass/balance/calibrated by NMI, U=xx
(k = 2), see also data yellow sheet
Absorbance/(Spectro)photometer/Calibrated against
traceable optical standard (i.e. PTB)
Quantity/Equipment/Calibration:
Quantity/Equipment/Calibration:
66
Yes
Matrix effect
No
67
Analyte
Calcium
The measurand
Unit
mg dL-1
Human serum
Measuring range
1.012.0 mg dL-1
LOD
LOQ
Repeatability
Mark the customers
requirements and give
their values
Within-lab reproducibility
Trueness
Measurement
uncertainty
Other-state
68
Full
Partial
Confirmation/Verification
69
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: ROCHE-Control serum type Precipath U
Spike of pure substance
Selectivity, interferences
6. Measuring range
Linearity
Upper limit
LOD
LOQ
7. Spread precision
Repeatability
Reproducibility (within lab)
Reproducibility (between lab)
8. Robustness
Variation of parameters
70
9. Quality control
Control charts
Participation in PT schemes
71
Calculations
LOD
LOQ
Repeatability
5
(c
i , obs
Within-lab reproducibilty
CV =
cQC
n ( n 1)
cQC
100 = 1.27 %
Trueness
Measurement uncertainty
Other - please state
12. Does the analytical procedure fulfil the requirement(s) for the intended use?
Parameter
Value requested by
the customer
(the same as stated in question 3)
Value obtained
during validation
The requirement
is fulfilled
Yes/No
1.27 %
YES
LOD
LOQ
Repeatability
Within-lab
reproducibility
Trueness
Measurement
uncertainty
Other
No
Unit
mg dL-1
int
cCD
WRWDOFDOFLXPFRQFHQWUDWLRQLQVHUXPVDPSOH>PJGL@
PDVVRICDC2>PJ@
MCD
PRODUPDVVRIFDOFLXP>JPRO@
SXULW\RICDC2>PDVVIUDFWLRQ@
V
QDOYROXPHRIFDOFLXPVWRFNVWDQGDUGVROXWLRQ>PL@
MCDC2
PRODUPDVVRICDC2>JPRO@
Vi
V
QDOYROXPHRIFDOLEUDWLRQVROXWLRQ>PL@
Ax
DEVRUEDQFHFRUUHVSRQGLQJWRVHUXPVDPSOH
A
DEVRUEDQFHFRUUHVSRQGLQJWRFDOLEUDWLRQVROXWLRQPJGL
AEODQN
DEVRUEDQFHFRUUHVSRQGLQJWREODQN
VI
YROXPHRIVHUXPVDPSOHXQGHULQYHVWLJDWLRQ>PL@
VLQW
LQWDNHYROXPHIURPVHUXPVDPSOH>PL@
73
Value
Unit
625.0
mg
MCa
40.078
g mol-1
0.9999
mass fraction
V500
500.00
mL
MCaCO3
100.0869
g mol-1
Vi
20.000
mL
V100
100.000
mL
Ax
0.323
no units
A-10
0.338
no units
Ablank
0.052
no units
Vf
0.100
mL
Vint
0.100
mL
Remark
74
Input quantity
Standard
uncertainty
Unit
0.2
mg
MCa
0.002
g mol-1
0.0058
mass fraction
V500
0.15
mL
MCaCO3
0.0024
g mol-1
Remark
Vi
0.043
mL
V100
0.058
mL
Ax
0.004
no units
A-10
0.002
no units
Ablank
0.004
no units
Vf
0.002
mL
Vint
0.002
mL
int
cCD PJGL
7. Calculate the combined standard uncertainty (uc) of the result and specify units
Using:
MDWKHPDWLFDOVROXWLRQ
6SUHDGVKHHWDSSURDFK
Input quantity
Value
Standard
uncertainty
Unit
625.0
0.2
mg
MCa
40.078
0.002
g mol-1
0.9999
0.0058
mass fraction
V500
500.00
0.15
mL
MCaCO3
100.0869
0.0024
g mol-1
Vi
20.000
0.043
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
CRPPHUFLDOVRIWZDUH
Remark
ucCD PJPRO
75
8. Calculate expanded uncertainty (Uc) and specify the coverage factor k and the
units
U(cCa) = k u (cCa) = 0.606 [mg dL-1], k = 2
9. Analyse the uncertainty contribution and specify the main three input quantities
contributing the most to Uc
1
76
Further readings
Guide to the Expression of Uncertainty in Measurement *8M VW HG
*HQHYH6ZLW]HUODQG
EurachemCitac Guide C* Qualtifying Uncertainty in Analytical Measurement
QGHG
6WDQGDUG RSHUDWLRQ SURFHGXUH IRU COLQLFDO FKHPLVWU\ 'HWHUPLQDWLRQ RI FDOFLXP E\
FDOFLXPRFUHVROSKWDOHLQFRPSOH[RQHPHWKRGKWWSZZKRVHRUJ
6 LLQNR 8 gUQHPDUN DQG R .HVVHO (YDOXDWLRQ RI PHDVXUHPHQW XQFHUWDLQW\ LQ
FOLQLFDOFKHPLVWU\*(RIMIRMM
-.UDJWHQCDOFXODWLQJVWDQGDUGGHYLDWLRQVDQGFRQGHQFHLQWHUYDOVZLWKDXQLYHUVDOO\
DSSOLFDEOHVSUHDGVKHHWWHFKQLTXHAnalyst
77
78
+#*
()*%
')
')
()&"
+#*
()*%
(*
()&"
"
*%)!&%
!
!
(*$!
()&"
+#*
()*%
79
Calibration
80
#
&'($
*
$'
!
($' %$
$*
&(# $*
&
Chapter 3
82
Measurand
Example number
Ex-08
Analytical procedure
Customers requirement
1-I
2 - Yellow
PART I
PART II
EX-08-2-Y-Ra226-waterAS-2006-Ver1.doc
PART III
3 - Green
PART IV
File is
attached
Yes No
9
9
9
9
Establishing traceability in
analytical chemistry
PART II
Addendum 1: By spreadsheet
approach
Addendum 2: By dedicated
software
PART III
Given
by the
lecturer
Each
participant
receives
own copy
and may
keep it
PART I
EX-08-3-G-Ra226-waterAS-2006-Ver1.doc
Remark
April 2007
83
'HWHUPLQDWLRQ RI 5DLQZDWHU
E\ DVSHFWURPHWU\
6FRSHRIWKHSUHVHQWDWLRQ
7KHDQDO\WLFDOSURFHGXUHDQGWKHFXVWRPHUVUHTXLUHPHQWV
$ERXWWKHFKHPLVWU\ DQGWKHPHDVXUHPHQWPHWKRG
0RGHOHTXDWLRQ
7KHDQDO\WLFDOSURFHGXUHDQGWKH
FXVWRPHUVUHTXLUHPHQWV
'HWHUPLQDWLRQRIUDGLXPLVRWRSHVE\%D62
FRSUHFLSLWDWLRQ IRUWKHSUHSDUDWLRQRIDOSKD
VSHFWURPHWULFVRXUFHV
-&/R]DQR))HUQDQGH]DQG-0**RPH]
-RXUQDORI5DGLRDQDO\WLFDO DQG1XFOHDU&KHPLVWU\
7KHTXDOLW\RIWKHUHVXOWVVKRXOGFRPSO\ZLWKWKH
UHTXLUHPHQWLQWKHUHYLVHGGLUHFWLYH(&RQWKH
TXDOLW\RIZDWHULQWHQGHGIRUKXPDQFRQVXPSWLRQ
LQSUHSDUDWLRQ
84
Analysis of GoldofAlloys
by in
Flame
Atomic
Absorption Spectrometry
Determination
Radium
Water
by -Spectrometry
5D
6LPLODU FKHPLFDO SURSHUWLHV DV&D
NQRZQ LVRWRSHV ZLWK PDVV
DUHIRXQG LQQDWXUH
(PLWWHG DOSKD SDUWLFOHV KDYH KLJK
SRWHQWLDO IRU FDXVLQJ ELRORJLFDO
GDPDJH
85
3UHSDUDWLRQ RI
VWDQGDUGV DQG VDPSOHV
$QDO\WLFDOSURFHGXUH
5DVWDQGDUGGLVF
6DPSOH
%DVWDQGDUGGLVF
$GGLWLRQRI%DWUDFHU
3E5D%D62 SUHFLSLWDWLRQ
)RUGHWHUPLQDWLRQRI
HIILFLHQF\RIDOSKD
VSHFWURPHWHU
:DVKLQJWKHSUHFLSLWDWH
'LVVROXWLRQ
5HSUHFLSLWDWLRQ
0LFURILOWUDWLRQ
)RUGHWHUPLQDWLRQ
UHFRYHU\RI
UDGLRFKHPLFDO
VHSDUDWLRQ
*DPPDFRXQWLQJ
IRUGHWHUPLQDWLRQRI
UHFRYHU\
$OSKDFRXQWLQJIRU
GHWHUPLQDWLRQRI5D
DVSHFWURPHWU\
+H
DSDUWLFOH
DSDUWLFOHVDUHHDVLO\
VWRSSHGE\DIHZ
PLFURQVRIDLU
$ YHU\ WKLQ VRXUFH
DOORZV DGHTXDWH
WUDQVPLVVLRQ RI WKH
DSDUWLFOHVWRWKH
GHWHFWRUVXUIDFH
86
Analysis of GoldofAlloys
by in
Flame
Atomic
Absorption Spectrometry
Determination
Radium
Water
by -Spectrometry
0RGHOHTXDWLRQ
0HDVXUDQG
8QLW
%T /
$ 5D
W5D
35D
u
5FKHP
u DGHW u 9VDPSOH
3%D VDPSOH
5FKHP
GHW
W 5D 6WG
35D 6WG
u P5D 66 u $5D 66
55D 6WG
X $5D
$5D
W 5D
35D
u D GHW u 9VDPSOH
X35D XDGHW
X9
3
9
5D GHW
5FKHP
X5
FKHP
5FKHP
N u X $5D
87
Analytical procedure
Determination of activity concentration of Ra-226 in drinking
water.
The quality of the results should comply with the requirements
in the revised Directive 98/83/EC on the quality of water
intended for human consumption
PART I ..................................................................................................................... 89
Description of the analytical procedure
PART II .................................................................................................................... 96
The customers requirements concerning the quality of the measurement result
PART III ................................................................................................................... 97
Validation of the measurement procedure relevant equations and
measurement data
PART IV ................................................................................................................... 98
Measurement uncertainty of the result relevant equations and measurement
data
88
)RUWKHGHWHUPLQDWLRQRIRDLQZDWHUWKHIROORZLQJSXEOLVKHGSURFHGXUHLVXVHG
Determination of radium isotopes by BaSO4 coprecipitation for the preparation of
alpha-spectrometric sources
-CLR]DQR))HUQDQGH]DQG-M**RPH]
-RXUQDORIRDGLRDQDO\WLFDODQG1XFOHDUCKHPLVWU\223
1. Scope
1.1 General
TKH SURFHGXUH LV VSHFLHG IRU WKH GHWHUPLQDWLRQ RI RD LQ ZDWHU ZLWK DFWLYLW\
FRQFHQWUDWLRQGULQNLQJZDWHUUDLQZDWHUJURXQGZDWHUDQGVXUIDFHZDWHULQUDQJHRI
%TL
IQFHUWDLQFDVHVWKHUDQJHRIDSSOLFDWLRQPD\EHFKDQJHGE\YDULDWLRQVLQWKHZRUNLQJ
FRQGLWLRQV HJ VDPSOH YROXPH SUHFRQFHQWUDWLRQ WHFKQLTXHV VHQVLWLYLW\ UDQJHV RI
GHWHFWRUVHWF
1.2 Interferences
IQ WKH FDVH RI RD PHDVXUHPHQW E\ VSHFWURPHWU\ H[WHQVLYH FKHPLFDO VHSDUDWLRQ
SULRUWRFRXQWLQJWRUHPRYHSHDNLQWHUIHUHQFHVIURPRWKHUDOSKDHPLWWHUVLVUHTXLUHG
2. Principle
$ FRSUHFLSLWDWLRQ SURFHGXUH IRU WKH SUHSDUDWLRQ RI DOSKD VSHFWURPHWULF VRXUFH IRU
UDGLXPXVLQJ%D62DVFDUULHUIRUGHWHUPLQDWLRQRIRDLQZDWHULVXVHGTKHXVHRI
%DDVDVXLWDEOHWUDFHUIRUGHWHUPLQDWLRQRIUHFRYHU\RIWKHUDGLRFKHPLFDOSURFHGXUH
E\ JDPPD VSHFWURPHWU\ LV DSSOLHG ([SHULPHQWDO SURWRFRO LV VFKHPDWLFDOO\ VKRZQ LQ
)LJXUH
89
3. Apparatus
90
$OSKDVSHFWURPHWHUZLWKORZEDFNJURXQGVLOLFRQVXUIDFHGHWHFWRU
+P*HJDPPDGHWHFWRU
$QDO\WLFDOEDODQFHd =0.001
CHQWULIXJHDQGPLFHQWULIXJHWXEV
)XPHKRRG
+RWSODWH
MDJQHWLFVWLUUHUSODWHEDUVDQGUHWULHYHU
)LOWHUDSSDUDWXV
*ODVVEHDNHUVYROXPHWULFDVNDQGJUDGXDWHGF\OLQGHUVDVVRUWHGVL]HV
PLSHWWHVDVVRUWHGVL]HV
PPPGLDPHWHUSRO\SURS\OHQHOWHUV
6WDLQOHVVVWHHOGLVNV
PHWULVOLGHVZDWFKJODVVHV
4. Reagents
ML[HGVWDQGDUGVRXUFHIRUGHWHFWRUFDOLEUDWLRQGSPk
RDVWDQGDUGVROXWLRQ1I6T6RM
$FWLYLW\%TJRYHUDOOk
%DWUDFHU
$FWLYLW\N%TJk
:RUNLQJVROXWLRQ%TJ
+62FRQFHQWUDWHG
PEVROXWLRQPJPL
%DFDUULHUVROXWLRQPJPL
M('T$M1D2+
1D62VROXWLRQVDWXUDWHG
IQGLFDWRUS+
$FHWLFDFLG
%D62VHHGLQJVXVSHQVLRQ
91
$OORZWRVLWDWOHDVWPLQ
)LOWHUWKHFROORLGDOVXVSHQVLRQRIRD%D62WKURXJKDSUHZHWWHGPSRUH
VL]HPPSRO\SURS\OHQHOWHU
$IWHUWKHVDPSOHKDVOWHUHGULQVHWKHFHQWULIXJHZDOOVDQGWKHOWHUKROGHUZLWK
XOWUDSXUHZDWHU
RHPRYHOWHUDQGDOORZWRDLUGU\
MRXQWWKHOWHURQDVWDLQOHVVVWHHOGLVFXVLQJGRXEOHVLGHGWDSHRUJOXHVWLFNRU
FRYHUWKHVRXUFHZLWK9<16IRLO
92
MHDVXUHLQWRPLFHQWULIXJHWXEHJRIRDVWDQGDUGVROXWLRQ
$GGDSSUR[LPDWHOO\WKHVDPHDPRXQWRI%DVWDQGDUGDVXVHGSHUVDPSOH
$GGPLRI%DFDULHUVROXWLRQ
$GGDSSURSULDWHYROXPHRIFRQFHQWUDWHG+62
$GGPLRIPEVROXWLRQ
CHQWULIXJHDWUSPIRUYHPLQXWHV
PRXURXWVXSHUQDWDQWOLTXLG
:DVK VLGHV DQG WKH ZDOOV RI WKH FHQWULIXJH WXEH ZLWK XOWUDSXUH ZDWHU DQG
FHQWULIXJHDWUSPIRUPLQ
PRXURXWVXSHUQDWDQWWDNHFDUHQRWWRGLVWXUEWKHSUHFLSLWDWH
$GGPLM('T$M1D2+
'LVROYHWKHSUHFLSLWDWH
$GGDFHWLFDFLGWRDGMXVWS+
$GGPLRIVDWXUDWHG1D62
$GGPLRI%DVHHGLQJVROXWLRQ
MLFUROWUDWLRQRIVXVSHQVLRQ
:DVKLQJOWHUZLWKZDWHUIROORZHGE\GU\LQJ
MRXQWWKHOWHURQDVWDLQOHVVVWHHOGLVFXVLQJGRXEOHVLGHGWDSHRUJOXHVWLFNRU
FRYHUWKHVRXUFHZLWK9<16IRLO
93
9. Calculation
9.1 Sample recovery calculation
'HWHUPLQDWLRQRIUHFRYHU\E\JDPPDVSHFWURPHWU\LVFDOFXODWHGDVIROORZV
Rchem
PBa-133sample
tBa-133sample mBa-133sample
RFKHP
P%DVDPSOH
t%DVDPSOH
m%DVDPSOH
P%D6WG
t%D6WG
m%D6WG
GHW =
tRa-226Std
tBa-133Std
mBa-133Std
PBa-133Std
UDGLRFKHPLFDO\LHOGUHFRYHU\
SHDNDUHDRI%DLQWKHVDPSOH
WLPHRIWKHVDPSOHPHDVXUHPHQW>V@
PDVVRIDGGHG%DLQWKHVDPSOH>J@
SHDNDUHDRI%DLQEDULXPVWDQGDUGGLVF
WLPHRIPHDVXUHPHQWRI%DLQEDULXPVWDQGDUGGLVF>V@
PDVVRIDGGHG%DLQEDULXPVWDQGDUGGLVF>J@
PRa-226Std
mRa-226SS ARa-226SS
RRa-226Std
94
HIFLHQF\RIDOSKDGHWHFWRU
UDGLXPVWDQGDUGGLVFUHFRYHU\
SHDNDUHDRIRDLQVWDQGDUGGLVF
WLPHRIPHDVXUHPHQWRIVWDQGDUGGLVF>V@
PDVVRIDGGHGRDLQVWDQGDUGVROXWLRQ>J@
DFWLYLW\FRQFHQWUDWLRQRIRDLQVWDQGDUGVROXWLRQ>%TJ@
ARD
PRD
tRD
VVDPSOH
GHW
RFKHP
tRa-226
e det
PRa-226
Vsample
Rchem
$FWLYLW\FRQFHQWUDWLRQRIRDLQWKHVDPSOHLQ>%TL@
SHDNDUHDRIRD
WLPHRIPHDVXUHPHQW>V@
YROXPHRIWKHVDPSOH>L@
FRUUHFWHGHIFLHQF\RIDOSKDGHWHFWRU
UDGLRFKHPLFDO\LHOGUHFRYHU\
95
Nuclide
Reference concentration
Natural
Ra-226
0.5 Bq L-1
This table includes the most common natural and articial radionuclide Reference concentrations for other radionuclides can be
calculated using the dose coefcients for adults laid down in Annex III Table A of Directive 96/29/Euratom or more recent information
recognised by the competent authorities in the Member State, and by assuming an intake of 730 litres per year.
Limit of detection
Notes
Ra-226
0.04 Bq L-1
Note 1
Note 2
Note 1: the limit of detection should be calculated according to ISO 11929-7, Determination of the detection limit and decision thresholds
for ionizing radiation measurements - Part 7: Fundamentals and general applications, with probabilities of errors of 1st and 2nd kind of
0.05 each
Note 2: measurement uncertainties should be calculated and reported as complete standard uncertainties, or as expanded standard
uncertainties with an expansion factor of 1.96, according to the ISO Guide for the Expression of Uncertainty in Measurement (ISO, Geneva
1993, corrected reprint Geneva, 1995)
96
Equation
LLD =
tBkg
Measurement data
Input quantity
Unit
Value
Rchem
0.803
det
0.2453
Bkg
tBkg
Vsample
97
Equations
u ( ARa-226 )
ARa-226
u ( Rchem )
Rchem
u ( edet )
edet
u (Vsample )
u (PRa-226 ) u ( e det )
=
+
+
PRa-226 e det
Vsample
2
u (PBa-133Std )
=
+
PBa-133Std
u (mBa-133Std )
mBa-133Std
u (mRa-226SS )
u (PRa-226Std )
=
+
P
mRa-226SS
Ra-226Std
u (ARa-226 ) = k (ARa-226 )
98
u (Rchem )
+
Rchem
u PBa-133sample
+
PBa-133sample
u (ARa-226SS )
+
A
Ra-226SS
u mBa-133sample
+
mBa-133sample
u ( RRa-226Std )
+
R
Ra-226Std
PRa-226 Std
Rchem
det
RRa-226Std
-
PBa-133 Std
PBa-133 sample
Bq g-1
Unit
PRa-226
tBa-133 sample
tBa-133Std
time of measurement
tRa-226
ARa-226 SS
mRa-226 SS
mBa-133 sample
mBa-133Std
Vsample
Input quantity
Measurement data
12 785
5090
10 914
7516
3000
3000
300 000
2729
0.010
0.112
0.301
1.0
Value
113
71
104
87
0.001
0.001
0.001
0.002
(u)
Standard
uncertainty
Type of
uncertainty
normal
rectangular
Type of distribution
triangular
99
TrainMiC Exercises
Analytical procedure
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
intended for human consumption
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
100
Ra-226
Measurand
Units
Bq L-1
Type of calibration
standard addition
internal standard
Model equation
TKHDFWLYLW\FRQFHQWUDWLRQRIRDLQVDPSOH%TLLVFDOFXODWHGE\
A Ra-226 =
tRa-226
e det
PRa-226
Vsample
Rchem
ARD
DFWLYLW\FRQFHQWUDWLRQRIRDLQWKHVDPSOH>%TL@
PRD
SHDNDUHDRIRD
tRD
WLPHRIPHDVXUHPHQW>V@
YROXPHRIWKHVDPSOH>L@
GHW
FRUUHFWHGHIFLHQF\RIDOSKDGHWHFWRU
RFKHP
UDGLRFKHPLFDO\LHOGUHFRYHU\
Rchem =
PBa-133sample
tBa-133sample mBa-133sample
tBa-133Std mBa-133Std
PBa-133Std
RHFRYHU\REWDLQHGE\JDPPDVSHFWURPHWU\LVFDOFXODWHGDVIROORZV
RFKHP
UDGLRFKHPLFDO\LHOGUHFRYHU\
P%DVDPSOH
SHDNDUHDRI%DLQWKHVDPSOH
t%DVDPSOH
WLPHRIWKHVDPSOHPHDVXUHPHQW>V@
m%DVDPSOH
PDVVRIDGGHG%DLQWKHVDPSOH>J@
P%D6WGD
SHDNDUHDRI%DLQEDULXPVWDQGDUGGLVF
101
t%D6WG
WLPHRIPHDVXUHPHQWRI%DVWDQGDUGGLVF>V@
m%D6WG
PDVVRIDGGHG%DLQEDULXPVWDQGDUGGLVF>J@
$OSKDVSHFWURPHWHUHIFLHQF\LVFDOFXODWHGDVIROORZV
GHW =
tRa-226Std
PRa-226Std
mRa-226SS ARa-226SS
RRa-226Std
GHW
HIFLHQF\RIDOSKDGHWHFWRU
RRD6WG
UDGLXPVWDQGDUGGLVFUHFRYHU\
PRD6WG
SHDNDUHDRIRDRIVWDQGDUGGLVF
tRD6WG
WLPHRIPHDVXUHPHQWRIRDVWDQGDUGGLVF>V@
mRD66
PDVVRIDGGHGRDVWDQGDUGVROXWLRQ>J@
ARD66
RDDFWLYLW\FRQFHQWUDWLRQLQVWDQGDUGVROXWLRQ>%TJ@
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
Uncertainty of volumes
Uncertainty of weighing
4. List the reference standards needed and state the information regarding
traceability of the reference value
For the analyte
102
Name/Chemical Formula/Producer:
Name/Chemical Formula/Producer:
Name/Chemical Formula/Producer:
Quantity/Equipment/Calibration:
e.g. mass/balance/calibrated by NMI, U = xx
(k = 2) see also data yellow sheet
Quantity/Equipment/Calibration:
Yes
No
103
Analyte
Ra-226
The measurand
Unit
Bq L-1
Drinking water
Measuring range
0.0110 Bq L-1
LOD
LOQ
Mark the customers
requirements and give
their values
Repeatability
Within-lab reproducibility
Trueness
Measurement uncertainty
Other-state
104
Full
Partial
Confirmation/Verification
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
spiking of samples with pure substances and calculation of recovery
Compare with a reference method
Selectivity, interferences
6. Measuring range
Linearity
Upper limit
LOD
LOQ
7. Spread precision
Repeatability
Reproducibility (within lab)
Reproducibility (between lab)
105
8. Robustness
Variation of parameters
9. Quality control
Control charts
Participation in PT schemes
106
Calculations
LLD =
LOD
LOQ
Repeatability
Within-lab reproducibilty
Trueness
Measurement uncertainty
Other - please state
12. Does the analytical procedure fulfil the requirement(s) for the intended use?
Parameter
LOD
0.04 Bq L-1
LOQ
Repeatability
Value obtained
during validation
The requirement
is fulfilled
Yes/No
0.00025 Bq L-1
YES
Within-lab
reproducibility
Trueness
Measurement
uncertainty
Other
No
107
Unit
Bq L-1
Measurement procedure
'HWHUPLQDWLRQRIUDGLXPLVRWRSHVE\%D62FRSUHFLSLWDWLRQIRUWKHSUHSDUDWLRQRIDOSKD
VSHFWURPHWULFVRXUFHV
-CLR]DQR))HUQDQGH]DQG-M**RPH]
-RXUQDORIRDGLRDQDO\WLFDODQG1XFOHDUCKHPLVWU\223
Model equation:
TKHDFWLYLW\FRQFHQWUDWLRQRIRDLQWKHVDPSOH%TLLVFDOFXODWHGE\
A Ra-226 =
108
tRa-226
det
PRa-226
Vsample
Rchem
ARD
$FWLYLW\FRQFHQWUDWLRQRIRDLQWKHVDPSOH>%TL@
PRD
SHDNDUHDRIRD
tRD
WLPHRIPHDVXUHPHQW>V@
YROXPHRIWKHVDPSOH>L@
GHW
FRUUHFWHGHIFLHQF\RIDOSKDGHWHFWRU
RFKHP
UDGLRFKHPLFDO\LHOGUHFRYHU\
RHFRYHU\PHDVXUHGE\JDPPDVSHFWURPHWU\LVFDOFXODWHGDVIROORZV
Rchem =
PBa-133sample
tBa-133sample mBa-133sample
mBa-133Std
tBa-133Std
PBa-133Std
RFKHP
UDGLRFKHPLFDO\LHOGUHFRYHU\
P%DVDPSOH
PHDNDUHDRI%DLQWKHVDPSOH
t%DVDPSOH
WLPHRIWKHVDPSOHPHDVXUHPHQW>V@
m%DVDPSOH
PDVVRIDGGHG%DLQWKHVDPSOH>J@
P%D6WG
SHDNDUHDRI%DLQEDULXPVWDQGDUGGLVF
t%D6WG
WLPHRIPHDVXUHPHQWRI%DLQEDULXPVWDQGDUGGLVF>V@
m%D6WG
PDVVRIDGGHG%DLQEDULXPVWDQGDUGGLVF>J@
$OSKDVSHFWURPHWHUHIFLHQF\GHWHUPLQDWLRQLVFDOFXODWHGDVIROORZV
GHW =
tRa-226Std
PRa-226Std
mRa-226SS ARa-226SS
RRa-226Std
GHW
HIFLHQF\RIDOSKDGHWHFWRU
RRD6WG
UDGLXPVWDQGDUGGLVFUHFRYHU\
PRD6WG
SHDNDUHDRIRDLQVWDQGDUGGLVF
tRD6WG
WLPHRIPHDVXUHPHQWRIRDVWDQGDUGGLVF>V@
mRD66
PDVVRIDGGHGRDVWDQGDUGVROXWLRQ>J@
ARD66
RDDFWLYLW\FRQFHQWUDWLRQLQVWDQGDUGVROXWLRQ>%TJ@
109
Value
Unit
PRa-226
7516
tRa-226
300 000
det
0.2453
Vsample
1.0
Rchem
0.803
Remark
Standard
uncertainty
Unit
PRa-226
87
tRa-226
det
0.01392
Vsample
0.0020
Rchem
0.0142
Remark
Constant
A Ra-226 =
tRa 226
PRa-226
e det Vsample
7516
1
Rchem
1
= 0.127 Bq L-1
0.803
7. Calculate the combined standard uncertainty (uc ) of the result and specify units
Using:
110
MDWKHPDWLFDOVROXWLRQ
6SUHDGVKHHW$SSURDFK
Input quantity
Value
Standard
uncertainty
Unit
PRa-226
7516
87
tRa-226
300 000
det
0.2453
0.01392
Remark
CRPPHUFLDO6RIWZDUH
Vsample
1.0
0.0020
Rchem
0.803
0.0142
u ( ARa-226 )
ARa-226
u ( ARa-226 )
ARa-226
u (Vsample )
u (PRa-226 ) u ( edet )
=
+
+
PRa-226 edet
Vsample
2
87 0.01392
0.0020
=
+
+
7516 0.2453
1
u (Rchem )
+
Rchem
0.0142
+
= 0.00806
0.803
8. Calculate expanded uncertainty (Uc) and specify the coverage factor k and the
units
u (ARa-226 ) = k (ARa-226 )
U = 2 0.00806 = 0.016 Bq L-1
9. Analyse the uncertainty contribution and specify the main three input quantities
contributing the most to uc
1
111
Further readings
(CCRXQFLO'LUHFWLYHRI-XO\UHODWLQJWRWKHTXDOLW\RIZDWHULQWHQGHG
IRUKXPDQFRQVXPSWLRQOfc. J. Eur. Commun.L
(CCRXQFLO'LUHFWLYH(CRI1RYHPEHUTKHTXDOLW\RIZDWHULQWHQGHG
IRUKXPDQFRQVXPSWLRQOfc. J. Eur. Commun.L
(8R$T2M CRXQFLO RHJXODWLRQ (XUDWRP 1R RI -XO\
DPHQGLQJRHJXODWLRQ(XUDWRP1ROD\LQJGRZQPD[LPXPSHUPLWWHGOHYHOV
RI UDGLRDFWLYH FRQWDPLQDWLRQ RI IRRGVWXIIV DQG RI IHHGLQJVWXIIV IROORZLQJ D QXFOHDU
DFFLGHQW RU DQ\ RWKHU FDVH RI UDGLRORJLFDO HPHUJHQF\ Ofc. J. Eur. Commun. L
(8R$T2M (XURSHDQ CRPPLVVLRQ RHFRPPHQGDWLRQ (8R$T2M
Ofc. J. Eur. Commun. L
Guidelines for Drinking Water Quality, Recommendation YRO QG HG
:+2*HQHYD
Guidelines for Drinking Water Quality, Recommendation YRO UG FXUUHQW HG
LQFOXGLQJWKHUVWDGGHQGXP:+2*HQHYD$YDLODEOHIURPKWWSZZZZKRLQW
ZDWHUBVDQLWDWLRQBKHDOWK
-CLR]DQR))HUQDQGH]DQG-M**RPH]'HWHUPLQDWLRQRIUDGLXPLVRWRSHVE\
%D62FRSUHFLSLWDWLRQIRUWKHSUHSDUDWLRQRIDOSKDVSHFWURPHWULFVRXUFHVJ. Radioanalyt.
Nucl. Chem.
< 6SDVRYD 6 PRPPp L %HQHGLN DQG 8 :lWMHQ 8QFHUWDLQW\ %XGJHW IRU RD
$FWLYLW\ FRQFHQWUDWLRQ LQ:DWHU E\$OSKD 6SHFWURPHWU\ Acta. Chim. Slov.
L%HQHGLN<6SDVRYDM9DVLOHDQG8:lWMHQ'HWHUPLQDWLRQRI 8 8DQG
RD LQ ERWWOHG GULQNLQJ ZDWHU E\ DOSKD VSHFWURPHWU\ LQ C' Proceedings of the 7th
International Conference on Nuclear and Radiochemistry 1RC $XJXVW
%XGDSHVW+XQJDU\
112
!
113
114
!#
"
!
!!
!
!
"
$
!
!!
!
!
115
116
&/
#'#.)! . .#)(
.
.
..
'
.
-'*&
-'*&
.
-'*&
'
-'*&
.
.
'
.
.
#( 1
#!!
-/'-+#!!
1*( /( ,.#(.2%
. 0
.
.
..
'
.
-'*&
-'*&
.
-'*&
'
-'*&
.
.
.
'
.
List of quantities:
Quantity
ARa-266
Unit
-1
Bq L
edet
Vsample
PRa-266
tRa-266
Definition
Time of measurement
Efficiency for alfa detector
Rchem
PBa-133sample
tBa-133sample
mBa-133sample
tBa-133Std
mBa-133Std
PBa-133Std
PRa-226Std
tRa-226Std
mRa-226SS
ARa-226SS
RRa-226Std
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:
T\SH%UHFWDQJXODUGLVWULEXWLRQ
9DOXHJ
+DOIZLGWKRIOLPLWVJ
PBa-133Std:
T\SH$VXPPDULVHG
MHDQ
6WDQGDUG8QFHUWDLQW\
PRa-226Std:
T\SH$VXPPDULVHG
MHDQ
6WDQGDUG8QFHUWDLQW\
tRa-226Std:
CRQVWDQW
9DOXHV
118
mRa-226SS:
T\SH%UHFWDQJXODUGLVWULEXWLRQ
9DOXHJ
+DOIZLGWKRIOLPLWVJ
ARa-226SS:
T\SH$VXPPDULVHG
MHDQ
6WDQGDUG8QFHUWDLQW\
RRa-226Std:
T\SH$VXPPDULVHG
MHDQ
6WDQGDUG8QFHUWDLQW\
Uncertainty budgets:
ARa-266: Activity of Ra-266 in sample
Quantity
Value
Standard
Uncertainty
Distribution
Sensitivity
Coefficient
Uncertainty
Contribution
Index
PRa-266
7516.0
86.0
normal
17 10-6
3.3 %
tRa-266
300.0 103 s
Vsample
1.00000 L
2.04 10-3 L
triangular
-0.13
0.1 %
104
normal
-12 10
-1
-1.2 10 Bq L
2.3 %
577 10-6 g
rectangular
0.42
0.0 %
-6
-3
PBa-133sample
10 914
tBa-133sample
3000.0 s
mBa-133sample
0.301200 g
tBa-133Std
3000.0 s
mBa-133Std
0.112800 g
577 10-6 g
rectangular
-1.1
0.7 %
PBa-133Std
5090.0
71.0
normal
25 10-6
4.9 %
PRa-226Std
12785
113
normal
-9.9 10-6
2.0 %
tRa-226Std
2000.0 s
mRa-226SS
0.010220 g
577 10-6 g
rectangular
12
79.9%
ARa-226SS
2729.0
10.7
normal
47 10-6
0.4 %
RRa-226Std
0.9344
0.0150
normal
0.14
6.5 %
ARa-266
-1
0.12719 Bq L
8.04 10 Bq L
-3
-1
119
Value
Standard
Uncertainty
Distribution
Sensitivity
Coefficient
Uncertainty
Contribution
Index
PRa-226Std
12 785
113
normal
19 10-6
2.2 10-3
2.2 %
tRa-226Std
2000.0 s
mRa-226SS
0.010220 g
577 10-6 g
rectangular
not valid!
-0.014
normal
-90 10
-960 10
0.4 %
-0.26
-3.9 10
7.2 %
ARa-226SS
2729.0
10.7
RRa-226Std
0.9344
0.0150
normal
edet
0.2453
0.0146
-6
90.1 %
-6
-3
Value
Standard
Uncertainty
Distribution
Sensitivity
Coefficient
Uncertainty
Contribution
Index
PBa-133sample
10 914
104
normal
74 10-6
7.7 10-3
28.8 %
tBa-133sample
3000.0 s
mBa-133sample
0.301200 g
577 10-6 g
rectangular
-2.7
-1.5 10-3
1.2 %
tBa-133Std
3000.0 s
mBa-133Std
0.112800 g
577 10-6 g
rectangular
7.1
4.1 10-3
8.3 %
-160 10
-0.011
61.7 %
PBa-133Std
5090.0
71.0
normal
Rchem
0.8030
0.0143
-6
Result:
120
Quantity
Value
Expanded
Uncertainty
Coverage factor
Coverage
ARa-266
0.127 Bq L-1
0.016 Bq L-1
2.00
95 %
Chapter 4
Example number
Ex-04
Analytical procedure
Customers requirement
122
1-I
File number,
type and name
Ex-04-1-IPesticidesFood-LCMS2006-Ver1.ppt
2 - Yellow
PART II
PART III
3 - Green
PART IV
Ex-04-3-GPesticidesFood-LCMS2006-Ver1.doc
PART I
Ex-04-2-YPesticidesFood-LCMS2006-Ver1.doc
File is
attached
Yes No
Given by the
leacturer
9
Each
participant
receives own
copy and may
keep it
9
9
9
PART I
PART II
PART III
Remark
0
1
April 2007
123
124
06 PDVV
VSHFWURPHWHU
GHWHFWVLGHQWLILHV
DQGTXDQWLILHV WKH
DQDO\WHV
125
6DPSOH 3UHSDUDWLRQ
JRIKRPRJHQL]HGVDPSOHLVH[WUDFWHGZLWKPORIDFHWRQH
XVLQJKLJKVSHHGEOHQGHU
0L[WXUHLVILOWHUHGDQGWKHYROXPHRIH[WUDFWLVPHDVXUHG
PORIH[WUDFWLVH[WUDFWHGZLWKPOGLFKORURPHWKDQH
SHWUROHXPHWKHUPL[WXUHRUJDQLFOD\HULVILOWHUHGWKURXJK D
OD\HURIVRGLXPVXOSKDWHIRUGU\LQJSXUSRVH
:DWHUSKDVHLVVDWXUDWHGZLWK1D&O DQGH[WUDFWHGWZLFHZLWKPO
RIGLFKORURPHWKDQH
2UJDQLFH[WUDFWVDUHGULHG
6ROYHQWLVHYDSRUDWHGWRDOPRVWGU\QHVVDQGWKHVDPSOHLV
GLVVROYHGLQPORIPHWKDQRO
6DPSOHLVILOWHUHGWKURXJKDV\ULQJHILOWHUDQGDQDO\VHGXVLQJ/&
06V\VWHP
126
,QWKH/&06V\VWHPWKHVDPSOHVDUHVHSDUDWHGFKURPDWRJUDSKLFDOO\
(OXHQWDFHWRQWULOH%DQG EXIIHUVROXWLRQP0DPPRQLXPDFHWDWH
IRUPLFDFLG$DVHOXHQW
7KHJUDGLHQWSURJUDP%!PLQ%PLQDW
POPLQ
$QDO\VHGVXEVWDQFHVZHUHWKHQLRQL]HGXVLQJ WKH(6,SURFHGXUHDQG
DQDO\VHGZLWKWKHLRQWUDS06XVLQJIUDJPHQWDWLRQRITXDVLPROHFXODU
LRQV>0+@
8VLQJWKHPJNJ VWDQGDUGVROXWLRQDQGRWKHUGLOXWLRQVWKHFDOLEUDWLRQ
VROXWLRQVDUHSUHSDUHGLQPHWKDQRO LQWKHFRQFHQWUDWLRQ UDQJHRI
PJNJ
&DOLEUDWLRQJUDSKVDUHFRPSLOHGXVLQJSHDNDUHDVRIFHUWDLQFKDUDFWHULVWLF
IUDJPHQWLRQVRQGLIIHUHQWFRQFHQWUDWLRQV
0RGHO (TXDWLRQ
Z
Z
ZF
9
9H
9
0
ZF u 9 u U u 9H
9 u P
PDVVIUDFWLRQRIH[WUDFWDEOHSHVWLFLGHLQVDPSOH
PJRISHVWLFLGHSHUNJRIVDPSOH>PJNJ@
PDVVIUDFWLRQRIH[WUDFWDEOHSHVWLFLGHLQDQDO\VHGH[WUDFW
>PJNJ@ IRXQG IURP WKH FDOLEUDWLRQ JUDSK
WKHYROXPHRIILQDOH[WUDFWLQPHWKDQRO>PO@
GHQVLW\RIPHWKDQRO>JPO@
WKHIXOOYROXPHRIDFHWRQHH[WUDFW>PO@
WKHYROXPHRIDFHWRQHH[WUDFWWREHSXULILHG>PO@
PDVVRIKRPRJHQLVHGVDPSOHWREHH[WUDFWHG>J@
127
Analytical procedure
Determination of concentration of imazalil and thiabendazole
in tangerines by liquid chromatography mass spectrometry.
The quality of the results should comply with the requirements
in the EU directives 93/58/EEC and 00/42/EEC/ on pesticide
residues analysis
128
TKHREMHFWLYHRIWKLVDQDO\VLVLVSRVWUHJLVWUDWLRQFRQWURODQGPRQLWRULQJRILPD]DOLODQG
WKLDEHQGD]ROHSRODUSHVWLFLGHVEDVHGRQMD[LPXPRHVLGXHLLPLWVMRLVVHWE\WKH
(8'LUHFWLYHV((CDQG((C
6DPSOHSUHSDUDWLRQSURFHGXUHLVPRGLHG$2$CRIFLDOPHWKRG$QDO\VLVZDV
FDUULHGRXWRQDQLCM6V\VWHPXVLQJDVHOIGHYHORSHGFKURPDWRJUDSKLFPHWKRG
1. Scope
$ PRGLHG$2$C VDPSOH SUHSDUDWLRQ SURFHGXUH ZDV XVHG WR VXLWH LCM6
M6DQDO\VLVTKHDQDO\VLVZDVFDUULHGRXWXVLQJOLTXLGFKURPDWRJUDSKLFVHSDUDWLRQDQG
DWPRVSKHULFSUHVVXUHHOHFWURVSUD\LRQLVDWLRQZLWKWDQGHPPDVVVSHFWURPHWULFGHWHFWLRQ
$P(6ILCM6M6
6DPSOH SUHSDUDWLRQ SURFHGXUH LV VXLWDEOH IRU EHUULHV IUXLWV DQG YHJHWDEOHV FRQWDLQLQJ
OHVVWKHQRIIDWDQGPRUHWKDQRIZDWHUZDWHUFDQEHDGGHGLILWVFRQWHQWLV
LQVXIFLHQW$OO LQ DOO UHVLGXHV RI SRODU SHVWLFLGHV DUH DQDO\VHG LQ WKLV DQDO\WLFDO
SURFHGXUHIQWKLVH[DPSOHRQO\WZRRIWKHPZLOOEHGLVFXVVHGLQGHWDLOLPD]DOLODQG
WKLDEHQGD]ROH
2. Principle
$Q DOLTXRW RI KRPRJHQL]HG VDPSOH LV H[WUDFWHG ZLWK DFHWRQH DQG OWHUHG$ SRUWLRQ
RI WKH H[WUDFW LV VXEMHFWHG WR OLTXLGOLTXLG FOHDQXS VWHS FRQVLVWLQJ RI RQH H[WUDFWLRQ
ZLWK SHWUROHXP HWKHU CGLFKORURPHWKDQH PL[WXUH DQG WZR H[WUDFWLRQV ZLWK
GLFKORURPHWKDQHIURPVDWXUDWHG1DCOVROXWLRQ2UJDQLFH[WUDFWVDUHGULHGXVLQJDQK\GURXV
VRGLXPVXOSKDWHTKHQWKHVROYHQWLVH[FKDQJHGWRPHWKDQROWKURXJKHYDSRUDWLRQDQG
GLVVROYLQJTKHREWDLQHGH[WUDFWLVDQDO\VHGXVLQJLCM6
IQWKHLCM6V\VWHPWKHVDPSOHVDUHVHSDUDWHGFKURPDWRJUDSKLFDOO\XVLQJDFHWRQWULOH
%DQGEXIIHUVROXWLRQPMDPPRQLXPDFHWDWHIRUPLFDFLG$DVHOXHQW
TKHJUDGLHQWSURJUDPPHZDVDVIROORZV%!PLQ%PLQDW
PL PLQ$QDO\VHG VXEVWDQFHV ZHUH WKHQ LRQLVHG WKURXJK WKH (6I SURFHGXUH DQG
DQDO\VHGZLWKWKHLRQWUDSM6XVLQJIUDJPHQWDWLRQRITXDVLPROHFXODULRQV>M+@
CDOLEUDWLRQJUDSKVDUHFRPSLOHGXVLQJSHDNDUHDVRIFHUWDLQFKDUDFWHULVWLFIUDJPHQWLRQV
RQGLIIHUHQWFRQFHQWUDWLRQV
TKHUHVXOWLVFDOFXODWHGLQPJRISHVWLFLGHUHVLGXHSHUNJRIVDPSOHRUSSP
129
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 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
130
3. Interferences
(6I SURFHGXUH LV GHSHQGHQW RQ LRQL]DWLRQ HIFLHQFLHV RI WKH VSHFLHV TKH LRQLVDWLRQ
HIFLHQFLHV FDQ EH DIIHFWHG E\ FRHOXWLQJ SRODU PDWUL[ FRPSRQHQWV TKXV VDPSOH
SUHSDUDWLRQDQGLQPRVWSDUWFKURPDWRJUDSKLFVHSDUDWLRQVKRXOGEHDEOHWRFRSHZLWK
WKHVHFLUFXPVWDQFHV)RUWKLVUHDVRQUHWHQWLRQWLPHVVKRXOGEHUHDVRQDEO\ODUJHFRPSDUHG
WRWKHGHDGYROXPHRIWKHFROXPQIQDGGLWLRQVXLWDEOHEXIIHUVROXWLRQVKRXOGEHXVHG
TKH EHVW ZD\V WR FRUUHFW WKHVH HIIHFWV DUH XVLQJ PDWUL[ PDWFKHGFDOLEUDWLRQ VWDQGDUG
DGGLWLRQ RU ODEHOOHG LQWHUQDO VWDQGDUGV +RZHYHU WKHVH PHDQV ZLOO PDNH WKH DQDO\VLV
SURFHGXUHVLJQLFDQWO\PRUHFRPSOH[DQGDUHQRWXVHGLQWKHFXUUHQWSURFHGXUH
4. Reagents
1000 mg kg-1 individual pesticide standard solutions
PUHSDUHSHVWLFLGHVWDQGDUGVROXWLRQVE\GLVVROYLQJPJRIVXEVWDQFHLQJRIDFHWRQH
PJNJLQPLYLDOV
20 mg kg-1 combined pesticide standard solution
:HLJKJRIHDFKLQGLYLGXDOSHVWLFLGHVWDQGDUGVROXWLRQLQWRPLYLDODQGOOLWXS
ZLWKPHWKDQROJLQWKHFDVHRIWZRFRPSRQHQWV
Calibration solutions
8VLQJWKHPJNJVWDQGDUGVROXWLRQDQGRWKHUGLOXWLRQVWKHFDOLEUDWLRQVROXWLRQVFDQ
EHSUHSDUHGLQPHWKDQRO6XLWDEOHQXPEHURIVROXWLRQVVKRXOGEHSUHSDUHGLQWKHUDQJHRI
PJNJ
Solvents/eluent:
*UDGLHQWJUDGHPHWKDQROXOWUDSXUHZDWHUDPPRQLXPDFHWDWHDQGIRUPLFDFLGVXLWDEOH
IRULCM6EXIIHUSHWUROHWKHUGLFKORURPHWKDQHDQGDFHWRQHIRUUHVLGXHDQDO\VLVRU
*C+PLCJUDGHLIVXLWDELOLW\FKHFNHG
Other:
1DCO1D62SXUHIRUSHVWLFLGHDQDO\VLVHJKHDWHGEHIRUHXVH
131
6. Calculation
TKHUHVLGXHFRQWHQWwLQWKHVDPSOHLVIRXQGDFFRUGLQJWRWKHIROORZLQJHTXDWLRQ
wFLVIRXQGIURPWKHFDOLEUDWLRQJUDSK
w=
w
wF
V
Ve
V
m
wc V10 Ve
V50 m
PDVV IUDFWLRQ RI H[WUDFWDEOH SHVWLFLGH LQ VDPSOH PJ RI SHVWLFLGH SHU NJ RI
VDPSOH>PJNJ@
PDVVIUDFWLRQRIH[WUDFWDEOHSHVWLFLGHLQDQDO\VHGH[WUDFW>PJNJ@
WKHYROXPHRIQDOH[WUDFWLQPHWKDQRO>PL@
GHQVLW\RIPHWKDQROH[WUDFW>JPL@
WKeIXOOYROXPeRIDFeWRQee[WUDFW>PL@
WKeYROXPeRIDFeWRQee[WUDFWWREeSXULeG>PL@
PDVVRIKRPRJeQLVeGVDPSOeWREee[WUDFWeG>J@
7. Results
CDOFXODWLRQV DUe SeUIRUPeG XVLQJ FDOLEUDWLRQ JUDSK DQG WKe PRGeO eTXDWLRQ JLYeQ
DERYe 2EWDLQeG UeVXOWV DUe FRPSDUeG DJDLQVW MRLV VeW E\ (8 CRXQFLO PJ NJ
IRUERWKSeVWLFLGeVTKeVDPSOeVDWRURYeUMRLPXVWEeUeDQDO\VeGDQGRURWKeUZLVe
FRQUPeG
132
133
134
Relative intensity
(% of base peak)
EI-GC-MS
(relative)
>50 %
10 %
20 %
>2050 %
15 %
25 %
>1020 %
20 %
30 %
10 %
50 %
50 %
wexp
wtheor
100 %
STDEV =
n x 2
AVERAGE =
( x)
n(n 1)
n
STDEV
RSD =
100 %
AVERAGE
e[SeULPeQWDOO\PeDVXUeGPDVVIUDFWLRQRIWKeSeVWLFLGeUeVLGXeLQWKe
VDPSOeLQWKeUeFRYeU\VWXGLeVWKeSeVWLFLGeLVVSLNeGLQWRWKeVDPSOe
KRPRJeQDWe>PJNJ@
WKeRUeWLFDOO\ FDOFXODWeG PDVV IUDFWLRQ RI WKe SeVWLFLGe UeVLGXeV LQ WKe
VSLNeGVDPSOe>PJNJ@
WKeQXPEeURIGDWDSRLQWVLQWKeVeW
STDEV
VWDQGDUGGeYLDWLRQ>@
AVERAGE
DYeUDJeYDOXeRIWKeGDWDVeW>@
RSD
UeODWLYeVWDQGDUGGeYLDWLRQ>@
we[S
wWKeRU
135
Measurement data
Imazalil
Thiabendazole
wexp
(mg kg-1)
wtheor
(mg kg-1)
0.06427
R
(%)
R
(%)
Imazalil
Thiabendazole
Peak area
Peak area
wexp
(mg kg-1)
wtheor
(mg kg-1)
0.05597
0.03120
0.04244
3 996 669
300 802
0.07516
0.05871
0.03281
0.04452
3 459 066
281 164
0.04812
0.05821
0.03181
0.04413
3 838 651
230 775
0.10238
0.07342
0.04095
0.05567
3 727 188
274 366
0.04201
0.06088
0.03400
0.04616
3 414 893
296 724
0.05741
0.06241
0.03331
0.04732
3 553 740
258 916
AVERAGE recovery
AVERAGE recovery
STDEV of recovery
STDEV of recovery
* The recovery determinations were carried out two per day on three consecutive days.
136
urnd =
2
2
+ urel_meth
urel_rec
100 %
d = w wref
uref =
udev =
s
n1
d2
n
2
2
usys = uref
+ udev
uZ
VWDQGDUGXQFeUWDLQW\RIPDVVIUDFWLRQRISeVWLFLGe>PJNJ@
uV\V
V\VWePDWLFFRPSRQeQWRIXQFeUWDLQW\>PJNJ@
uUQG
UDQGRPFRPSRQeQWRIXQFeUWDLQW\>PJNJ@
uUeOBUeF
UeODWLYeXQFeUWDLQW\RIUeFRYeU\>@
uUeOBPeWK
UeODWLYeXQFeUWDLQW\RIDQDO\VLVPeWKRG>@
SeVWLFLGePDVVIUDFWLRQLQVWDQGDUGVDPSOeDVREWDLQeGZLWKWKePeDVXUePeQW
SURFeGXUe>PJNJ@
GLIIeUeQFe LQ PDVV IUDFWLRQ EeWZeeQ RXU ODERUDWRU\ DQG UeIeUeQFe YDOXe
ODERUDWRU\ELDV>PJNJ@
UeIeUeQFePDVVIUDFWLRQRISeVWLFLGeLQWKeUeIeUeQFeVDPSOe>PJNJ@
d
wUeI
s
nO
n
uGeY
uUeI
WKeVWDQGDUGGeYLDWLRQRIWKeUeVXOWVRIWKeSDUWLFLSDQWVRIWKeLQWeUODERUDWRU\
FRPSDULVRQ>PJNJ@
WKe QXPEeU RI ODERUDWRULeV ZKR WRRN SDUW LQ LQWeUODERUDWRU\ FRPSDULVRQ
ILC
QXPEeURIFRPSOeWeGILCV
XQFeUWDLQW\PDQLIeVWeGE\WKeGeYLDWLRQRIWKeODERUDWRU\VUeVXOWIURPWKe
UeIeUeQFeYDOXe>PJNJ@
XQFeUWDLQW\RIWKeUeIeUeQFeYDOXe>PJNJ@
137
Measurement data
138
Imazalil
Thiabendazole
urel_rec
27 %
2%
urel_meth
10 %
6%
1.3350 mg kg-1
3.5230 mg kg-1
wref
1.2975 mg kg-1
3.2863 mg kg-1
0.0530 mg kg-1
0.5571 mg kg-1
nl
Comments
The relative standard deviation of recovery
calculated from parallel measurement results (two
measurements per day on three consecutive days)
The relative standard deviation of results obtained
for the same solution from repeated injections of
the same solution
TrainMiC Exercises
Analytical procedure
Determination of concentration of imazalil and thiabendazole
in tangerines by liquid chromatography-mass spectrometry.
The quality of the results should comply with the requirements
in pesticide residues analysis directives and guidelines
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
139
Measurand
Units
mg kg-1 (ppm)
Measurement
procedure
Type of calibration
standard curve
Standard addition
internal standard
Model equation
w=
w
wF
V
140
wc V10 Ve
V50 m
PDVVIUDFWLRQRIe[WUDFWDEOeSeVWLFLGeLQVDPSOePJRISeVWLFLGeSeUNJRI
VDPSOe>PJNJ@
PDVVIUDFWLRQRIe[WUDFWDEOeSeVWLFLGeLQDQDO\VeGe[WUDFW>PJNJ@IRXQGIURP
WKeFDOLEUDWLRQFXUYe
WKeYROXPeRIQDOe[WUDFWLQPeWKDQRO>PL@
GeQVLW\RIPeWKDQRO>JPL@
Ve
WKeIXOOYROXPeRIDFeWRQee[WUDFW>PL@
V
WKeYROXPeRIDFeWRQee[WUDFWWREeSXULeG>PL@
PDVVRIKRPRJeQLVeGVDPSOeWREee[WUDFWeG>J@
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
4. List the reference standards needed and state the information regarding
traceability of the reference value
For the analyte
1
Name/ChemicalFormula/
Producer:
Name/ChemicalFormula/
Producer:
None
Yes
No
141
142
Tangerines
Measuring range
Measurement
uncertainty
Identity/confirmation: retention time (compared with
standard) + MS^2 fragmentation: imazalil (297 201),
thiabendazole (202 175) + additional qualifier ion
comparison if necessary. Guidance document refers to
sufficient confirmation when MS^2 is used and ion ratios in
standard and sample agree within the limits specified in
Table 3 (Yellow sheet, Part II).
Other - state
143
144
Full
Partial
Confirmation/Verification
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
At approximate concentration level of 0.05 mg kg-1
Compare with a reference method
Selectivity, interferences
Chromatographic separation and mass-spectrometric identification (including MS^2 confirmation of
identity)
Test with different matrices
The method has been proved via ILC to perform with tangerine, orange and tomato
Other please specify
Confirmation of identity: chromatographic retention time and MS^2 confirmation of identity
6. Measuring range
Linearity
Imazalil: 0.0040.9 mg kg-1; Thiabendazole: 0.0030.7 mg kg-1
Upper limit
Imazalil: 0.9 mg kg-1; Thiabendazole: 0.7 mg kg-1
LOD
Imazalil: 0.004 mg kg-1; Thiabendazole: 0.003 mg kg-1
LOQ
7. Spread precision
Repeatability
Instrumental: standard deviation of the measurement method: 10 % for imazalil and 6 % for
thiabendazole (repeated injection of the same standard solution).
Reproducibility (within Lab)
Full procedure: standard deviation of recovery experiments carried out on three consecutive days
27 % for imazalil, 2 % for thiabendazole (full sample preparation included )
Reproducibility (between Lab)
in ILC the difference between results were 5.6 and 4.4 % for imazalil and thiabendazole respectively
145
8. Robustness
Variation of parameters
Variation of some of the parameters: during method development two different columns were used
(C182504.6 5, C18150150 2.1), mobile phase composition and velocity were changed in
increments and obtained data analysedd, final extract volumes of 10 and 20 mL were utilized.
9. Quality control
Control charts
Participation in PT schemes
146
LOD
Calculations
Since the method permits in principle to obtain significantly lower LOD values
than requested by the customer, LOD was estimated in a conservative way by
taking the lowest points on the respective calibration graphs as LOD estimates.
Values obtained:
Imazalil: 0.004 mg kg-1
Thiabendazole: 0.003 mg kg-1
LOQ
Repeatability
Within-lab
reproducibility
Average recovery; for data and equations see first document
Imazalil 104 %
Thiabendazole 73 %
R=
Trueness
wexp
wtheor
100 %
Measurement
uncertainty
Other - please
state
147
12. Does the analytical procedure fulfil the requirement(s) for the intended use?
Parameter
LOD
Value obtained
during validation
The requirement
is fulfilled
Yes/No
0.004 mg kg-1
0.003 mg kg-1
Yes
Yes
70110 %
Imazalil 104 %
Thiabendazole 73 %
Yes
Yes
MS^2 spectrum in
sample is similar to
standard
Yes
LOQ
Repeatability
Within-lab
reproducibility
Trueness
Measurement
Other
No
148
Unit
mg kg-1
Model equation
w=
wc V10 Ve
V50 m
PDVVIUDFWLRQRISeVWLFLGeLQVDPSOe>PJNJ@
wF
PDVVIUDFWLRQRISeVWLFLGeLQDQDO\VeGe[WUDFW>PJNJ@
V
WKeYROXPeRIQDOe[WUDFWLQPeWKDQRO>PL@
Ve
GeQVLW\RIPeWKDQRO>JPL@
V
WKeYROXPeRIDFeWRQee[WUDFWWREeSXULeG>PL@
PDVVRIKRPRJeQLVeGVDPSOeWREee[WUDFWeG>J@
WKeIXOOYROXPeRIDFeWRQee[WUDFW>PL@
149
8QFeUWDLQW\ eVWLPDWLRQ LV FDUULeG RXW XVLQJ WKe 1RUGWeVW PeWKRG IQ SULQFLSOe WKe
1RUGWeVW DSSURDFK FDQ Ee UeJDUGeG DV D VSeFLDO FDVe RI WKe I62 PeWKRG ZKeUe YeU\
JeQeUDOXQFeUWDLQW\VRXUFeVDUeFRQVLGeUeG
TKePDLQeTXDWLRQ
uw = usys 2 + urnd 2
uZ
VWDQGDUGXQFeUWDLQW\RIPDVVIUDFWLRQRISeVWLFLGe>PJNJ@
uV\V
V\VWePDWLFFRPSRQeQWRIXQFeUWDLQW\>PJNJ@
uUQG
UDQGRPFRPSRQeQWRIXQFeUWDLQW\>PJNJ@
TKeWZRPDLQXQFeUWDLQW\VRXUFeVDUe
8QFeUWDLQW\uV\VZKLFKLVGXeWRWKeV\VWePDWLFeIIeFWVODERUDWRU\ELDVDQGPeWKRG
ELDVIQWKeRULJLQDOGRFXPeQWLWLVGeQRWeGDOVRDVubiasTKLVFRPSRQeQWLVIRXQGIURP
DQDO\VLVRICRMVRUIURPSDUWLFLSDWLQJLQILCV
8QFeUWDLQW\uUQGZKLFKLVGXeWRWKeUDQGRPeIIeFWVZLWKLQODERUDWRU\EeWZeeQGD\
UeSURGXFLELOLW\IQWKeRULJLQDOGRFXPeQWLWLVGeQRWeGDOVRDVuRZTKLVFRPSRQeQWLV
IRXQGIURPURXWLQeEeWZeeQGD\UeSURGXFLELOLW\PRQLWRULQJRIWKePeWKRGXVLQJeJD
FRQWUROFKDUW
TKeFRPSRQeQWuV\VLQWXUQLVIRXQGDFFRUGLQJWRWKeIROORZLQJIRUPXOD
uw = udev 2 + uref 2
ZKeUe uGeY GeQRWeV XQFeUWDLQW\ PDQLIeVWeG E\ WKe GeYLDWLRQ RI WKe ODERUDWRU\V UeVXOW
IURPWKeUeIeUeQFeYDOXeGeQRWeGE\RMSELDVLQWKeRULJLQDOGRFXPeQWDQGuUeIGeQRWeV
WKeXQFeUWDLQW\RIWKeUeIeUeQFeYDOXeGeQRWeGDVuFUeILQWKeRULJLQDOGRFXPeQW
TKeTXDQWLFDWLRQRIWKeXQFeUWDLQW\FRPSRQeQWVLVFDUULeGRXWDFFRUGLQJWRWKeIROORZLQJ
IRUPXODe
150
urnd =
2
2
urel_rec
+ urel_meth
100 %
d = w wref
uref =
udev =
s
n1
d2
n
uUeOBUeF
UeODWLYeXQFeUWDLQW\RIUeFRYeU\>@
uUeOBPeWK
UeODWLYeXQFeUWDLQW\RIDQDO\VLVPeWKRG>@
SeVWLFLGe PDVV IUDFWLRQ LQ D UeIeUeQFe VDPSOe DV GeWeUPLQeG E\ WKe
PeDVXUePeQWSURFeGXUe>PJNJ@
UeIeUeQFePDVVIUDFWLRQRISeVWLFLGeLQWKeUeIeUeQFeVDPSOe>PJNJ@
wUeI
GLIIeUeQFe LQ PDVV IUDFWLRQ EeWZeeQ RXU ODERUDWRU\ DQG UeIeUeQFe YDOXe
>PJNJ@
WKeVWDQGDUGGeYLDWLRQIRUUeIeUeQFeYDOXe>PJNJ@
nO
WKeQXPEeURIODERUDWRULeVZKRWRRNSDUWLQILC
n
uGeY
QXPEeURIFRPSOeWeGILCVn LQRXUFDVe
XQFeUWDLQW\PDQLIeVWeGE\WKeGeYLDWLRQRIWKeODERUDWRU\VUeVXOWIURPWKe
UeIeUeQFeYDOXe>PJNJ@
XQFeUWDLQW\RIWKeUeIeUeQFeYDOXe>PJNJ@
uUeI
151
Value
Imazalil
Thiabendazole
wc
2.801
V10
Unit
Remark
7.398
mg kg-1
10
10
mL
0.791
0.791
g mL-1
Density of methanol
Ve
150
150
mL
V50
50
50
mL
49.8003
49.8003
Unit
Imazalil
Thiabendazole
uref
0.0375
0.3216
mg kg-1
udev
0.0375
0.2367
mg kg-1
urel_rec
27
urel_meth
10
Remark
systematic uncertainty component evaluated based
on the results of ILC
random component of uncertainty, calculated using
relative uncertainty (repeatability) of recovery and
method
relative standard deviation of recoveries calculated
using addition experiments
relative standard deviation of measuring method
(repeated analysis of the same solution)
w=
w
wF
V
Ve
V
m
wc V10 Ve
V50 m
PDVVIUDFWLRQRISeVWLFLGeLQVDPSOe>PJNJ@
PDVVIUDFWLRQRISeVWLFLGeLQDQDO\VeGe[WUDFW>PJNJ@
WKeYROXPeRIQDOe[WUDFWLQPeWKDQRO>PL@
GeQVLW\RIPeWKDQRO>JPL@
WKeIXOOYROXPeRIDFeWRQee[WUDFW>PL@
WKeYROXPeRIDFeWRQee[WUDFWWREeSXULeG>PL@
PDVVRIKRPRJeQLVeGVDPSOeWREee[WUDFWeG>J@
TKe1RUGWeVWPeWKRGGReVQRWUeTXLUeVeSDUDWeXQFeUWDLQW\eYDOXDWLRQIRUeDFKLQSXW
TXDQWLW\
152
w(imazalil) =
w( thiabendazole) =
7. Calculate the combined standard uncertainty (uw ) of the result and specify units
MDWKePDWLFDOVROXWLRQ
Using:
Uncertainty
components
Value
6SUeDGVKeeWDSSURDFK
Standard
uncertainty
Unit
usys (imazalil)
0.0530
mg kg-1
urnd (imazalil)
0.3844
mg kg-1
usys (thiabendazole)
0.3993
mg kg-1
urnd(thiabendazole)
0.2228
mg kg-1
CRPPeUFLDOVRIWZDUe
Remark
systematic uncertainty component
evaluated based on the results of ILC
random component of uncertainty,
calculated using relative uncertainty
(repeatability) of recovery and method
systematic uncertainty component
evaluated based on the results of ILC
random component of uncertainty,
calculated using relative uncertainty
(repeatability) of recovery and method
8QFeUWDLQW\LVIRXQGDFFRUGLQJWRWKeWKe1RUGWeVWDSSURDFKXVLQJWKeIROORZLQJ
VeWRIeTXDWLRQV
uZ
2
2
uw = usys
+ urnd
urnd =
2
2
urel_rec
+ urel_meth
100 %
d = w wref
uref =
udev =
s
n1
d2
n
2
2
usys = uref
+ udev
uV\V
uUQG
uUeOBUeF
uUeOBPeWK
w
d
wUeI
s
nO
n
VWDQGDUGXQFeUWDLQW\RIPDVVIUDFWLRQRI
SeVWLFLGe>PJNJ@
V\VWePDWLFFRPSRQeQWRIXQFeUWDLQW\>PJ
NJ@
UDQGRPFRPSRQeQWRIXQFeUWDLQW\>PJNJ@
UeODWLYeXQFeUWDLQW\RIUeFRYeU\>@
UeODWLYeXQFeUWDLQW\RIDQDO\VLVPeWKRG>@
SeVWLFLGePDVVIUDFWLRQLQVDPSOe>PJNJ@
GLIIeUeQFeLQPDVVIUDFWLRQEeWZeeQRXU
ODERUDWRU\DQGUeIeUeQFeYDOXe>PJNJ@
UeIeUeQFePDVVIUDFWLRQRISeVWLFLGeLQ
VDPSOe>PJNJ@
WKeVWDQGDUGGeYLDWLRQIRUUeIeUeQFeYDOXe
>PJNJ@
WKeQXPEeURIODERUDWRULeVZKRWRRNSDUWLQ
ILC
QXPEeURIFRPSOeWeGILCV
153
uGeY
uUeI
XQFeUWDLQW\PDQLIeVWeGE\WKeGeYLDWLRQRI
WKeODERUDWRU\VUeVXOWIURPWKeUeIeUeQFe
YDOXe>PJNJ@
XQFeUWDLQW\RIWKeUeIeUeQFeYDOXe>PJNJ@
8. Calculate expanded uncertainty (Uw ) and specify the coverage factor k and the units
Imazalil
uw = 0.053032 + 0.38442 = 0.388 mg kg -1
urnd =
27 % 2 + 10 % 2
1.3350 = 0.3844 mg kg -1
100 %
d = 1.3350 1.2975 = 0.0375 mg kg -1
0.0530
uref =
= 0.0375 mg kg -1
2
udev =
0.03752
= 0.0375 mg kg -1
1
Thiabendazole
2 %2 + 6 %2
3.860 = 0.2228 mg kg -1
100 %
d = 3.5230 3.2863 = 0.2367 mg kg -1
0.5571
uref =
= 0.3216 mg kg -1
2
udev =
0.2367 2
= 0.2367 mg kg -1
1
154
9. Analyse the uncertainty contribution and specify the main three input quantities
contributing the most to uw
1
155
Further readings
156
Chapter 5
158
Measurand
Example number
Ex-07
Bertil Magnusson
Analytical procedure
Customer requirement
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
3 - Green
2 - Yellow
1-I
Ex-07-2-YNH4-waterPhotometry2006-Ver1.doc
Ex-07-3-GNH4-waterPhotometry2006-Ver1.doc
File is
attached
Yes No
PART I
PART II
PART III
PART IV
PART I
PART II
Addendum 1: By spreadsheet
approach
PART III
Remark
Given by the
lecturer
Each participant
receives own
copy and may
keep it
0
1
April 2007
159
3KRWRPHWULFGHWHUPLQDWLRQRI
DPPRQLXPLQGULQNLQJZDWHU
6FRSHRIWKHSUHVHQWDWLRQ
7KHDQDO\WLFDOSURFHGXUHDQGWKHFXVWRPHUVUHTXLUHPHQWV
$ERXWWKHFKHPLVWU\ DQGWKHPHDVXUHPHQWPHWKRG
0RGHOHTXDWLRQ
7KHDQDO\WLFDOSURFHGXUHDQGWKH
FXVWRPHUVUHTXLUHPHQWV
:DWHUTXDOLW\ 'HWHUPLQDWLRQRIDPPRQLXPQLWURJHQ
0HWKRGE\IORZDQDO\VLV&)$DQG),$DQG
VSHFWURPHWULFGHWHFWLRQ
,62
7KHTXDOLW\RIWKHUHVXOWVVKRXOGFRPSO\ZLWKWKH
UHTXLUHPHQWLQWKHGLUHFWLYH(&RQWKHTXDOLW\RI
ZDWHULQWHQGHGIRUKXPDQFRQVXPSWLRQLQSUHSDUDWLRQ
160
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
0HDVXUHPHQWSURFHGXUH
$PPRQLXPSUHVHQWLQWKHVDPSOHUHDFWVLQDONDOLQH
VROXWLRQZLWKK\SRFKORULWHWRIRUPFKORUDPLQHV
7KHFKORUDPLQHVIRUPHGUHDFWVXQGHUFDWDO\VLVRI
QLWURSUXVVLGH ZLWKVDOLF\ODWH DWDWHPSHUDWXUHRI&
WRIRUPDEOXHJUHHQ LQGRSKHQROG\H
7KHDEVRUEDQFHRIWKHQLWURSUXVVLGH LVTXDQWLWDWLYHO\
PHDVXUHGLQDIORZSKRWRPHWHUDWQPE\
FRPSDULQJZLWKDFDOLEUDWLRQFXUYH
,QVWUXPHQWDOVHWXS
5HDFWLRQFRLO
6DPSOH
5HDJHQW
5HDJHQW
89
GHWHFWRU
5HDJHQW
161
0RGHO(TXDWLRQ
& >$VDPSOH E E@ IGLO 5
4XDQWLW\
&
162
8QLW
PJ/ 1
'HILQLWLRQ
&RQFHQWUDWLRQRI1+ LQWKHVDPSOHVROXWLRQ
$VDPSOH
$8
$EVRUEDQFHRIWKHVDPSOHVROXWLRQ
E
$8
E
$8/PJ
1 6ORSHRIFDOLEUDWLRQOLQH
IGLO
XQLWOHVV
'LOXWLRQ IDFWRU
XQLWOHVV
5HFRYHU\IDFWRURIWKHDQDO\VLV
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
N u XF 1+
163
Analytical procedure
Determination of concentration of ammonium in drinking water
by flow analysis (CFA and FIA) and spectrometric detection.
The quality of the results should comply with the requirements
in the Directive 98/83/EC on the quality intended for human
consumption
164
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
1. Scope
TKLVIQWeUQDWLRQDO6WDQGDUGVSeFLeVPeWKRGVVXLWDEOeIRUWKeGeWeUPLQDWLRQRIDPPRQLXP
QLWURJeQLQYDULRXVW\SeVRIZDWeUVJURXQGGULQNLQJVXUIDFeDQGZDVWeZDWeUVLQPDVV
FRQFeQWUDWLRQUDQJLQJIURPWRPJLLQWKeXQGLOXWeGVDPSOeDSSO\LQJeLWKeU)I$
CODXVeRUC)$CODXVe+eUeWKeC)$LVSUeVeQWeG
IQ D FRQWLQXRXVO\ RZLQJ JDVVeJPeQWeG FDUULeU VWUeDP DPPRQLXP SUeVeQW LQ WKe
VDPSOeUeDFWVLQDONDOLQeVROXWLRQZLWKK\SRFKORULWeZKLFKKDVSUeYLRXVO\EeeQOLEeUDWeG
IURPGLFKORURLVRF\XDQXUDWe
TKe FKORUDPLQeV IRUPeG UeDFWV XQGeU FDWDO\VLV RI QLWURSUXVVLGe ZLWK VDOLF\ODWe DW D
WePSeUDWXUeRICWRIRUPDEOXeJUeeQLQGRSKeQROG\eZKLFKLVTXDQWLWDWLYeO\
PeDVXUeGLQDRZSKRWRPeWeUDWQP
165
Calibration solutions
PUeSDUe FDOLEUDWLRQ VROXWLRQV E\ GLOXWLQJ WKe DPPRQLXP VWDQGDUG VROXWLRQV $W OeDVW
YeFDOLEUDWLRQVWDQGDUGVSeUZRUNLQJUDQJeDUeUeFRPPeQGeG$VDQe[DPSOeLIVL[
VWDQGDUGDUeDSSOLeGSURFeeGIRUWKeZRUNLQJUDQJeVPJL1DVIROORZV
166
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
6. Procedure
Instrument set-up
PULRUWRPeDVXUePeQWFRQWLQXRXVO\UXQWKeUeDJeQWVROXWLRQVIRUDSSUR[LPDWeO\PLQ
WKURXJKWKeV\VWePDQGUeFRUGWKeEDVeOLQeTKeV\VWePLVRSeUDWLRQDOZKeQWKeEDVeOLQe
GReVQRWVKRZDQ\GULIW$VDWLVIDFWRU\VLJQDOWRQRLVeUeODWLRQVKRXOGEeREWDLQeG
PeUIRUP WKe FDOLEUDWLRQ ZLWK WKe EODQN VROXWLRQV DQG WR eTXLGLVWDQW FDOLEUDWLRQ
VROXWLRQVIRUDQDSSURSULDWeFRQFeQWUDWLRQUDQJeIWVKRXOGEeVWUeVVeGWKDWWKeOLQeDULW\
RIWKeFDOLEUDWLRQFXUYeLVRIWeQOLPLWeGCRUUeFWWKeDEVRUEDQFeYDOXeVRIWKeFDOLEUDWLRQ
VROXWLRQV E\ VXEWUDFWLQJ WKe DEVRUEDQFe YDOXe RI WKe EODQN FDOLEUDWLRQ VROXWLRQ )RU
SORWWLQJ RI D FDOLEUDWLRQ FXUYe RU IRU FDOFXODWLRQ RI WKe FDOLEUDWLRQ IXQFWLRQ XVe WKe
UeVXOWLQJYDOXeVWRJeWKeUZLWKWKeDQDO\WeFRQFeQWUDWLRQVRIWKeFDOLEUDWLRQVROXWLRQV
$QDO\VeWKeWeVWVDPSOeVLQWKeVDPeZD\DVWKeFDOLEUDWLRQVROXWLRQVZLWKWKeFRQWLQXRXV
RZV\VWeP
7. Method of calculation
ReDGWKeYDOXeVRIWKeDQDO\WeFRQFeQWUDWLRQVRIWKeWeVWVDPSOeVROXWLRQVWKeUeDJeQWEODQN
VROXWLRQDQGWKeEODQNWeVWVROXWLRQIURPWKeFDOLEUDWLRQJUDSKRUFDOFXODWeWKePIURPWKe
FDOLEUDWLRQIXQFWLRQCRUUeFWWKeDQDO\WeFRQFeQWUDWLRQVRIWKeWeVWVDPSOeVROXWLRQVE\
VXEWUDFWLQJWKeDQDO\WeFRQFeQWUDWLRQVRIWKeUeDJeQWEODQNVROXWLRQVRUWKeEODQNWeVWVROXWLRQ
CRUUeFWIRUGLOXWLRQVWeSVLIDSSURSULDWeReSRUWUeVXOWVDPPRQLDe[SUeVVeGDVQLWURJeQ
LQPJL
167
Ammonium
10 %
Precision of
parametric value
(Note 2)
10 %
Limit of detection of
parametric value
(Note 3)
10 %
Note 1
TUXeQeVV LV WKe V\VWePDWLF eUURU DQG LV WKe GLIIeUeQFe EeWZeeQ WKe PeDQ
YDOXeRIWKeODUJeQXPEeURIUeSeDWeGPeDVXUePeQWVDQGWKeWUXeYDOXe
Note 2
PUeFLVLRQ LV WKe UDQGRP eUURU DQG LV XVXDOO\ e[SUeVVeG DV WKe VWDQGDUG
GeYLDWLRQ ZLWKLQ DQG EeWZeeQ EDWFK RI WKe VSUeDG RI UeVXOWV DERXW WKe
PeDQ$FFeSWDEOeSUeFLVLRQLVWZLFeWKeUeODWLYeVWDQGDUGGeYLDWLRQ
TKeVeWeUPVDUeIXUWKeUGeQeGLQI62
Note 3:
168
LLPLWRIGeWeFWLRQLVeLWKeU
WKUee WLPeV WKe UeODWLYe ZLWKLQ EDWFK VWDQGDUG GeYLDWLRQ RI D QDWXUDO
VDPSOeFRQWDLQLQJDORZFRQFeQWUDWLRQRIWKeSDUDPeWeURU
Ye WLPeV WKe UeODWLYe ZLWKLQ EDWFK VWDQGDUG GeYLDWLRQ RI D EODQN
VDPSOe
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
Measurement data
$V\QWKeWLFFRQWUROVDPSOeDWDOeYeORIPJLKDVEeeQUXQIRURYeUDSeULRGRI
PRQWKVTKeUeVXOWVLQPJLDUeJLYeQLQWKeWDEOeEeORZ
Measurement data
ReVXOWVIURPWZRFRQWUROVDPSOeVDUeJLYeQLQWKeWDEOeEeORZ
Unit
QC1
QC2
Mean value
mg L-1
0.114
0.605
mg L-1
0.005
0.021
27
28
Time period
months
Nominal value
mg L-1
0.100
0.600
169
170
Year/Exercise
Nominal value
xref
[Mg l-1]
laboratory result xi
[mg L-1]
Bias
[%]
sR
[%]
Number of
labs
1999/1
81
83
2.4
10
31
1999/2
73
75
2.7
36
2000/1
264
269
1.9
32
2000/2
210
213
1.4
10
35
2001/1
110
112
1.8
36
2001/2
140
144
2.9
11
34
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
171
172
unitless
unitless
Recovery factor of
the analysis
0.9900
0.9902
AU L
mg-1
Dilution factor
0.0143
0.2560
0.2465
Value
AU
AU
mg L-1
Unit
fdil
b1
b0
Asample
Concentration of
NH4+ in the sample
solution
Absorbance of the
sample solution
Intercept of
calibration line
Slope of calibration
line unit AU
divided by mg N L-1
Quantity
Measurement data
0.0058
0.00
0.0070
0.0021
0.0015
0.0031
Standard
uncertainty
(u)
0.59
0.00
0.71
14
0.58
1.3
Relative standard
uncertainty
(%)
Type of
uncertainty
normal
rectangular
Type of distribution
triangular
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
TrainMiC Exercises
Analytical procedure
Determination of concentration of ammonium in drinking
water by continuous flow analysis (CFA) and spectrometric
detection
The quality of the results should comply with the requirements
in the Directive 98/83/EC on the quality of water intended for
human consumption
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 solution
Addendum II: By dedicated software
173
Ammonium
Measurand
Units
mg L-1
ISO 11732:2005 using the continuous flow analysis and photometric detection
Type of calibration
standard curve
standard addition
internal standard
Model equation
C AVDPSOeEEfGLOR
C
AVDPSOe
CRQFeQWUDWLRQRI1+LQWKeVDPSOeVROXWLRQ>PJL@
$EVRUEDQFeRIWKeVDPSOeVROXWLRQ>$8@
b
IQWeUFeSWRIFDOLEUDWLRQOLQe>$8@
b
6ORSeRIFDOLEUDWLRQOLQe>$8GLYLGeGE\PJL@
fGLO
'LOXWLRQIDFWRU
ReFRYeU\IDFWRURIWKeDQDO\VLV
TKeFDOLEUDWLRQOLQeeYDOXDWeGE\OLQeDUUeJUeVVLRQLVEDVeGRQYeVWDQGDUGVLQWKeUDQJe
PJL
TKeGLOXWeVWDQGDUGVROXWLRQRIPJLLVSUeSDUeGIURPDVWRFNVROXWLRQRIPJ
LTKLVVWRFNVROXWLRQLVSUeSDUeGIURPDPPRQLXPFKORULGe
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.
174
Absorbance of the sample - here the main source is the drift contributing about 20%
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
4. List the reference standards needed and state the information regarding
traceability of the reference value
For the analyte
1
Name/ChemicalFormula/Producer:
Name/ChemicalFormula/Producer:
Quantity/Equipment/Calibration:
Quantity/Equipment/Calibration:
Quantity/Equipment/Calibration:
Yes
No
Participating in PT rounds
2
3
175
Analyte
Ammonium
The measurand
Unit
mg L-1
Drinking water
Measuring range
LOQ
Repeatability
Mark the customers
requirements and give
their values
Within-lab
reproducibility
Trueness
Measurement
uncertainty
Other-state
176
Full
Partial
Confirmation/Verification
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
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
Selectivity, interferences
6. Measuring range
Linearity
Upper limit
LOD
LOQ
7. Spread precision
Repeatability
Reproducibility (within lab)
Reproducibility (between lab)
8. Robustness
Variation of parameters
177
9. Quality control
Control charts
Participation in PT schemes
178
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
Calculations
s = 0.004 mg L-1
LOD
LOD = 5s = 0.02 mg L-1
LOQ
Repeatability
Within-lab reproducibilty
Trueness
Measurement uncertainty
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
12. Does the analytical procedure fulfil the requirement(s) for the intended use?
Value obtained
during validation
The requirement
is fulfilled
Yes/No
0.05 mg L-1
0.02 mg L-1
Yes
Within-lab
reproducibility
4%
Yes
Trueness
10 %
2-3 %
Yes
Parameter
LOD
LOQ
Repeatability
Measurement
uncertainty
Other
No
180
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
Unit
mg L-1
Model equation
C = AVDPSOe b b fGLO / R
C
AVDPSOe
FRQFeQWUDWLRQRI1+LQWKeVDPSOeVROXWLRQ>PJL@
DEVRUEDQFeRIWKeVDPSOeVROXWLRQ>$8@
b
LQWeUFeSWRIFDOLEUDWLRQOLQe>$8@
b
VORSeRIFDOLEUDWLRQOLQe>$8GLYLGeGE\PJL@
fGLO
GLOXWLRQIDFWRU
UeFRYeU\IDFWRURIWKeDQDO\VLV
181
Value
Unit
Asample
0.256
AU
b0
0.01734
AU
b1
986.3
AU L mg-1
fdil
unitless
0.99
unitless
Remark
Standard
uncertainty
Unit
Remark
Asample
1.49 10-3
AU
b0
0.00207
AU
b1
0.0070
AU L mg-1
fdil
unitless
0.0058
unitless
C=
182
0.256 0.01734
1 0.99 = 0.247 mg L-1
986.3
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
7. Calculate the combined standard uncertainty (uc) of the result and specify units
Using:
MDWKePDWLFDOVROXWLRQ
6SUeDGVKeeW$SSURDFK
Input
quantity
Value
Standard
uncertainty
Unit
Asample
0.256
1.49 10-3
AU
b0
0.01435
0.00207
AU
b1
0.9902
0.0070
AU L mg-1
fdil
Unitless
0.99
0.01
Unitless
CRPPeUFLDO6RIWZDUe
Remark
8. Calculate expanded uncertainty (Uc) and specify the coverage factor k and the
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
9. Analyse the uncertainty contribution and specify the main three input quantities
contributing the most to Uc
1
2
3
183
Further readings
(1VWDQGDUGI62
(CCRXQFLO'LUeFWLYe(CRI1RYePEeUTKeTXDOLW\RIZDWeULQWeQGeG
IRUKXPDQFRQVXPSWLRQOfc. J. Eur. Commun.L
% MDJQXVVRQ T 1l\NNL + +RYLQG DQG M .U\VeOO Handbook for Calculation of
Measurement Uncertainty in Environmental LaboratoriesQGeGI661
1RUGWeVWWeFKQLFDOUeSRUWKWWSZZZQRUGLFLQQRYDWLRQQeWQRUGWeVWOeUWeFSGI
184
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
Model equation:
{ The main equation }
C = (Asample - b0) / b1 fdil / R;
{ Nitrogen- Ammonium ion stock solution - 1000 mg N L-1. Prepared from ammonium
chloride.}
Cst_0 = mNH4Cl / V1000 PNH4Cl fNH4Clconv 1000;
{ Ammonium standard solution - 10 mg N/L. Prepared from ammonium stock solution.
The standard solution is further used for preparation of the calibration standard
solutions. }
Cst = Cst_0 V1 / V100;
{ Concentrations of calibration standard solutions 0.1 to 1 mg N L-1.
1 to 10 mL of the standard solution is transferred to 100 mL volumetric asks.
The reagents are added and the solution is made up to the mark. The solution is left to
stand for 60 min and then the absorbance at 655 nm is measured. }
C1 = Cst (V1_st / V1_100);
C2 = Cst (V2_st / V2_100);
C3 = Cst (V3_st / V3_100);
C4 = Cst (V4_st / V4_100);
C5 = Cst (V5_st / V5_100);
fdil = 1;
{in this case the sample was not diluted}
{ Photometric measurements
It is assumed that the uncertainty of all photometric measurements consists of three
components (on the example Asample):
Repeatability uncertainty (included in Asample_rep);
Uncertainty due to drift (Asample_drift)
Uncertainty due to rounding of the reading (Asample_round) (The photometer use din this
example has three decimal places)
The absorbance of blank is not subtracted but all the measurements are made against
blank}
{ Absorbance of sample solution }
Asample = Asample_rep+Asample_drift+Asample_round;
185
{ The regression equations for nding the slope (b1) and intercept (b0) of the calibration
line }
AC = C1 A1 + C2 A2 + C3 A3 +C4 A4 + C5 A5;
AvgC=(C1+C2+C3+C4+C5)/n;
AvgA=(A1+A2+A3+A4+A5)/n;
CC=C1 C1+C2 C2+C3 C3+C4 C4+C5 C5;
b1=(AC-n AvgC AvgA)/(CC-n AvgC AvgC);
b0=AvgA-b1 AvgC
List of quantities:
186
Quantity
Unit
Definition
mg N L-1
Asample
AU
b0
AU
b1
AU L mg-1
fdil
unitless
Dilution factor
unitless
Cst_0
mg N mL
mNH4Cl
Weight of NH4Cl
V1000
mL
PNH4Cl
unitless
Purity of NH4Cl
fNH4Clconv
unitless
Cst
mg N L-1
V1
mL
Volume of 1 mL pipette
V100
mL
C1
mg N L
V1_st
mL
V1_100
mL
C2
mg N L
V2_st
mL
V2_100
mL
C3
mg N L-1
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
Quantity
Unit
Definition
V3_st
mL
V3_100
mL
C4
mg N L
V4_st
mL
V4_100
mL
C5
mg N L-1
V5_st
mL
V5_100
mL
AC
A1
AU
A2
AU
A3
AU
A4
AU
A5
AU
Asample_rep
Asample_drift
Asample_round
AvgC
mg N L
unitless
AvgA
AU
CC
R:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXeXQLWOeVV
+DOIZLGWKRIOLPLWVXQLWOeVV
mNH4Cl:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXeJ
+DOIZLGWKRIOLPLWVJ
187
V1000:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
PNH4Cl:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXeXQLWOeVV
+DOIZLGWKRIOLPLWVXQLWOeVV
fNH4Clconv:
CRQVWDQW
9DOXe
V1:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
V100:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
V1_st:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
V1_100:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
V2_st:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
V2_100:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
188
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
V3_st:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
V3_100:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
V4_st:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
V4_100:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
V5_st:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXePL
+DOIZLGWKRIOLPLWVPL
V5_100:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
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:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXe
+DOIZLGWKRIOLPLWV
A1:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXe$8
+DOIZLGWKRIOLPLWV$8
A2:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXe$8
+DOIZLGWKRIOLPLWV$8
A3:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXe$8
+DOIZLGWKRIOLPLWV$8
A4:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXe$8
+DOIZLGWKRIOLPLWV$8
A5:
T\Se%UeFWDQJXODUGLVWULEXWLRQ
9DOXe$8
+DOIZLGWKRIOLPLWV$8
n:
CRQVWDQW
9DOXeXQLWOeVV
190
Determination of Ammonium in Water by Continuous Flow Analysis (CFA) and Spectrometric Detection
Uncertainty budgets:
C
CRQFeQWUDWLRQRI1+LQWKeVDPSOeVROXWLRQ
Quantity Value
Standard
uncertainty
Distribution
Sensitivity Uncertainty
coefficient contribution
Asample
0.25600 AU
1.48 10-3 AU
b0
0.01435 AU
2.07 10-3 AU
b1
0.99023
AU L mg-1
7.01 10-3
AU L mg-1
fdil
1.0 unitless
0.0 unitless
0.99000 unitless
5.77 10-3
unitless
rectangular
-0.25
Cst_0
995.01 mg mL-1
2.96 mg mL-1
mNH4Cl
3.81900 g
1.15 10-3 g
rectangular
0.065
75 10-6 mg L-1
V1000
1.000000 mL
577 10-6 mL
rectangular
-0.25
PNH4Cl
0.99500 unitless
2.89 10-3
unitless
rectangular
0.25
fNH4Clconv
0.26185152642501
unitless
Cst
9.9501 mg L-1
0.0649 mg L-1
V1
1.00000 mL
5.77 10-3 mL
rectangular
0.25
V100
100.0000 mL
0.0577 mL
rectangular
-2.5 10-3
C1
0.099501 mg L-1
V1_st
1.00000 mL
5.77 10-3 mL
rectangular
0.035
V1_100
100.0000 mL
0.0577 mL
rectangular
-350 10-6
C2
0.19900 mg L-1
V2_st
2.0000 mL
0.0289 mL
rectangular
0.031
V2_100
100.0000 mL
0.0577 mL
rectangular
-620 10-6
0.0 %
C3
0.39800 mg L-1
V3_st
4.0000 mL
0.0577 mL
rectangular
0.023
17.9 %
V3_100
100.0000 mL
0.0577 mL
rectangular
-910 10-6
0.0 %
Index
0.0 %
20.9 %
0.0 %
191
Standard
uncertainty
Quantity Value
Distribution
Sensitivity Uncertainty
coefficient contribution
Index
C4
0.59701 mg L-1
V4_st
6.00000 mL
8.66 10-3 mL
rectangular
0.014
V4_100
100.0000 mL
0.0577 mL
rectangular
-850 10-6
0.0 %
C5
0.99501 mg L-1
V5_st
10.0000 mL
0.0144 mL
rectangular
-2.7 10-3
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
Asample_drift
0.0
1.30 10-3
normal
1.0
Asample_round 0.0
289 10-6
rectangular
1.0
AC
1.5720 -
0.0108 -
A1
0.108000 AU
577 10-6 AU
rectangular
-0.36
A2
0.214000 AU
577 10-6 AU
rectangular
-0.32
A3
0.412000 AU
866 10-6 AU
rectangular
-0.23
A4
0.60600 AU
1.15 10-3 AU
rectangular
-0.14
A5
0.99790 AU
1.15 10-3 AU
rectangular
0.027
31 10-6 mg L-1
AvgC
0.45771 mg L-1
5.0 unitless
AvgA
0.467580 AU
404 10-6 AU
CC
1.5544 -
0.0211 -
0.24650 mg L-1
18.2 %
0.0 %
Results:
192
Quantity
Value
Expanded
uncertainty
Coverage factor
Coverage
0.2465 mg L-1
2.5 % (relative)
2.00
manual
Appendix 1
TrainMiC Exercises (white pages)
193
TrainMiC Exercises
Analytical procedure:
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
195
)LOeQDPeT(MPL$T(:KLWeT9M8$
9eUVLRQ(1
PUeSDUeGE\TUDLQMLC
(GLWRUV1LQeWDMDMFeQPKLOLSTD\ORU
IVVXeGMDUFK
)RUXVeDWWKeTUDLQMLCFRXUVeVRQO\
196
standard curve
Standard addition
internal standard
Model equation
197
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
2
3
4
5
4. List the reference standards needed and state the information regarding
traceability of the reference value
For the analyte
1
Name/ChemicalFormula/Producer:
Name/ChemicalFormula/Producer:
Quantity/Equipment/Calibration:
e.g. mass/balance/calibrated by NMI, U = xx
(k = 2) see also data yellow sheet
Quantity/Equipment/Calibration:
Quantity/Equipment/Calibration:
Quantity/Equipment/Calibration:
Yes
198
No
199
LOD
LOQ
Mark the customers
requirements and give
their values
Repeatability
Within-lab reproducibility
Trueness
Measurement uncertainty
Other-state
200
Full
Partial
Confirmation/Verification
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
Selectivity, interferences
6. Measuring range
Linearity
Upper limit
LOD
LOQ
7. Spread precision
Repeatability
Reproducibility (within lab)
Reproducibility (between lab)
8. Robustness
Variation of parameters
201
9. Quality control
Control charts
Participation in proficiency testing schemes
202
Calculations
LOD
LOQ
Repeatability
Within-lab reproducibilty
Trueness
Measurement uncertainty
Other - please state
12. Does the analytical procedure fulfil the requirement(s) for the intended use?
Parameter
Value obtained
during validation
The requirement
is fulfilled
Yes/No
LOD
LOQ
Repeatability
Within-lab
reproducibility
Trueness
Measurement
Other
No
203
Model equation:
204
Value
Unit
Remark
Standard
uncertainty
Unit
Remark
7. Calculate the combined standard uncertainty (uc) of the result and specify units
Using:
Input
quantity
MDWKePDWLFDOVROXWLRQ
Value
Standard
uncertainty
6SUeDGVKeeWDSSURDFK
Unit
CRPPeUFLDOVRIWZDUe
Remark
8. Calculate expanded uncertainty (Uc) and specify the coverage factor k and the
units
205
9. Analyse the uncertainty contribution and specify the main three input quantities
contributing the most to Uc
1
2
3
206
207
Appendix 2
Briefing of the trainees on the example session
209
7UDLQ0L&H[DPSOHVHVVLRQ
,QWURGXFWLRQ
,QWURGXFWLRQWRWKH7UDLQ0L&
H[DPSOHVHVVLRQ
,QWURGXFWLRQWRWKHDQDO\WLFDOSURFHGXUHZHZLOOEH
ZRUNLQJRQ
,QWURGXFWLRQWRWKH7UDLQ0L&
H[DPSOHVHVVLRQ
210
$7UDLQ0L&H[DPSOH LQFOXGHV
$OOWKHLQSXWLQIRUPDWLRQ QHHGHGWRGRWKHWKUHHH[HUFLVHV
LH
$ERXWWKHDQDO\WLFDOSURFHGXUH
$ERXWWKHFXVWRPHUVUHTXLUHPHQWVRQWKHTXDOLW\RIWKH
PHDVXUHPHQWUHVXOWV
0HDVXUHPHQWGDWD
7KLVLVNQRZQDV\HOORZSDJHV
,QWURGXFWLRQWRWKH7UDLQ0L&
H[DPSOHVHVVLRQ
$7UDLQ0L&H[DPSOH DOVRLQFOXGHV
$OLVWRITXHVWLRQVIRUZKLFK\RXVKRXOGILQGWKHDQVZHUV
LQWKH\HOORZ SDJHVVRPHWLPHVVRPHFDOFXODWLRQVDUHEH
QHHGHGWRR
4XHVWLRQVDUHJURXSHGDVIROORZV
([HUFLVH (VWDEOLVKLQJWUDFHDELOLW\LQDQDO\WLFDOFKHPLVWU\
([HUFLVH 6LQJOHODERUDWRU\YDOLGDWLRQRIPHDVXUHPHQW
SURFHGXUHV
([HUFLVH %XLOGLQJDQXQFHUWDLQW\EXGJHW
([HUFLVHVDUHNQRZQDVZKLWHSDJHV
,QWURGXFWLRQWRWKH7UDLQ0L&
H[DPSOHVHVVLRQ
211
([HUFLVH(VWDEOLVKLQJWUDFHDELOLW\
LQDQDO\WLFDOFKHPLVWU\
6SHFLI\LQJWKHDQDO\WH DQGWKHPHDVXUDQG
&KRRVLQJDVXLWDEOHPHDVXUHPHQWSURFHGXUHZLWKDVVRFLDWHGPRGHO
HTXDWLRQ
/LVWWKHLQSXWTXDQWLWLHVDFFRUGLQJWRWKHLULQIOXHQFHRQWKH
XQFHUWDLQW\RIWKHPHDVXUHPHQWILUVWWKHPRVWLPSRUWDQWRQHV$W
WKLVSRLQW\RXUMXGJHPHQWVKRXOGEHEDVHGRQ\RXUSUHYLRXV
H[SHULHQFHRQO\
/LVWWKHUHIHUHQFHVWDQGDUGVQHHGHGDQGVWDWHWKHLQIRUPDWLRQ
UHJDUGLQJWUDFHDELOLW\RIWKHUHIHUHQFHYDOXH
(VWLPDWLQJXQFHUWDLQW\DVVRFLDWHGZLWKWKHPHDVXUHPHQW
+RZZRXOG\RXSURYHWUDFHDELOLW\RI\RXUUHVXOW
$Q\RWKHUFRPPHQWVTXHVWLRQV
,QWURGXFWLRQWRWKH7UDLQ0L&
H[DPSOHVHVVLRQ
+RZWRRUJDQLVHRXUVHOYHVIRU
WKH7UDLQ0L&H[DPSOHVHVVLRQ"
)RUPLQJ WKHJURXSVHDFKFRQVLVWLQJRIPD[LPXP
SDUWLFLSDQWV
(DFKJURXSQRPLQDWHVD UHSRUWHU
(DFKRI\RXZLOOJHW
WKH\HOORZSDJH LQSXWLQIRUPDWLRQDQG
WKHZKLWHSDJH ([HUFLVHVRQWUDFHDELOLW\YDOLGDWLRQ
DQGPHDVXUHPHQWXQFHUWDLQW\
,QWURGXFWLRQWRWKH7UDLQ0L&
H[DPSOHVHVVLRQ
212
+RZWRRUJDQLVHRXUVHOYHVIRUWKH
7UDLQ0L&H[DPSOHVHVVLRQWLPHZLVH"
PLQXWHVDUHDYDLODEOHIRUWKHJURXSZRUNSHUH[HUFLVH
$IWHUZDUGVDOOWKHUHSRUWHUVZLOOEHDVNHGWRUHSRUWWKHDQVZHUVDQGWR
H[SODLQWRWKHRWKHUVDERXWWKHTXHVWLRQVDQGFRPPHQWVKLVKHUJURXS
ZDVGLVFXVVLQJGXULQJWKHH[HUFLVHPLQXWHVDUHDYDLODEOHIRU D
GLVFXVVLRQ
,03257$17
WKHUHSRUWLQJ GLVFXVVLRQSDQHOLVQRWDERXWFRUUHFWZURQJDQVZHUV
EXWDERXWVKDULQJ\RXUTXHVWLRQVH[SHULHQFHVLGHDVVXJJHVWLRQVDQG
FRPPHQWV\RXZRXOGEHKDYLQJGXULQJWKHH[HUFLVHVHVVLRQZLWKDOOWKH
DWWHQGHHVLQFOXGLQJWKHWUDLQHUV
,QWURGXFWLRQWRWKH7UDLQ0L&
H[DPSOHVHVVLRQ
([HUFLVH6LQJOHODERUDWRU\YDOLGDWLRQ
RIPHDVXUHPHQWSURFHGXUHV
3$57,*(1(5$/,668(6
6SHFLI\WKHPHDVXUHPHQWSURFHGXUHDQDO\WHPHDVXUDQG DQGXQLWV
6SHFLI\WKHVFRSH
5HTXLUHPHQWRQWKHPHDVXUHPHQWSURFHGXUH
2ULJLQRIWKHPHDVXUHPHQWSURFHGXUH
3$57,,3$5$0(7(5672%(9$/,'$7('
6HOHFWLYLW\,QWHUIHUHQFH5HFRYHU\
0HDVXULQJUDQJH
6SUHDG 3UHFLVLRQ
5REXVWQHVV
4XDOLW\&RQWURO
2WKHUSDUDPHWHUVWREHWHVWHG
3$57,,,620(&$/&8/$7,216$1'&21&/86,216
&DOFXODWLRQRISDUDPHWHUVUHTXHVWHGE\WKHFXVWRPHU
'RHVWKHDQDO\WLFDOSURFHGXUHIXOILOWKHUHTXLUHPHQWVIRUWKHLQWHQGHGXVH"
,QWURGXFWLRQWRWKH7UDLQ0L&
H[DPSOHVHVVLRQ
213
([HUFLVH%XLOGLQJDQXQFHUWDLQW\EXGJHW
6SHFLI\WKHPHDVXUDQG DQGXQLWV
'HVFULEHWKHPHDVXUHPHQWSURFHGXUHDQGSURYLGHWKHDVVRFLDWHG
PRGHOHTXDWLRQ
,GHQWLI\DOOSRVVLEOHVRXUFHVRIXQFHUWDLQW\
(YDOXDWHYDOXHVRIHDFKLQSXWTXDQWLW\
(YDOXDWHWKHVWDQGDUGXQFHUWDLQW\RIHDFKLQSXWTXDQWLW\
&DOFXODWHWKHYDOXHRIWKHPHDVXUDQGXVLQJWKHPRGHOHTXDWLRQ
&DOFXODWHWKHFRPELQHGVWDQGDUGXQFHUWDLQW\XFRIWKHUHVXOWDQG
VSHFLI\XQLWV
&DOFXODWHWKHH[SDQGHGXQFHUWDLQW\8FDQGVSHFLI\WKHFRYHUDJH
IDFWRUNDQGWKHXQLWV
$QDO\VHWKHXQFHUWDLQW\FRQWULEXWLRQDQGVSHFLI\WKHPDLQWKUHH
LQSXWTXDQWLWLHVFRQWULEXWLQJWKHPRVWWR8F
,QWURGXFWLRQWRWKH7UDLQ0L&
H[DPSOHVHVVLRQ
,QWURGXFWLRQWRWKHDQDO\WLFDOSURFHGXUH
ZHZLOOEHZRUNLQJRQWRGD\
0HDVXUHPHQWV RI [[[[ LQ[[[[ E\ [[[[
,QWURGXFWLRQWRWKH7UDLQ0L&
H[DPSOHVHVVLRQ
214
Notes
215
Notes
216
Abstract
CDVeVWXGLeVRQWUDFeDELOLW\PeDVXUePeQWXQFeUWDLQW\DQGYDOLGDWLRQIRUPeDVXUePeQWV
RIJROGLQJROGDOOR\VFDOFLXPLQVeUXPUDGLXPLQZDWeUSRODUSeVWLFLGeVLQIRRGDQG
DPPRQLXPLQZDWeUDUeSUeVeQWeGLQWKLVUeSRUW$GGLWLRQDOO\WKeLGeDDQGVWUXFWXUeRI
WKeTUDLQMLCe[DPSOeVZKLFKFRPSOePeQWWKeTUDLQMLCWKeRUeWLFDOSUeVeQWDWLRQV
DUeGeVFULEeGLQGeWDLOWRJLYeDFRPSOeWeRYeUYLeZRIWKeTUDLQMLCWeDFKLQJPDWeULDO