ISO 13167

Water quality — Plutonium, americium, curium and neptunium — Test method using alpha spectrometry

ISO 13167:2015 specifies a test method for measuring actinides (238Pu, 239+240Pu, 241Am, 242Cm, 243+244Cm and 237Np) in water samples by alpha spectrometry following a chemical separation. The method can be used for any type of environmental study or monitoring. The volume of the test portion required depends on the assumed activity of the sample and the desired detection limit. The detection limit of the test method is 5 × 10−3 to 5 × 10−4 Bq/l for a volume of the test portion of 0,1 l to 5 l with a counting time of two to ten days.

Qualité de l'eau — Plutonium, américium, curium et neptunium — Méthode d'essai par spectrométrie alpha

ISO 13167:2015 décrit une méthode d'essai permettant de mesurer les actinides (238Pu, 239+240Pu, 241Am, 242Cm, 243+244Cm et 237Np) dans des échantillons d'eau, par spectrométrie alpha après séparation chimique. Cette méthode peut être utilisée pour tout type d'étude ou de surveillance environnementale. Le volume de la prise d'essai requise dépend de l'activité supposée de l'échantillon et de la limite de détection souhaitée.

General Information

• Status: Not Published
• ICS: 13.060.60 - Examination of physical properties of water
• ICS: 13.280 - Radiation protection
• ICS: 17.240 - Radiation measurements
• Technical Committee: ISO/TC 147/SC 3 - Radioactivity measurements
• Drafting Committee: ISO/TC 147/SC 3/WG 16 - Alpha spectrometry
• Current Stage: 6000 - International Standard under publication
• Completion Date: 03-May-2023

Relations

• Revises: ISO 13167:2015 - Water quality — Plutonium, americium, curium and neptunium — Test method using alpha spectrometry
• Effective Date: 01-Jan-2022

Standards Content (Sample)

ISO/FDIS 13167:20222023(E)
ISO/TC 147/SC3
2023-02-21
Second edition
Secretariat: AFNOR
Water quality — Plutonium, americium, curium and neptunium — Test method using
alpha spectrometry

Qualité de l'eau — Plutonium, americium, curium and neptunium — Méthode d'essai par

spectrométrie alpha
Second edition
Date: 2022-12-23
---------------------- Page: 1 ----------------------
ISO/FDIS 13167:20222023(E)
© ISO 2022 2023

All rights reserved. Unless otherwise specified, or required in the context of its implementation, no

part of this publication may be reproduced or utilized otherwise in any form or by any means,

electronic or mechanical, including photocopying, or posting on the internet or an intranet, without

prior written permission. Permission can be requested from either ISO at the address below or

ISO's member body in the country of the requester.
ISO Copyright Office
CP 401 • CH-1214 Vernier, Geneva
Phone: + 41 22 749 01 11
Email: [e-mail]
Website: www.iso.org
Published in Switzerland.
ii © ISO 2022 – All rights reserved
ii © ISO 2023 – All rights reserved
---------------------- Page: 2 ----------------------
ISO/FDIS 13167:20222023(E)
Contents

Foreword ...................................................................................................................................................................... viii

Introduction.................................................................................................................................................................... ix

1 Scope .................................................................................................................................................................... 1

2 Normative references .................................................................................................................................... 1

3 Terms, definitions and symbols ................................................................................................................. 2

3.1 Terms and definitions .................................................................................................................................... 2

3.2 Symbols ............................................................................................................................................................... 2

4 Principle ............................................................................................................................................................. 4

5 Sampling, handling and storage ................................................................................................................. 5

6 Reagents and apparatus ................................................................................................................................ 5

6.1 Reagents ............................................................................................................................................................. 5

6.2 Laboratory equipment .................................................................................................................................. 5

7 Procedure ........................................................................................................................................................... 6

7.1 Chemical separation ....................................................................................................................................... 6

7.2 Preparation of the counting source .......................................................................................................... 6

7.2.1 General ................................................................................................................................................................ 6

7.2.2 Electrodeposition method ............................................................................................................................ 6

7.2.3 Co-precipitation method ............................................................................................................................... 6

7.3 Background determination ......................................................................................................................... 7

7.4 Counting efficiency determination ........................................................................................................... 7

7.5 Measurement .................................................................................................................................................... 7

8 Quality assurance and quality control program .................................................................................. 7

8.1 General ................................................................................................................................................................ 7

8.2 Variables that can influence the measurement .................................................................................... 7

8.3 Instrument verification ................................................................................................................................. 7

8.4 Contamination .................................................................................................................................................. 8

8.5 Interference control ....................................................................................................................................... 8

8.6 Method verification ........................................................................................................................................ 8

8.7 Demonstration of analyst capability ........................................................................................................ 8

9 Expression of results ...................................................................................................................................... 8

9.1 General ................................................................................................................................................................ 8

9.2 Tracer activity added ..................................................................................................................................... 9

9.3 Count rate and net count rate ..................................................................................................................... 9

9.4 Total recovery................................................................................................................................................... 9

9.5 Activity concentration of the measurand ............................................................................................... 9

9.6 Combined uncertainties ............................................................................................................................. 10

9.7 Decision threshold ....................................................................................................................................... 11

9.8 Detection limit ............................................................................................................................................... 11

9.9 Probabilistically symmetric coverage interval ................................................................................. 12

9.9.1 Limits of the probabilistically symmetric coverage interval ....................................................... 12

© ISO 2022 – All rights reserved iii
© ISO 2023 – All rights reserved iii
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ISO/FDIS 13167:20222023(E)

9.9.2 The shortest coverage interval ................................................................................................................ 12

10 Test report ...................................................................................................................................................... 13

Annex A (normative) Chemical separation of actinides on anionic resin ............................................. 15

A.1 Principle .......................................................................................................................................................... 15

A.2 Apparatus ........................................................................................................................................................ 15

A.3 Reagents .......................................................................................................................................................... 15

A.4 Procedure ........................................................................................................................................................ 16

A.4.1 General ............................................................................................................................................................. 16

A.4.2 Separation of plutonium and neptunium ............................................................................................ 16

A.4.3 Elution of plutonium and neptunium .................................................................................................... 16

A.4.4 Separation of americium and curium ................................................................................................... 17

A.4.5 Purification of americium and curium ................................................................................................. 17

Annex B (normative) Chemical separation of actinides by specific resins ........................................... 19

B.1 Principle .......................................................................................................................................................... 19

B.2 Apparatus ........................................................................................................................................................ 19

B.3 Reagents .......................................................................................................................................................... 19

B.4 Procedure ........................................................................................................................................................ 20

B.4.1 General ............................................................................................................................................................. 20

B.4.2 Extraction of americium and curium .................................................................................................... 20

B.4.3 Elution of plutonium and neptunium .................................................................................................... 21

B.4.4 Oxalate decomposition ............................................................................................................................... 21

Annex C (normative) Preparation of the source by electrodeposition .................................................. 22

C.1 Principle .......................................................................................................................................................... 22

C.2 Apparatus ........................................................................................................................................................ 22

C.3 Reagents .......................................................................................................................................................... 22

C.4 Procedure ........................................................................................................................................................ 22

C.4.1 Assembly of the electrodeposition cell ................................................................................................. 23

C.4.2 Analyte deposition ....................................................................................................................................... 23

Annex D (normative) Preparation of alpha source by lanthanide fluoride micro-

precipitation .................................................................................................................................................. 27

D.1 Principle .......................................................................................................................................................... 27

D.2 Apparatus ........................................................................................................................................................ 27

D.3 Reagents .......................................................................................................................................................... 27

iv © ISO 2022 – All rights reserved
iv © ISO 2023 – All rights reserved
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ISO/FDIS 13167:20222023(E)

D.4 Procedure ........................................................................................................................................................ 27

243

Annex E (informative) Use of Am as a yield tracer for curium isotopes ........................................... 29

E.1 Principle .......................................................................................................................................................... 29

E.2 Procedure ........................................................................................................................................................ 29

E.3 Calculation ...................................................................................................................................................... 29

E.4 On-going quality assurance ...................................................................................................................... 30

Annex F (informative) Potential interferences............................................................................................... 32

Bibliography ................................................................................................................................................................. 35

Foreword ...................................................................................................................................................................... viii

Introduction.................................................................................................................................................................... ix

1 Scope .................................................................................................................................................................... 1

2 Normative references .................................................................................................................................... 1

3 Terms, definitions and symbols ................................................................................................................. 2

3.1 Terms and definitions .................................................................................................................................... 2

3.2 Symbols ............................................................................................................................................................... 2

4 Principle ............................................................................................................................................................. 4

5 Sampling, handling and storage ................................................................................................................. 5

6 Reagents and apparatus ................................................................................................................................ 5

6.1 Reagents ............................................................................................................................................................. 5

6.2 Laboratory equipment .................................................................................................................................. 5

7 Procedure ........................................................................................................................................................... 6

7.1 Chemical separation ....................................................................................................................................... 6

7.2 Preparation of the counting source .......................................................................................................... 6

7.2.1 General ................................................................................................................................................................ 6

7.2.2 Electrodeposition method ............................................................................................................................ 6

7.2.3 Co-precipitation method ............................................................................................................................... 6

7.3 Background determination ......................................................................................................................... 7

7.4 Counting efficiency determination ........................................................................................................... 7

7.5 Measurement .................................................................................................................................................... 7

8 Quality assurance and quality control program .................................................................................. 7

8.1 General ................................................................................................................................................................ 7

8.2 Variables that can influence the measurement .................................................................................... 7

8.3 Instrument verification ................................................................................................................................. 7

8.4 Contamination .................................................................................................................................................. 8

8.5 Interference control ....................................................................................................................................... 8

© ISO 2022 – All rights reserved v
© ISO 2023 – All rights reserved v
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ISO/FDIS 13167:20222023(E)

8.6 Method verification ........................................................................................................................................ 8

8.7 Demonstration of analyst capability ........................................................................................................ 8

9 Expression of results ...................................................................................................................................... 8

9.1 General ................................................................................................................................................................ 8

9.2 Tracer activity added ..................................................................................................................................... 9

9.3 Count rate and net count rate ..................................................................................................................... 9

9.4 Total recovery................................................................................................................................................... 9

9.5 Activity concentration of the measurand ............................................................................................... 9

9.6 Combined uncertainties ............................................................................................................................. 10

9.7 Decision threshold ....................................................................................................................................... 11

9.8 Detection limit ............................................................................................................................................... 11

9.9 Probabilistically symmetric coverage interval ................................................................................. 12

9.9.1 Limits of the probabilistically symmetric coverage interval ....................................................... 12

9.9.2 The shortest coverage interval ................................................................................................................ 12

10 Test report ...................................................................................................................................................... 13

Annex A (normative) Chemical separation of actinides on anionic resin ............................................. 15

A.1 Principle .......................................................................................................................................................... 15

A.2 Apparatus ........................................................................................................................................................ 15

A.3 Reagents .......................................................................................................................................................... 15

A.4 Procedure ........................................................................................................................................................ 16

A.4.1 General ............................................................................................................................................................. 16

A.4.2 Separation of plutonium and neptunium ............................................................................................ 16

A.4.3 Elution of plutonium and neptunium .................................................................................................... 16

A.4.4 Separation of americium and curium ................................................................................................... 17

A.4.5 Purification of americium and curium ................................................................................................. 17

Annex B (normative) Chemical separation of actinides by specific resins ........................................... 19

B.1 Principle .......................................................................................................................................................... 19

B.2 Apparatus ........................................................................................................................................................ 19

B.3 Reagents .......................................................................................................................................................... 19

B.4 Procedure ........................................................................................................................................................ 20

B.4.1 General ............................................................................................................................................................. 20

B.4.2 Extraction of americium and curium .................................................................................................... 20

B.4.3 Elution of plutonium and neptunium .................................................................................................... 21

B.4.4 Oxalate decomposition ............................................................................................................................... 21

Annex C (normative) Preparation of the source by electrodeposition .................................................. 22

C.1 Principle .......................................................................................................................................................... 22

vi © ISO 2022 – All rights reserved
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ISO/FDIS 13167:20222023(E)

C.2 Apparatus ........................................................................................................................................................ 22

C.3 Reagents .......................................................................................................................................................... 22

C.4 Procedure ........................................................................................................................................................ 22

C.4.1 Assembly of the electrodeposition cell ................................................................................................. 23

C.4.2 Analyte deposition ....................................................................................................................................... 23

Annex D (normative) Preparation of alpha source by lanthanide fluoride micro-

precipitation .................................................................................................................................................. 27

D.1 Principle .......................................................................................................................................................... 27

D.2 Apparatus ........................................................................................................................................................ 27

D.3 Reagents .......................................................................................................................................................... 27

D.4 Procedure ........................................................................................................................................................ 27

243

Annex E (informative) Use of Am as a yield tracer for curium isotopes ........................................... 29

E.1 Principle .......................................................................................................................................................... 29

E.2 Procedure ........................................................................................................................................................ 29

E.3 Calculation ...................................................................................................................................................... 29

E.4 On-going quality assurance ...................................................................................................................... 30

Annex F (informative) Potential interferences............................................................................................... 32

Bibliography ................................................................................................................................................................. 35

© ISO 2022 – All rights reserved vii
© ISO 2023 – All rights reserved vii
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ISO/FDIS 13167:20222023(E)
Foreword

ISO (the International Organization for Standardization) is a worldwide federation of national standards

bodies (ISO member bodies). The work of preparing International Standards is normally carried out

through ISO technical committees. Each member body interested in a subject for which a technical

committee has been established has the right to be represented on that committee. International

organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO

collaborates closely with the International Electrotechnical Commission (IEC) on all matters of

electrotechnical standardization.

The procedures used to develop this document and those intended for its further maintenance are

described in the ISO/IEC Directives, Part 1. In particular, the different approval criteria needed for the

different types of ISO documents should be noted. This document was drafted in accordance with the

editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives 2 (see

www.iso.org/directives).

Attention is drawn to the possibility that some of the elements of this document may be the subject of

patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any

patent rights identified during the development of the document will be in the Introduction and/or on

the ISO list of patent declarations received (see www.iso.org/patentswww.iso.org/patents).

Any trade name used in this document is information given for the convenience of users and does not

constitute an endorsement.

For an explanation onof the voluntary nature of standards, the meaning of ISO specific terms and

expressions related to conformity assessment, as well as information about ISO's adherence to the World

Trade organizationOrganization (WTO) principles in the Technical Barriers to Trade (TBT)), see the

following URL: www.iso.org/iso/foreword.htmlwww.iso.org/iso/foreword.html.

This document was prepared by ISO/TC 147, Water quality, Subcommittee SC 3, Radioactivity

measurements.
This second edition cancels and replaces the first edition (ISO 13167:2015)
...

FINAL
INTERNATIONAL ISO/FDIS
DRAFT
STANDARD 13167
ISO/TC 147/SC 3
Water quality — Plutonium,
Secretariat: AFNOR
americium, curium and neptunium —
Voting begins on:
2023-03-07 Test method using alpha spectrometry
Voting terminates on:
Qualité de l'eau — Plutonium, americium, curium et neptunium —
2023-05-02
Méthode d'essai par spectrométrie alpha
RECIPIENTS OF THIS DRAFT ARE INVITED TO
SUBMIT, WITH THEIR COMMENTS, NOTIFICATION
OF ANY RELEVANT PATENT RIGHTS OF WHICH
THEY ARE AWARE AND TO PROVIDE SUPPOR TING
DOCUMENTATION.
IN ADDITION TO THEIR EVALUATION AS
Reference number
BEING ACCEPTABLE FOR INDUSTRIAL, TECHNO-
ISO/FDIS 13167:2023(E)
LOGICAL, COMMERCIAL AND USER PURPOSES,
DRAFT INTERNATIONAL STANDARDS MAY ON
OCCASION HAVE TO BE CONSIDERED IN THE
LIGHT OF THEIR POTENTIAL TO BECOME STAN-
DARDS TO WHICH REFERENCE MAY BE MADE IN
NATIONAL REGULATIONS. © ISO 2023
---------------------- Page: 1 ----------------------
ISO/FDIS 13167:2023(E)
FINAL
INTERNATIONAL ISO/FDIS
DRAFT
STANDARD 13167
ISO/TC 147/SC 3
Water quality — Plutonium,
Secretariat: AFNOR
americium, curium and neptunium —
Voting begins on:
Test method using alpha spectrometry
Voting terminates on:
Qualité de l'eau — Plutonium, americium, curium et neptunium —
Méthode d'essai par spectrométrie alpha
COPYRIGHT PROTECTED DOCUMENT
© ISO 2023

All rights reserved. Unless otherwise specified, or required in the context of its implementation, no part of this publication may

be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on

the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address below

or ISO’s member body in the country of the requester.
RECIPIENTS OF THIS DRAFT ARE INVITED TO
ISO copyright office
SUBMIT, WITH THEIR COMMENTS, NOTIFICATION
OF ANY RELEVANT PATENT RIGHTS OF WHICH
CP 401 • Ch. de Blandonnet 8
THEY ARE AWARE AND TO PROVIDE SUPPOR TING
CH-1214 Vernier, Geneva
DOCUMENTATION.
Phone: [phone]
IN ADDITION TO THEIR EVALUATION AS
Reference number
Email: [e-mail]
BEING ACCEPTABLE FOR INDUSTRIAL, TECHNO­
ISO/FDIS 13167:2023(E)
Website: www.iso.org
LOGICAL, COMMERCIAL AND USER PURPOSES,
DRAFT INTERNATIONAL STANDARDS MAY ON
Published in Switzerland
OCCASION HAVE TO BE CONSIDERED IN THE
LIGHT OF THEIR POTENTIAL TO BECOME STAN­
DARDS TO WHICH REFERENCE MAY BE MADE IN
© ISO 2023 – All rights reserved
NATIONAL REGULATIONS. © ISO 2023
---------------------- Page: 2 ----------------------
ISO/FDIS 13167:2023(E)
Contents Page

Foreword ..........................................................................................................................................................................................................................................v

Introduction .............................................................................................................................................................................................................................. vi

1 Scope ................................................................................................................................................................................................................................. 1

2 Normative references ..................................................................................................................................................................................... 1

3 Terms, definitions and symbols .......................................................................................................................................................... 2

3.1 Terms and definitions ...................................................................................................................................................................... 2

3.2 Symbols ......................................................................................................................................................................................................... 2

4 Principle ........................................................................................................................................................................................................................ 3

5 Sampling, handling and storage .......................................................................................................................................................... 4

6 Reagents and apparatus .............................................................................................................................................................................. 4

6.1 Reagents ....................................................................................................................................................................................................... 4

6.2 Laboratory equipment ..................................................................................................................................................................... 4

7 Procedure ....................................................................................................................................................................................................................5

7.1 Chemical separation .......................................................................................................................................................................... 5

7.2 Preparation of the counting source ..................................................................................................................................... 5

7.2.1 General ........................................................................................................................................................................................ 5

7.2.2 Electrodeposition method ......................................................................................................................................... 5

7.2.3 Co­precipitation method ............................................................................................................................................. 5

7.3 Background determination ......................................................................................................................................................... 6

7.4 Counting efficiency determination ....................................................................................................................................... 6

7.5 Measurement ........................................................................................................................................................................................... 6

8 Quality assurance and quality control program ............................................................................................................... 6

8.1 General ........................................................................................................................................................................................................... 6

8.2 Variables that can influence the measurement ......................................................................................................... 6

8.3 Instrument verification .................................................................................................................................................................. 6

8.4 Contamination ........................................................................................................................................................................................ 6

8.5 Interference control ........................................................................................................................................................................... 7

8.6 Method verification ............................................................................................................................................................................ 7

8.7 Demonstration of analyst capability ................................................................................................................................... 7

9 Expression of results ....................................................................................................................................................................................... 7

9.1 General ........................................................................................................................................................................................................... 7

9.2 Tracer activity added ........................................................................................................................................................................ 7

9.3 Count rate and net count rate .................................................................................................................................................... 7

9.4 Total recovery ......................................................................................................................................................................................... 8

9.5 Activity concentration of the measurand ....................................................................................................................... 8

9.6 Combined uncertainties ................................................................................................................................................................. 9

9.7 Decision threshold .............................................................................................................................................................................. 9

9.8 Detection limit ..................................................................................................................................................................................... 10

9.9 Probabilistically symmetric coverage interval ...................................................................................................... 10

9.9.1 Limits of the probabilistically symmetric coverage interval .................................................. 10

9.9.2 The shortest coverage interval ........................................................................................................................... 11

10 Test report ...............................................................................................................................................................................................................11

Annex A (normative) Chemical separation of actinides on anionic resin .................................................................13

Annex B (normative) Chemical separation of actinides by specific resins ..............................................................16

Annex C (normative) Preparation of the source by electrodeposition ........................................................................19

Annex D (normative) Preparation of alpha source by lanthanide fluoride micro-

precipitation ..........................................................................................................................................................................................................22

243

Annex E (informative) Use of Am as a yield tracer for curium isotopes .............................................................24

iii
© ISO 2023 – All rights reserved
---------------------- Page: 3 ----------------------
ISO/FDIS 13167:2023(E)

Annex F (informative) Potential interferences .....................................................................................................................................26

Bibliography .............................................................................................................................................................................................................................28

© ISO 2023 – All rights reserved
---------------------- Page: 4 ----------------------
ISO/FDIS 13167:2023(E)
Foreword

ISO (the International Organization for Standardization) is a worldwide federation of national standards

bodies (ISO member bodies). The work of preparing International Standards is normally carried out

through ISO technical committees. Each member body interested in a subject for which a technical

committee has been established has the right to be represented on that committee. International

organizations, governmental and non­governmental, in liaison with ISO, also take part in the work.

ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of

electrotechnical standardization.

The procedures used to develop this document and those intended for its further maintenance are

described in the ISO/IEC Directives, Part 1. In particular, the different approval criteria needed for the

different types of ISO documents should be noted. This document was drafted in accordance with the

editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).

Attention is drawn to the possibility that some of the elements of this document may be the subject of

patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of

any patent rights identified during the development of the document will be in the Introduction and/or

on the ISO list of patent declarations received (see www.iso.org/patents).

Any trade name used in this document is information given for the convenience of users and does not

constitute an endorsement.

For an explanation of the voluntary nature of standards, the meaning of ISO specific terms and

expressions related to conformity assessment, as well as information about ISO's adherence to

the World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT), see

www.iso.org/iso/foreword.html.

This document was prepared by ISO/TC 147, Water quality, Subcommittee SC 3, Radioactivity

measurements.

This second edition cancels and replaces the first edition (ISO 13167:2015), which has been technically

revised.
The main changes are as follows:

— addition of a description for determination of bias in the chemical recoveries of americium and

curium.

Any feedback or questions on this document should be directed to the user’s national standards body. A

complete listing of these bodies can be found at www.iso.org/members.html.
© ISO 2023 – All rights reserved
---------------------- Page: 5 ----------------------
ISO/FDIS 13167:2023(E)
Introduction

Radionuclides are present throughout the environment; thus, water bodies (e.g. surface waters, ground

waters, sea waters) contain radionuclides, which can be of either natural or anthropogenic origin.

3 14 40

— Naturally-occurring radionuclides, including H, C, K and those originating from the thorium

210 210 222 226 228 227 231 234 238
and uranium decay series, in particular Pb, Po, Rn, Ra, Ra, Ac, Pa, U, and U,

can be found in water bodies due to either natural processes (e.g. desorption from the soil, runoff

by rain water) or released from technological processes involving naturally occurring radioactive

materials (e.g. mining, mineral processing, oil, gas, and coal production, water treatment and the

production and use of phosphate fertilisers).
55 59 63 90 99

— Anthropogenic radionuclides such as Fe, Ni, Ni, Sr, Tc, transuranic elements (e.g., Np, Pu,

60 137

Am, and Cm), and some gamma emitting radionuclides such as Co and Cs can also be found in

natural waters. Small quantities of anthropogenic radionuclides can be discharged from nuclear

facilities to the environment as a result of authorized routine releases. The radionuclides present

[1]

in liquid effluents are usually controlled before being discharged to the environment and water

bodies. Anthropogenic radionuclides used in medical and industrial applications can be released

to the environment after use. Anthropogenic radionuclides are also found in waters due to

contamination from fallout resulting from above­ground nuclear detonations and accidents such as

those that have occurred at the Chornobyl and Fukushima nuclear facilities.

Radionuclide activity concentrations in water bodies can vary according to local geological

characteristics and climatic conditions and can be locally and temporally enhanced by releases from

[2],[3]

nuclear facilities during planned, existing and emergency exposure situations. Some drinking

water sources can thus contain radionuclides at activity concentrations that can present a human

health risk. The World Health Organization (WHO) recommends to routinely monitor radioactivity in

[4]

drinking waters and to take proper actions when needed to minimize the health risk.

National regulations usually specify the activity concentration limits that are authorized in drinking

waters, water bodies and liquid effluents to be discharged to the environment. These limits can vary

for planned, existing and emergency exposure situations. As an example, during either a planned

238 239 240 241 243 244 237
or existing situation, the WHO guidance level for Pu, Pu, Pu, Am, Cm, Cm, Np in
−1[3] 242 −1 −1[3]

drinking water is 1 Bq·l . For Cm the GL is 10 Bq·l .Bq·l . Compliance with these limits is

assessed by measuring radioactivity in water samples and by comparing the results obtained, with

[5] [6]

their associated uncertainties, as specified by ISO/IEC Guide 98-3 and ISO 5667­20 .

NOTE 1 If the value is not specified in Annex 6 of Reference [4], the value has been calculated using the formula

provided in Reference [4] and the dose coefficient data from References [7] and [8].

NOTE 2 The guidance level calculated in Reference [4] is the activity concentration that, with an intake of

−1 −1

2 l·d of drinking water for one year, results in an effective dose of 0,1 mSv·a to members of the public. This is

an effective dose that represents a very low level of risk to human health and which is not expected to give rise to

[4]
any detectable adverse health effects.
238 239 240 241 242 243 244
This document contains methods to determine Pu, Pu, Pu, Am, Cm, Cm, Cm,
237

Np in water samples. It has been developed to support laboratories that need either a certification

or accreditation to determine these nuclides in water samples. A certification or accreditation are

sometimes required by local and national authorities as well as some customers. The certification and

accreditation are provided by an independent body.

The methods described in this document can be used for various types of waters. Minor modifications

such as sample volume and counting time can be made if needed to ensure that the characteristic

limit, decision threshold, detection limit and uncertainties are below the required limits. This can be

done for several reasons such as emergency situations, lower national guidance limits and operational

requirements.
© ISO 2023 – All rights reserved
---------------------- Page: 6 ----------------------
FINAL DRAFT INTERNATIONAL STANDARD ISO/FDIS 13167:2023(E)
Water quality — Plutonium, americium, curium and
neptunium — Test method using alpha spectrometry

WARNING — Persons using this document should be familiar with normal laboratory practices.

This document does not purport to address all of the safety problems, if any, associated with its

use. It is the responsibility of the user to establish appropriate safety and health practices and to

determine the applicability of any other restrictions.

IMPORTANT — It is essential that tests conducted according to this test method be carried out

by suitably trained staff.
1 Scope
238 239+240 241 242
This document specifies a test method for measuring actinides ( Pu, Pu, Am, Cm,
243+244 237

Cm and Np) in water samples by alpha spectrometry following a chemical separation.

This method can be used for any type of environmental study or monitoring after appropriate sampling

and handling, and test sample preparation.

The detection limit of the test method is 5 × 10−3 to 5 × 10−4 Bq l for a volume of test portion

between 0,1 l to 5 l with a counting time of two to ten days. This is lower than the WHO criteria for safe

­1 [4]
consumption of drinking water (1 or 10) Bq·l depending on radionuclide.

The methods described in this document are applicable in the event of an emergency situation.

2 Normative references

The following documents are referred to in the text in such a way that some or all of their content

constitutes requirements of this document. For dated references, only the edition cited applies. For

undated references, the latest edition of the referenced document (including any amendments) applies.

ISO/IEC Guide 98­3, Uncertainty of measurement — Part 3: Guide to the expression of uncertainty in

me a s ur ement (GUM: 1995)

ISO/IEC Guide 99, International vocabulary of metrology — Basic and general concepts and associated

terms (VIM)

ISO 5667­1, Water quality — Sampling — Part 1: Guidance on the design of sampling programmes and

sampling techniques

ISO 5667­3, Water quality — Sampling — Part 3: Preservation and handling of water samples

ISO 5667­10, Water quality — Sampling — Part 10: Guidance on sampling of waste water

ISO 80000­10, Quantities and units — Part 10: Atomic and nuclear physics

ISO 11929­1, Determination of the characteristic limits (decision threshold, detection limit and limits of

the coverage interval) for measurements of ionizing radiation — Fundamentals and application — Part 1:

Elementary applications

ISO/IEC 17025, General requirements for the competence of testing and calibration laboratories

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ISO/FDIS 13167:2023(E)
3 Terms, definitions and symbols
3.1 Terms and definitions
No terms and definitions are listed in this document.

ISO and IEC maintain terminology databases for use in standardization at the following addresses:

— ISO Online browsing platform: available at https:// www .iso .org/ obp
— IEC Electropedia: available at https:// www .electropedia .org/
3.2 Symbols

For the purposes of this document, the symbols given in ISO/IEC Guide 98-3, ISO/IEC Guide 99

ISO 80000-10, ISO 11929-1 and the following shall apply.
Symbol Description Unit
A Activity of the tracer added Bq
α Probability of the false positive decision
β Probability of the false negative decision
Activity concentration of the measurand measured in the sample
c Bq∙l
* ­1
Decision threshold of the measurand
Bq∙l
# ­1
Detection limit of the measurand
Bq∙l

Lower and upper limits of the probabilistically symmetric coverage interval of the

 ­1
Bq∙l
cc,
measurand, respectively
<> ­1

Lower and upper limits of the shortest coverage interval of the measurand, respectively

Bq∙l
cc,
 Possible or assumed true quantity values of the measurand ­1
Bq∙l
c Activity concentration of the tracer solution at the moment of separation Bq∙l
ε Counting efficiency
243

Correction factor for possible bias for curium isotopes using Am as a tracer or for

237 236 241
Np using Pu as a tracer. For plutonium isotopes or for Am, f is equal to 1

Φ Distribution function of the standardized normal distribution; Φ(k p ) = p applies

1−γ Probability for the coverage interval of the measurand

Quantiles of the standardized normal distribution for the probabilities p (for instance p

= 1−α, 1− β or 1−γ/2)
215
Decay constant of the isotope (ex: λ is the decay constant of Po)
215
m Sample mass kg
m Mass of tracer solution g

Number of counts measured of the background on the alpha spectrum for a given time in

N Counts
the region of interest of the measurand.

Number of counts measured of the background on the alpha spectrum for a given time in

N Counts
the region of interest of the tracer.

Number of counts measured on the alpha spectrum for a given time in the region of

N Counts
interest of the measurand.

Number of counts measured on the alpha spectrum for a given time in the region of

N Counts
interest of the tracer.

P Probability of the isotope decaying by alpha particle emission (branching ratio)

r Background count rate in the region of interest of the measurand Bq
r Background count rate in the tracer region of interest of the tracer Bq
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ISO/FDIS 13167:2023(E)
Symbol Description Unit
R Total recovery
R Chemical recovery
r Gross count rate in the region of interest of the measurand Bq
r Net count rate of the measurand Bq
net
r Net count rate of the tracer Bq
netT
r Gross count rate in the region of interest of the tracer Bq
t Radiological half­life of the isotope of interest s
1/2
t Counting time of the background by alpha spectrometry s
t Time elapsed between separation and counting s
t Sample counting time by alpha spectrometry s
U Expanded uncertainty
u Standard uncertainty
uc() Standard uncertainty of the activity concentration of the measurand Bq∙l

Standard uncertainty of the estimator c as a function of an assumed true value c of

 A A
uc Bq∙l
the measurand
V Sample volume l
4 Principle

The actinide isotopes included in this document are deposited as a thin source for measurement by

alpha spectrometry by means of a grid chamber detector or a semi-conductor detector type equipment.

The sources are usually prepared by electrodeposition or co-precipitation after chemical separation

[9],[10],[11],[12]
and purification of the actinides isotopes present in the test portion.

Specific chemical separation and purification procedures are required to avoid interference from

the presence of other α-emitters, and stable nuclides in the sample, in quantities that are often

larger than the actinide isotopes of interest. Actinides can be pre-concentrated by iron hydroxide co-

precipitation at pH 8. The resulting precipitate is dissolved with an acidic solution and passed through

an ion exchange, or extraction chromatography resin (see Annexes A and B) to purify the analyte from

potential interferences. The potential radiological interferences for the measurement of the various

radionuclides relevant to this method are listed in Annex F.

After purification, a micro-precipitation with cerium fluoride (CeF ) is performed or the analytes are

electrodeposited. The actinides of interest are measured by alpha spectrometry for a suitable counting

period. The activity concentrations of the actinides of interest are calculated and reported (see Clause 9

for more details).
These procedures allow the main sources of interference to be removed, namely:

— the salt content of the water sample, especially hydrolysable elements, in order to prepare the

thinnest deposited source;

— other α-emitting radionuclides, such as uranium and thorium isotopes, whose emissions can

interfere with those of actinide isotopes of interest.

The total yield for each analysis (product of chemical separation yield and detection efficiency) is

236

determined by adding a standard solution of tracer: Pu can be used for plutonium isotopes and

237 242 243

Np, Pu can be used for plutonium isotopes only and Am can be used for americium and curium

isotopes. Enough tracer is added to obtain a good statistical precision and be easily distinguished from

a blank sample (e.g. about 100 mBq is often suitable).

The procedure shall include a reduction/oxidation cycle to adjust the tracer and the analytes to the

same oxidation state.
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ISO/FDIS 13167:2023(E)
243

It is possible to quantify curium isotopes on the basis of Am tracer recovery, or neptunium on the

236

basis of Pu tracer recovery. This can lead to a potential bias that shall be quantified using a standard

solution, participation in inter-laboratory comparison tests, or establishment of the bias factor (see

Annex E).
235 236 238 239 237 245

NOTE Np, Np, Np and Np can be used as yield tracers for Np (if available), and Cm as a yield

tracer for other Cm isotopes but the test method of this document does not cover these measurements.

5 Sampling, handling and storage

Sampling, handling, and storage of the water shall be done as specified in ISO 5667-1, ISO 5667-3

and ISO 5667-10, and guidance is given for the different types of water in References [13] to [20]. It is

important that the laboratory receives a sample that is truly representative and has not been damaged

or modified during transportation or storage.

The sample is filtered to remove suspended matter using a 0,45 μm filter. A smaller pore size filter can

also be used, but the filtration can be more tedious and time consuming. The sample shall be acidified

after filtration to pH < 2 with HNO .
6 Reagents and apparatus
6.1 Reagents

The chemical reagents and equipment are described in Annexes A and B for chemical separation and in

Annexes C and D for the preparation of the deposited source.

Except for the certified standard solutions, all the chemical reagents needed to carry out this procedure

shall be analytical grade.
6.2 Laboratory equipment
Usual laboratory equipment including the following:
6.2.1 Vacuum filtration system.
6.2.2 Filters, of pore size 0,45 µm or smaller.
6.2.3 Glass beakers.
6.2.4 Centrifuge.
6.2.5 Multi-hole vacuum box, for example, 12 positions. (optional)
6.2.6 Analytical balance, accuracy 0,1 mg.
6.2.7 Centrifuge tubes/bottles, for example, 50 ml and 500 ml in volume.
6.2.8 Pipettes.
6.2.9 Hot plate
...