ISO 15597:2025

Petroleum and related products — Determination of chlorine and bromine content — Wavelength-dispersive X-ray fluorescence spectrometry

This document specifies a method for the determination of the chlorine and bromine content of liquid petroleum products, synthetic oils and fluids, and additives for petroleum products (including used oils) that are soluble in organic solvents of negligible or accurately known chlorine/bromine content. The method is applicable to products or additives with chlorine content in the range of a mass fraction of 0,000 5 % to 0,100 0 %, and bromine contents in the range of a mass fraction of 0,001 0 % to 0,100 0 %.

Produits pétroliers et produits connexes — Détermination de la teneur en chlore et en brome — Spectrométrie par fluorescence X dispersive en longueur d'onde

La présente Norme internationale décrit une méthode permettant le dosage du chlore et du brome dans les produits pétroliers liquides, les fluides et huiles synthétiques et les additifs pour produits pétroliers (y compris les huiles usagées), ces produits étant solubles dans des solvants organiques à teneur en chlore/brome négligeable ou précisément connue. Cette méthode est applicable aux produits ou additifs dont la teneur en chlore est comprise entre 0,000 5 % (m/m) et 0,100 0% (m/m), et dont la teneur en brome est comprise entre 0,001 0 % (m/m) et 0,100 0 % (m/m). Les autres éléments présents ne perturbent généralement pas l'analyse; toutefois le plomb, à des teneurs supérieures à 0,150 0 % (m/m), peut interférer (voir note 2). NOTE 1 Pour les besoins de la présente Norme internationale, l'expression «% (m/m)» est utilisée pour désigner la fraction massique d'un produit. NOTE 2 Les lubrifiants usagés peuvent poser des problèmes particuliers en raison de la présence, à des concentrations relativement élevées, d'une grande diversité d'éléments pouvant potentiellement provoquer des interférences. Pour les lubrifiants usagés, la limite inférieure de dosage peut se situer à 0,005 0 % (m/m), même si les dispositions du dernier paragraphe de 9.3 sont appliquées.

General Information

• Status: Published
• Publication Date: 12-Aug-2025
• ICS: 75.080 - Petroleum products in general
• Technical Committee: ISO/TC 28 - Petroleum and related products, fuels and lubricants from natural or synthetic sources
• Drafting Committee: ISO/TC 28/WG 24 - Elemental analysis
• Current Stage: 6060 - International Standard published
• Start Date: 13-Aug-2025
• Due Date: 07-May-2026
• Completion Date: 13-Aug-2025

Relations

• Revises: ISO 15597:2001 - Petroleum and related products — Determination of chlorine and bromine content — Wavelength-dispersive X-ray fluorescence spectrometry
• Effective Date: 11-May-2024

Standards Content (Sample)

International
Standard
ISO 15597
Second edition
Petroleum and related products —
2025-08
Determination of chlorine and
bromine content — Wavelength-
dispersive X-ray fluorescence
spectrometry
Produits pétroliers et produits connexes — Détermination de la
teneur en chlore et en brome — Spectrométrie par fluorescence X
dispersive en longueur d'onde
Reference number
© ISO 2025
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. de Blandonnet 8
CH-1214 Vernier, Geneva
Phone: [phone]
Email: [e-mail]
Website: www.iso.org
Published in Switzerland
ii
Contents Page
Foreword .iv
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 1
5 Reagents and materials . 2
6 Apparatus . 2
7 Sampling . 3
8 Calibration solutions . 3
8.1 General .3
8.2 Preparation of stock solutions .3
8.2.1 Chlorine and bromine stock solutions .3
8.2.2 Bismuth solution.4
8.3 Preparation of standard solutions .4
8.4 Preparation of calibration solutions .4
8.5 Storage of standards . .4
9 Calibration . 4
9.1 General .4
9.2 Measurements .4
9.3 Calibration curves .5
9.4 Checking .5
10 Procedure . 6
11 Calculation . 6
12 Expression of results . 6
13 Precision . 6
13.1 General .6
13.2 Repeatability, r.6
13.3 Reproducibility, R .6
14 Test report . 7
Bibliography . 8

iii
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 document 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).
ISO draws attention to the possibility that the implementation of this document may involve the use of (a)
patent(s). ISO takes no position concerning the evidence, validity or applicability of any claimed patent
rights in respect thereof. As of the date of publication of this document, ISO had not received notice of (a)
patent(s) which may be required to implement this document. However, implementers are cautioned that
this may not represent the latest information, which may be obtained from the patent database available at
www.iso.org/patents. ISO shall not be held responsible for identifying any or all such patent rights.
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 Technical Committee ISO/TC 28, Petroleum and related products, fuels and
lubricants from natural or synthetic sources.
This second edition cancels and replaces the first edition (ISO 15597:2001), which has been technically
revised.
The main changes are as follows:
— in 5.5, permission added to allow use of other sources of bismuth;
— throughout the entire document, the notation used in X-ray lines has been changed from Siegbahn to
IUPAC notation;
— Clause 3 (Terms and definitions) has been added;
— Bibliography has been added.
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.

iv
International Standard ISO 15597:2025(en)
Petroleum and related products — Determination of chlorine
and bromine content — Wavelength-dispersive X-ray
fluorescence spectrometry
WARNING — The use of this document may involve hazardous materials, operations and equipment.
This document does not purport to address all of the safety problems associated with its use. It is the
responsibility of the user of this document to establish appropriate safety and health practices and
determine the applicability of regulatory limitations prior to use.
1 Scope
This document specifies a method for the determination of the chlorine and bromine content of liquid
petroleum products, synthetic oils and fluids, and additives for petroleum products (including used oils)
that are soluble in organic solvents of negligible or accurately known chlorine/bromine content. The method
is applicable to products or additives with chlorine content in the range of a mass fraction of 0,000 5 % to
0,100 0 %, and bromine contents in the range of a mass fraction of 0,001 0 % to 0,100 0 %.
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 3170, Hydrocarbon Liquids — Manual sampling
ISO 3171, Petroleum liquids — Automatic pipeline sampling
3 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/
4 Principle
The test portion and a bismuth solution as internal standard are mixed in a given mass ratio and exposed, in
a sample cell, to the primary radiation of an X-ray tube.
The count rates of the chlorine K-L2,3 at 0,472 9 nm and bismuth M4-N6 at 0,490 9 nm, or bromine K-L2,3 at
0,104 1 nm and bismuth L3–M4,5 at 0,114 4 nm fluorescence are excited, the count rate of the background
radiation at 0,480 7 nm or 0,108 5 nm are measured, and the ratio of these net count rates is calculated. The
chlorine or bromine content of the sample is determined from calibration curves prepared on the basis of
either chlorine or bromine calibration standards, or both.
Other elements do not generally interfere, although lead can interfere at contents above a mass fraction of
0,150 0 % (see note in 9.2).
NOTE Used lubricants can pose particular problems due to the range of potentially interfering elements
at relatively high concentrations. For used lubricants generally, the lower limit of sensitivity can be a mass
fraction of 0,005 0 % even when the provisions of the last paragraph of 10.3 are applied
5 Reagents and materials
5.1 White oil (light paraffin oil), high purity grade, sulfur content 1 mg/kg maximum.
5.2 Chlorine compound, 1-chlorooctane or another oil-soluble chlorine compound of accurately known
chlorine content, used for the preparation of the primary standards. The chlorine content shall be accurately
known to the nearest mass fraction of 0,01 %.
5.3 Bromine compound, 1,1,2,2-tetrabromoethane or another oil-soluble bromine compound of
accurately known bromine content, used for the preparation of the primary standards. The bromine content
shall be accurately known to the nearest mass fraction of 0,01 %.
WARNING — 1,1,2,2-tetrabromoethane is extremely toxic by inhalation and ingestion. Appropriate
precautions for the handling operations of opening the container and weighing shall be followed.
5.4 Certified reference materials, obtained from a supplier conforming to ISO 1
...

International
Standard
ISO 15597
Second edition
Petroleum and related products —
Determination of chlorine and
bromine content — Wavelength-
dispersive X-ray fluorescence
spectrometry
Produits pétroliers et produits connexes — Détermination de la
teneur en chlore et en brome — Spectrométrie par fluorescence X
dispersive en longueur d'onde
PROOF/ÉPREUVE
Reference number
© ISO 2025
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. de Blandonnet 8
CH-1214 Vernier, Geneva
Phone: [phone]
Email: [e-mail]
Website: www.iso.org
Published in Switzerland
PROOF/ÉPREUVE
ii
Contents Page
Foreword .iv
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 1
5 Reagents and materials . 2
6 Apparatus . 2
7 Sampling . 3
8 Calibration solutions . 3
8.1 General .3
8.2 Preparation of stock solutions .3
8.2.1 Chlorine and bromine stock solutions .3
8.2.2 Bismuth solution.4
8.3 Preparation of standard solutions .4
8.4 Preparation of calibration solutions .4
8.5 Storage of standards . .4
9 Calibration . 4
9.1 General .4
9.2 Measurements .4
9.3 Calibration curves .5
9.4 Checking .5
10 Procedure . 6
11 Calculation . 6
12 Expression of results . 6
13 Precision . 6
13.1 General .6
13.2 Repeatability, r.6
13.3 Reproducibility, R .6
14 Test report . 7
Bibliography . 8
PROOF/ÉPREUVE
iii
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 document 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).
ISO draws attention to the possibility that the implementation of this document may involve the use of (a)
patent(s). ISO takes no position concerning the evidence, validity or applicability of any claimed patent
rights in respect thereof. As of the date of publication of this document, ISO had not received notice of (a)
patent(s) which may be required to implement this document. However, implementers are cautioned that
this may not represent the latest information, which may be obtained from the patent database available at
www.iso.org/patents. ISO shall not be held responsible for identifying any or all such patent rights.
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 Technical Committee ISO/TC 28, Petroleum and related products, fuels and
lubricants from natural or synthetic sources.
This second edition cancels and replaces the first edition (ISO 15597:2001), which has been technically
revised.
The main changes are as follows:
— in 5.5, permission added to allow use of other sources of bismuth;
— throughout the entire document, the notation used in X-ray lines has been changed from Siegbahn to
IUPAC notation;
— Clause 3 (Terms and definitions) has been added;
— Bibliography has been added.
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.
PROOF/ÉPREUVE
iv
International Standard ISO 15597:2025(en)
Petroleum and related products — Determination of chlorine
and bromine content — Wavelength-dispersive X-ray
fluorescence spectrometry
WARNING — The use of this document may involve hazardous materials, operations and equipment.
This document does not purport to address all of the safety problems associated with its use. It is the
responsibility of the user of this document to establish appropriate safety and health practices and
determine the applicability of regulatory limitations prior to use.
1 Scope
This document specifies a method for the determination of the chlorine and bromine content of liquid
petroleum products, synthetic oils and fluids, and additives for petroleum products (including used oils)
that are soluble in organic solvents of negligible or accurately known chlorine/bromine content. The method
is applicable to products or additives with chlorine content in the range of a mass fraction of 0,000 5 % to
0,100 0 %, and bromine contents in the range of a mass fraction of 0,001 0 % to 0,100 0 %.
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 3170, Petroleum liquids — Manual sampling.
ISO 3171, Petroleum liquids — Automatic pipeline sampling
3 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/
4 Principle
The test portion and a bismuth solution as internal standard are mixed in a given mass ratio and exposed, in
a sample cell, to the primary radiation of an X-ray tube.
The count rates of the chlorine K-L2,3 at 0,472 9 nm and bismuth M4-N6 at 0,490 9 nm, or bromine K-L2,3 at
0,104 1 nm and bismuth L3–M4,5 at 0,114 4 nm fluorescence are excited, the count rate of the background
radiation at 0,480 7 nm or 0,108 5 nm are measured, and the ratio of these net count rates is calculated. The
chlorine or bromine content of the sample is determined from calibration curves prepared on the basis of
either chlorine or bromine calibration standards, or both.
Other elements do not generally interfere, although lead can interfere at contents above a mass fraction of
0,150 0 % (see note in 9.2).
PROOF/ÉPREUVE
NOTE Used lubricants can pose particular problems due to the range of potentially interfering elements
at relatively high concentrations. For used lubricants generally, the lower limit of sensitivity can be a mass
fraction of 0,005 0 % even when the provisions of the last paragraph of 10.3 are applied
5 Reagents and materials
5.1 White oil (light paraffin oil), high purity grade, sulfur content 1 mg/kg maximum.
5.2 Chlorine compound, 1-chlorooctane or another oil-soluble chlorine compound of accurately known
chlorine content, used for the preparation of the primary standards. The chlorine content shall be accurately
known to the nearest mass fraction of 0,01 %.
5.3 Bromine compound, 1,1,2,2-tetrabromoethane or another oil-soluble bromine compound of
accurately known bromine content, used for the preparation of the primary standards. The bromine content
shall be accurately known to the nearest mass fraction of 0,01 %.
WARNING — 1,1,2,2-tetrabromoethane is extremely toxic by inhalation and ingestion. Appropriate
precautions for the handling operations of opening the container and weighing shall be followed.
5.4 Certified reference ma
...

ISO 15597:2025(en)
ISO/TC 28
Secretariat: NEN
Date: 2025-05-2106-18
Petroleum and related products — Determination of chlorine and bromine content — Wavelength-
dispersive X-ray fluorescence spectrometry
Produits pétroliers et produits connexes — Dosage du chlore et du brome — Spectrométrie par fluorescence X
dispersive en longueur d'onde
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. de Blandonnet 8
CH-1214 Vernier, Geneva
Phone: [phone]
Email: [e-mail]
Website: www.iso.orgwww.iso.org
Published in Switzerland
ii
Contents
Foreword . iv
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 1
5 Reagents and materials . 2
6 Apparatus . 2
7 Samples and sampling . 3
8 Calibration solutions . 3
8.1 General . 3
8.2 Preparation of stock solutions . 3
8.2.1 Chlorine and bromine stock solutions . 3
8.2.2 Bismuth solution . 3
8.3 Preparation of standard solutions . 4
8.4 Preparation of calibration solutions . 4
8.5 Storage of standards . 4
9 Calibration . 4
9.1 General . 4
9.2 Measurements . 4
9.3 Calibration curves . 5
9.4 Checking . 5
10 Procedure . 6
11 Calculation . 6
12 Expression of results . 6
13 Precision . 6
13.1 General . 6
13.2 Repeatability, r . 6
13.3 Reproducibility, R . 6
14 Test report . 7
Bibliography . 9Foreword v
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 2
5 Reagents and materials . 2
6 Apparatus . 2
7 Sampling . 3
8 Calibration solutions . 3
8.1 General . 3
8.2 Preparation of stock solutions . 3
iii
8.2.1 Chlorine and bromine stock solutions . 3
8.2.2 Bismuth solution . 4
8.3 Preparation of standard solutions . 4
8.4 Preparation of calibration solutions . 5
8.5 Storage of standards . 5
9 Calibration . 5
9.1 General . 5
9.2 Measurements . 5
9.3 Calibration curves . 6
9.4 Checking . 6
10 Procedure . 6
11 Calculation . 7
12 Expression of results . 7
13 Precision . 7
13.1 General . 7
13.2 Repeatability, r . 7
13.3 Reproducibility, R . 7
14 Test report . 8
Bibliography . 9

iv
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 document should be noted. This document was drafted in accordance with the editorial rules of the
ISO/IEC Directives, Part 2 (see www.iso.org/directiveswww.iso.org/directives).
ISO draws attention to the possibility that the implementation of this document may involve the use of (a)
patent(s). ISO takes no position concerning the evidence, validity or applicability of any claimed patent rights
in respect thereof. As of the date of publication of this document, ISO had not received notice of (a) patent(s)
which may be required to implement this document. However, implementers are cautioned that this may not
represent the latest information, which may be obtained from the patent database available at
www.iso.org/patents.www.iso.org/patents. ISO shall not be held responsible for identifying any or all such
patent rights.
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.htmlwww.iso.org/iso/foreword.html.
This document was prepared by Technical Committee ISO/TC 28, Petroleum and related products, fuels and
lubricants from natural or synthetic sources.
This second edition cancels and replaces the first edition (ISO 15597:2001), which has been technically
revised.
The main changes are as follows:
— in 5.5, permission added to allow use of other sources of bismuth;
— throughout the entire document, the definitions ofnotation used in X-ray lines has been changed from
Siegbahn to IUPAC notation;
— Clause 3 (Terms and definitions) has been added;
— Bibliography has been added.
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.htmlwww.iso.org/members.html.
.
v
International Standard ISO 15597:2025(en)

Petroleum and related products — Determination of chlorine and
bromine content — Wavelength-dispersive X-ray fluorescence
spectrometry
WARNING — The use of this document may involve hazardous materials, operations and equipment. This
document does not purport to address all of the safety problems associated with its use. It is the responsibility
of the user of this document to establish appropriate safety and health practices and determine the
applicability of regulatory limitations prior to use.
1 Scope
This document specifies a method for the determination of the chlorine and bromine content of liquid
petroleum products, synthetic oils and fluids, and additives for petroleum products (including used oils) that
are soluble in organic solvents of negligible or accurately known chlorine/bromine content. The method is
applicable to products or additives with chlorine content in the range of a mass fraction of 0,000 5 % to
0,100 0 %, and bromine contents in the
...