Footwear - Critical substances potentially present in footwear and footwear components - Determination of organotin compounds in footwear materials (ISO 16179:2025)

This document specifies a test method for the qualification and quantification of organotin compounds by applying gas chromatography coupled with mass spectrometry. This test method is applicable to all types of footwear materials except metal hardware (see ISO/TR 16178).

Schuhe - Möglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische Substanzen - Bestimmung zinnorganischer Verbindungen in Schuhwerkstoffen (ISO 16179:2025)

Dieses Dokument legt ein Prüfverfahren zur qualitativen und quantitativen Bestimmung von zinnorganischen Verbindungen durch Anwendung von mit Massenspektrometrie gekoppelter Gaschromatographie fest. Dieses Prüfverfahren ist anwendbar für alle Arten von Schuhwerkstoffen, mit Ausnahme von Metallbeschlägen (siehe ISO/TR 16178).

Chaussures - Substances critiques potentiellement présentes dans les chaussures et les composants de chaussures - Détermination des composés organostanniques dans les matériaux de chaussures (ISO 16179:2025)

Le présent document spécifie une méthode d'essai pour la qualification et la quantification des composés organostanniques par chromatographie en phase gazeuse couplée à la spectrométrie de masse. Cette méthode d'essai est applicable à tous les types de matériaux de chaussures à l’exception des matériaux métalliques (voir l’ISO/TR 16178).

Obutev - Možna prisotnost kritičnih snovi v obutvi ali delih obutve - Ugotavljanje organskih sestavin v materialih obutve (ISO 16179:2025)

Ta dokument določa preskusno metodo za kvalifikacijo in kvantifikacijo organskih sestavin s plinsko kromatografijo v kombinaciji z masno spektrometrijo. Ta preskusna metoda se uporablja za vse vrste materialov obutve, razen kovinskih elementov (glej standard ISO/TR 16178).

General Information

Status
Published
Publication Date
25-Mar-2025
Current Stage
6060 - Definitive text made available (DAV) - Publishing
Start Date
26-Mar-2025
Completion Date
26-Mar-2025

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Standard
EN ISO 16179:2025
English language
22 pages
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SLOVENSKI STANDARD
01-junij-2025
Obutev - Možna prisotnost kritičnih snovi v obutvi ali delih obutve - Ugotavljanje
organskih sestavin v materialih obutve (ISO 16179:2025)
Footwear - Critical substances potentially present in footwear and footwear components
- Determination of organotin compounds in footwear materials (ISO 16179:2025)
Schuhe - Möglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische
Substanzen - Bestimmung zinnorganischer Verbindungen in Schuhwerkstoffen (ISO
16179:2025)
Chaussures - Substances critiques potentiellement présentes dans les chaussures et les
composants de chaussures - Détermination des composés organostanniques dans les
matériaux de chaussures (ISO 16179:2025)
Ta slovenski standard je istoveten z: EN ISO 16179:2025
ICS:
61.060 Obuvala Footwear
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN ISO 16179
EUROPEAN STANDARD
NORME EUROPÉENNE
March 2025
EUROPÄISCHE NORM
ICS 61.060 Supersedes CEN ISO/TS 16179:2012
English Version
Footwear - Critical substances potentially present in
footwear and footwear components - Determination of
organotin compounds in footwear materials (ISO
16179:2025)
Chaussures - Substances critiques potentiellement Schuhe - Möglicherweise in Schuhen und
présentes dans les chaussures et les composants de Schuhbestandteilen vorhandene kritische Substanzen -
chaussures - Détermination des composés Bestimmung zinnorganischer Verbindungen in
organostanniques dans les matériaux de chaussures Schuhwerkstoffen (ISO 16179:2025)
(ISO 16179:2025)
This European Standard was approved by CEN on 20 March 2025.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this
European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references
concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN
member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by
translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Türkiye and
United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2025 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 16179:2025 E
worldwide for CEN national Members.

Contents Page
European foreword . 3

European foreword
This document (EN ISO 16179:2025) has been prepared by Technical Committee ISO/TC 216
"Footwear" in collaboration with Technical Committee CEN/TC 309 “Footwear” the secretariat of which
is held by UNE.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by September 2025, and conflicting national standards
shall be withdrawn at the latest by September 2025.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
This document supersedes CEN ISO/TS 16179:2012.
Any feedback and questions on this document should be directed to the users’ national standards
body/national committee. A complete listing of these bodies can be found on the CEN website.
According to the CEN-CENELEC Internal Regulations, the national standards organizations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria,
Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland,
Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of
North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Türkiye and the
United Kingdom.
Endorsement notice
The text of ISO 16179:2025 has been approved by CEN as EN ISO 16179:2025 without any modification.

International
Standard
ISO 16179
Second edition
Footwear — Critical substances
2025-03
potentially present in footwear
and footwear components —
Determination of organotin
compounds in footwear materials
Chaussures — Substances critiques potentiellement présentes
dans les chaussures et les composants de chaussures —
Détermination des composés organostanniques dans les
matériaux de chaussures
Reference number
ISO 16179:2025(en) © ISO 2025
ISO 16179:2025(en)
© 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: +41 22 749 01 11
Email: copyright@iso.org
Website: www.iso.org
Published in Switzerland
ii
ISO 16179:2025(en)
Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 1
5 Reagents . 2
6 Apparatus and materials . 3
7 Preparation of the sample . 3
8 Procedure . 4
8.1 General .4
8.2 Preparation of the sodium tetraethylborate solution .4
8.3 Preparation of standard solutions .4
8.3.1 General .4
8.3.2 Internal standards — stock solution (1 000 mg/l of organotin cation) .5
8.3.3 Internal standards — working solution (10 mg/l of organotin cation) .6
8.3.4 Target compounds — stock solution (1 000 mg/l of organotin cation) .6
8.3.5 Target compounds — working solution (10 mg/l of organotin cation) .6
8.4 Preparation of the tropolone solution .6
8.5 Preparation of the buffer solution .6
8.6 Preparation of the calibration solutions .6
8.7 Sample preparation .7
8.8 Preparation of the blank solution .7
8.9 Gas chromatography .7
8.9.1 General .7
8.9.2 With MS .7
8.9.3 With MS/MS .8
9 Expression of the results . 8
9.1 Determination of the mass fraction of the tin organic compounds .8
9.2 Precision of the test method .9
10 Test report . 9
Annex A (informative) Gas chromatography apparatus and conditions for organotin analysis .10
Annex B (informative) Suitable conditions for mass spectroscopy .11
Annex C (informative) Reliability of the method .13
Bibliography . 14

iii
ISO 16179:2025(en)
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).
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 216, Footwear, in collaboration with the
European Committee for Standardization (CEN) Technical Committee CEN/TC 309, Footwear, in accordance
with the Agreement on technical cooperation between ISO and CEN (Vienna Agreement).
This second edition cancels and replaces the first edition (ISO/TS 16179:2012), which has been technically
revised.
The changes are as follows:
— the technical specification becomes an ISO standard;
— GC-MS/MS technique added in 8.9.3 and in Clause B.2;
— new extraction solvent in Clause 4;
— new Table 1 (certain substances added) in Clause 4;
— change in the safety instructions at the preparation of the sodium tetraethylborate solution in Clause 8;
— sample preparation reference to ISO 21061 in Clause 7;
— new Table 2 (certain substances added) in 8.3.1;
— deletion of the need for duplicate determinations in Clause 7;
— new Annex B for mass spectroscopy;
— deletion of the reference to ISO 22744-1 in the Bibliography.
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
ISO 16179:2025(en)
Introduction
Certain organotin compounds have been identified as carcinogenic. Thus, several countries have restricted
[1]
them in articles such as footwear, e.g. in the European Union by commission regulation (EU) 276/2010
[2]
amending regulation (EC) No 1907/2006 .
Further organotin compounds are restricted by footwear brands in their restricted substances lists (RSL).

v
International Standard ISO 16179:2025(en)
Footwear — Critical substances potentially present in
footwear and footwear components — Determination of
organotin compounds in footwear materials
1 Scope
This document specifies a test method for the qualification and quantification of organotin compounds by
applying gas chromatography coupled with mass spectrometry. This test method is applicable to all types of
footwear materials except metal hardware (see ISO/TR 16178).
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 3696, Water for analytical laboratory use — Specification and test methods
ISO 4787, Laboratory glass and plastic ware — Volumetric instruments — Methods for testing of capacity and for use
ISO 21061, Footwear — Chemical tests — General principles on the preparation of samples
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 organotin substances are extracted from the footwear material with methanol, in a medium-strength
acidic condition, using tropolone as a complexing agent.
In the previous version of this test method, the extraction solvent was a mixture of methanol-ethanol.
Comparisons have shown that methanol gives equivalent results to methanol-ethanol solution. It is still
possible to use extraction with methanol-ethanol solution.
The polar and high-boiling organotin is then converted to the corresponding volatile alkyl derivative, by
reaction with sodium tetraethylborate, NaB(Et) . Finally, it is detected and quantified by using a gas
chromatograph fitted with a mass selective detector [gas chromatograph with a single quadrupole mass
spectrometer (GC-MS) or gas chromatograph with a triple quadrupole mass spectrometer (GC-MS/MS)].
Table 1 indicates the list of target compounds which can be analysed with the method defined in this
document. This document is also applicable for further organotin substances provided that the method is
validated with the additional compounds.

ISO 16179:2025(en)
Table 1 — List of target compounds and internal standards that can be analysed
® b
Type of compound Compound CAS Registry Number
Monosubstituted Internal standard: n-heptyltin trichloride 59344-47-7
methyltin trichloride 993-16-8
n-butyltin trichloride 1118-46-3
n-octyltin trichloride 3091-25-6
phenyltin trichloride 1124-19-2
Disubstituted Internal standard: di-n-heptyltin dichloride 74340-12-8
dimethyltin dichloride 753-73-1
di-n-propyltin dichloride 867-36-7
di-n-butyltin dichloride 683-18-1
di-n-octyltin dichloride 3542-36-7
diphenyltin dichloride 1135-99-5
Trisubstituted Internal standard: tri-n-pentyltin chloride 3342-67-4
trimethyltin chloride 1066-45-1
tri-n-propyltin chloride 2279-76-7
a
tri-n-butyltin chloride 1461-22-9
tri-n-octyltin chloride 2587-76-0
triphenyltin chloride (or fentin chloride) 639-58-7
tricyclohexyltin chloride 3091-32-5
Tetrasubstituted Internal standard: tetra-n-propyltin 2176-98-9
tetra-n-ethyltin 597-64-8
tetra-n-butyltin 1461-25-2
a ®
If bis(tri-n-butyltin) oxide (TBTO), CAS RN 56-35-9, is present, it is detected as tri-n-butyltin.
b ® ®
CAS Registry Number (CAS RN ) is a trademark of the American Chemical Society (ACS). This information is given for the
convenience of users of this document and does not constitute an endorsement by ISO of the product named. Equivalent products
may be used if they can be shown to lead to the same results.
5 Reagents
Unless otherwise specified, use only reagents of recognized analytical grade and certified reference
st
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