Footwear - Critical substances potentially present in footwear and footwear components - Part 1: Determination of phthalate with solvent extraction (ISO 16181-1:2021)

This document specifies a test method to determine the qualitative and quantitative presence of
phthalate compounds (see Annex A) in footwear and footwear components.
NOTE 1 A list of relevant materials potentially containing phthalates can be found in ISO/TR 16178:2012,
Annex A or in CEN/TR 16417.
NOTE 2 This test method can also be used to determine phthalates other than those listed in Annex A, subject
to validation.

Schuhe - Möglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische Substanzen - Teil 1: Bestimmung von Phthalaten mit Lösemittelextraktion (ISO 16181-1:2021)

Dieses Dokument legt ein Prüfverfahren zur Bestimmung des qualitativen und quantitativen Vorliegens von Phthalatverbindungen (siehe Anhang A) in Schuhen und Schuhbestandteilen fest.
ANMERKUNG 1 Eine Liste der betroffenen Werkstoffe, die möglicherweise Phthalate enthalten, kann ISO/TR 16178:2012, Anhang A, oder CEN/TR 16417 entnommen werden.
ANMERKUNG 2 Dieses Prüfverfahren kann auch angewendet werden, um andere als die in Anhang A aufgeführten Phthalate zu bestimmen, Validierung vorausgesetzt.

Chaussures - Substances critiques potentiellement présentes dans les chaussures et les composants des chaussures - Partie 1: Détermination des phtalates dans les solvants d'extraction (ISO 16181-1:2021)

Obutev - Kritične snovi, ki so lahko v obutvi in sestavnih delih obutve - 1. del: Ugotavljanje ftalatov z ekstrakcijo topila (ISO 16181-1:2021)

General Information

Status
Published
Public Enquiry End Date
30-Nov-2019
Publication Date
04-May-2021
Technical Committee
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
22-Apr-2021
Due Date
27-Jun-2021
Completion Date
05-May-2021

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SLOVENSKI STANDARD
SIST EN ISO 16181-1:2021
01-junij-2021
Nadomešča:
SIST-TS CEN ISO/TS 16181:2011

Obutev - Kritične snovi, ki so lahko v obutvi in sestavnih delih obutve - 1. del:

Ugotavljanje ftalatov z ekstrakcijo topila (ISO 16181-1:2021)

Footwear - Critical substances potentially present in footwear and footwear components

- Part 1: Determination of phthalate with solvent extraction (ISO 16181-1:2021)
Schuhe - Möglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische

Substanzen - Teil 1: Bestimmung von Phthalaten mit Lösemittelextraktion (ISO 16181-

1:2021)

Chaussures - Substances critiques potentiellement présentes dans les chaussures et les

composants des chaussures - Partie 1: Détermination des phtalates dans les solvants

d'extraction (ISO 16181-1:2021)
Ta slovenski standard je istoveten z: EN ISO 16181-1:2021
ICS:
61.060 Obuvala Footwear
SIST EN ISO 16181-1:2021 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
SIST EN ISO 16181-1:2021
---------------------- Page: 2 ----------------------
SIST EN ISO 16181-1:2021
EN ISO 16181-1
EUROPEAN STANDARD
NORME EUROPÉENNE
April 2021
EUROPÄISCHE NORM
ICS 61.060 Supersedes CEN ISO/TS 16181:2011
English Version
Footwear - Critical substances potentially present in
footwear and footwear components - Part 1:
Determination of phthalate with solvent extraction (ISO
16181-1:2021)

Chaussures - Substances critiques potentiellement Schuhe - Möglicherweise in Schuhen und

présentes dans les chaussures et les composants des Schuhbestandteilen vorhandene kritische Substanzen -

chaussures - Partie 1: Détermination des phtalates par Teil 1: Bestimmung von Phthalaten mit

extraction au solvant (ISO 16181-1:2021) Lösemittelextraktion (ISO 16181-1:2021)
This European Standard was approved by CEN on 12 February 2021.

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, Turkey 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

© 2021 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 16181-1:2021 E

worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
SIST EN ISO 16181-1:2021
EN ISO 16181-1:2021 (E)
Contents Page

European foreword ....................................................................................................................................................... 3

---------------------- Page: 4 ----------------------
SIST EN ISO 16181-1:2021
EN ISO 16181-1:2021 (E)
European foreword

This document (EN ISO 16181-1:2021) 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 October 2021, and conflicting national standards shall

be withdrawn at the latest by October 2021.

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 16181:2011.

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, Turkey and the

United Kingdom.
Endorsement notice

The text of ISO 16181-1:2021 has been approved by CEN as EN ISO 16181-1:2021 without any

modification.
---------------------- Page: 5 ----------------------
SIST EN ISO 16181-1:2021
---------------------- Page: 6 ----------------------
SIST EN ISO 16181-1:2021
INTERNATIONAL ISO
STANDARD 16181-1
First edition
2021-03
Footwear — Critical substances
potentially present in footwear and
footwear components —
Part 1:
Determination of phthalate with
solvent extraction
Chaussures — Substances critiques potentiellement présentes dans les
chaussures et les composants des chaussures —
Partie 1: Détermination des phtalates par extraction au solvant
Reference number
ISO 16181-1:2021(E)
ISO 2021
---------------------- Page: 7 ----------------------
SIST EN ISO 16181-1:2021
ISO 16181-1:2021(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2021

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 2021 – All rights reserved
---------------------- Page: 8 ----------------------
SIST EN ISO 16181-1:2021
ISO 16181-1:2021(E)
Contents Page

Foreword ........................................................................................................................................................................................................................................iv

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

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

3 Terms and definitions ..................................................................................................................................................................................... 1

4 Principle ........................................................................................................................................................................................................................ 1

5 Reagents ........................................................................................................................................................................................................................ 2

5.1 Chemicals ..................................................................................................................................................................................................... 2

5.2 Standard solutions ............................................................................................................................................................................... 2

5.2.1 Target phthalates — Stock solution ................................................................................................................ 2

5.2.2 Internal standard — Stock solution ................................................................................................................ 2

5.2.3 Calibration solutions .................................................................................................................................................... 3

5.2.4 Extraction solution with internal standard (optional) ................................................................... 3

6 Apparatus ..................................................................................................................................................................................................................... 3

7 Sampling ........................................................................................................................................................................................................................ 4

8 Test procedure ........................................................................................................................................................................................................ 4

8.1 Extraction .................................................................................................................................................................................................... 4

8.1.1 Ultrasonic extraction .................................................................................................................................................... 4

8.1.2 Alternative extraction procedure for PVC materials ......................................................................... 4

8.1.3 Preparation of a method blank ............................................................................................................................ 5

8.2 Determination with GC-MS........................................................................................................................................................... 5

9 Expression of results ........................................................................................................................................................................................ 5

9.1 Calibration curve ................................................................................................................................................................................... 5

9.2 Determination of the phthalates content ......................................................................................................................... 5

9.2.1 For each phthalate .......................................................................................................................................................... 5

9.2.2 When a sum of phthalates is requested ....................................................................................................... 6

9.3 Performance of the test method .............................................................................................................................................. 6

10 Test report ................................................................................................................................................................................................................... 6

Annex A (informative) Information on some identified phthalates .................................................................................... 8

Annex B (informative) Information on some identified phthalates .................................................................................... 9

Annex C (informative) Suitable gas chromatography-mass spectrometry (GC-MS) apparatus

and detection limits for determination of phthalates ................................................................................................11

Annex D (informative) Results of the interlaboratories tests – Method using toluene

extraction (8.1.1) ...............................................................................................................................................................................................13

Annex E (informative) Example of a chromatogram for selected phthalates ..........................................................15

Annex F (informative) Comparison of extraction of phthalates by using toluene and THF .....................16

Bibliography .............................................................................................................................................................................................................................18

© ISO 2021 – All rights reserved iii
---------------------- Page: 9 ----------------------
SIST EN ISO 16181-1:2021
ISO 16181-1:2021(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).

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 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 first edition of ISO 16181-1, together with ISO 16181-2, cancels and replaces ISO/TS 16181:2011,

which has been technically revised.
The main changes compared to the previous edition are as follows:
— addition of number of phthalates from 7 to 26;
— addition of new Clause 2 and Clause 3, and renumbering of subsequent clauses;

— replacement of “n-hexane/acetone” with “toluene” and alternative “tetrahydrofuran” as extraction

solution;

— splitting of former Clause 3 into Clauses 5 and 6, with technical modification;

— technical revision of Clauses 4 and 5;
— deletion of 5.2.4;
— addition of Clause 9;
— addition of Annex D.

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 2021 – All rights reserved
---------------------- Page: 10 ----------------------
SIST EN ISO 16181-1:2021
INTERNATIONAL STANDARD ISO 16181-1:2021(E)
Footwear — Critical substances potentially present in
footwear and footwear components —
Part 1:
Determination of phthalate with solvent extraction

WARNING — The use of this document can involve hazardous materials, operations and

equipment. It does not purport to address all of the safety or environmental problems associated

with its use. It is the responsibility of users of this document to take appropriate measures

to ensure the safety and health of personnel and the environment prior to application of the

document, and to determine the applicability of regulatory limitations for this purpose.

1 Scope

This document specifies a test method to determine the qualitative and quantitative presence of

phthalate compounds (see Annex A) in footwear and footwear components.

NOTE 1 A list of relevant materials potentially containing phthalates can be found in ISO/TR 16178:2012,

Annex A or in CEN/TR 16417.

NOTE 2 This test method can also be used to determine phthalates other than those listed in Annex A, subject

to validation.
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 4787:2010, Laboratory glassware — Volumetric instruments — Methods for testing of capacity

and for use
3 Terms and definitions
No terms and definitions are listed in this document.

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

— ISO Online browsing platform: available at https:// www .iso .org/ obp
— IEC Electropedia: available at http:// www .electropedia .org/
4 Principle

The test sample is extracted using toluene at 60 °C in an ultrasonic bath for 1 h. An aliquot is then

analysed using a gas chromatograph (GC) with a mass selective detector (MS).
All the abbreviations of phthalates used are given in Annex A.

When compared with ISO 16181-2, the two analytical methods should give similar trends but not

necessarily the same absolute result. Therefore, in cases of dispute, the method in this document shall

be used in preference to ISO 16181-2.
© ISO 2021 – All rights reserved 1
---------------------- Page: 11 ----------------------
SIST EN ISO 16181-1:2021
ISO 16181-1:2021(E)
5 Reagents
5.1 Chemicals
Unless otherwise specified, use only reagents of recognized analytical grade.
5.1.1 Toluene, Chemical Abstract Service Registry Number® ( CAS RN®): 108-88-3.
5.1.2 Internal standard
Either of the following chemicals can be used as internal standard:
— Bis (2-Ethylhexyl) phtalates-3,4,5,6-D4 (CAS RN®: 93951-87-2);
— Diphenylphthalate (CAS RN® 84-62-8)

NOTE 1 Diphenylphthalate gives appropriate results in case of DEHP <1 %. In case of DEHP >1 % the results of

all other phthalates can be affected because of poor resolution between DEHP and Diphenylphthalate.

NOTE 2 Other internal standards have been found convenient as Di-n-propylphthalate-3-4-5-6 D4 (CAS

RN®: 358731-29-0).
5.1.3 Phthalates, see Annexes A and B.
5.1.4 Acetone, CAS RN®: 67-64-1.
5.1.5 Methanol, CAS RN®: 67-56-1.
5.1.6 Cyclohexane, CAS RN®: 110-82-7.
5.1.7 Tetrahydrofurane (THF), CAS RN®: 109-99-9.
5.1.8 n-hexane, CAS RN®: 110-54-3.
5.2 Standard solutions
5.2.1 Target phthalates — Stock solution

Based on its tasks a laboratory shall decide which phthalates from Table A.1 need to be determined.

Based on this decision, standard stock solution for each phthalate shall be available either as

commercially available certified mixes, individual components in solution or self-prepared individual

standard stock solutions of each phthalate in toluene (5.1.1).

Prepare, for example, standard stock solutions with concentrations of 1 000 µg/ml, weigh 50,0 mg of

each phthalate depending on the purity (Table A.1) into 50 ml volumetric flasks, fill the volumetric

flasks up to the mark with toluene (5.1.1) and mix thoroughly to dissolve completely the substance.

5.2.2 Internal standard — Stock solution

Prepare an internal standard stock solution that is in the same concentration range as the standard

stock solutions (5.2.1) by dissolving the internal standard (5.1.2) in toluene (5.1.1) according to 5.2.1.

1) CAS Registry Number (CAS RN) is a registered 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.
2 © ISO 2021 – All rights reserved
---------------------- Page: 12 ----------------------
SIST EN ISO 16181-1:2021
ISO 16181-1:2021(E)
5.2.3 Calibration solutions

Prepare at least five appropriate phthalate calibration solutions, each containing an equal amount of

the target phthalates (5.1.3) and an amount of internal standard (5.1.2) in toluene (5.1.1) respectively

in n-hexane (5.1.8).
An examples of calibration solutions are shown in Table 1 and 2.
Table 1 — Example of calibration solutions extraction (8.1.1)
Standard L1 L2 L3 L4 L5
Concentration of phthalate (µg/ml) 2,5 25 50 75 100
Volume of the phthalate stock solution (µl) (5.2.1) 25 250 500 750 1 000
Volume of the internal standard stock solution (µl) (5.2.2) 500
Concentration of the internal standard (µg/ml) 50
Volume of toluene (µl) (5.1.1) (completed to 10ml) 9 475 9 250 9 000 8 750 8 500
Table 2 — Example of calibration solutions with THF extraction (8.1.2)
Standard L1 L2 L3 L4 L5
Concentration of phthalate (µg/ml) 1,0 3,0 15 30 90
Volume of the phthalate stock solution (µl) (5.2.1) 10 30 150 300 900
Volume of the internal standard sto
...

SLOVENSKI STANDARD
oSIST prEN ISO 16181-1:2019
01-november-2019

Obutev - Kritične snovi, ki so lahko v obutvi in sestavnih delih obutve - 1. del:

Ugotavljanje ftalatov z ekstrakcijo topila (ISO/DIS 16181-1:2019)

Footwear - Critical substances potentially present in footwear and footwear components

- Part 1: Determination of phthalate with solvent extraction (ISO/DIS 16181-1:2019)

Schuhe - Möglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische
Substanzen - Teil 1: Bestimmung von Phthalaten mit Lösemittelextraktion (ISO/DIS
16181-1:2019)

Chaussures - Substances critiques potentiellement présentes dans les chaussures et les

composants des chaussures - Partie 1: Détermination des phtalates dans les solvants

d'extraction (ISO/DIS 16181-1:2019)
Ta slovenski standard je istoveten z: prEN ISO 16181-1
ICS:
61.060 Obuvala Footwear
oSIST prEN ISO 16181-1:2019 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
oSIST prEN ISO 16181-1:2019
---------------------- Page: 2 ----------------------
oSIST prEN ISO 16181-1:2019
DRAFT INTERNATIONAL STANDARD
ISO/DIS 16181-1
ISO/TC 216 Secretariat: UNE
Voting begins on: Voting terminates on:
2019-09-19 2019-12-12
Footwear — Critical substances potentially present in
footwear and footwear components —
Part 1:
Determination of phthalate with solvent extraction

Chaussures — Substances critiques potentiellement présentes dans les chaussures et les composants des

chaussures —
Partie 1: Détermination des phtalates dans les solvants d'extraction
ICS: 61.060
THIS DOCUMENT IS A DRAFT CIRCULATED
This document is circulated as received from the committee secretariat.
FOR COMMENT AND APPROVAL. IT IS
THEREFORE SUBJECT TO CHANGE AND MAY
NOT BE REFERRED TO AS AN INTERNATIONAL
STANDARD UNTIL PUBLISHED AS SUCH.
IN ADDITION TO THEIR EVALUATION AS
ISO/CEN PARALLEL PROCESSING
BEING ACCEPTABLE FOR INDUSTRIAL,
TECHNOLOGICAL, COMMERCIAL AND
USER PURPOSES, DRAFT INTERNATIONAL
STANDARDS MAY ON OCCASION HAVE TO
BE CONSIDERED IN THE LIGHT OF THEIR
POTENTIAL TO BECOME STANDARDS TO
WHICH REFERENCE MAY BE MADE IN
Reference number
NATIONAL REGULATIONS.
ISO/DIS 16181-1:2019(E)
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 SUPPORTING DOCUMENTATION. ISO 2019
---------------------- Page: 3 ----------------------
oSIST prEN ISO 16181-1:2019
ISO/DIS 16181-1:2019(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2019

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
Fax: +41 22 749 09 47
Email: copyright@iso.org
Website: www.iso.org
Published in Switzerland
ii © ISO 2019 – All rights reserved
---------------------- Page: 4 ----------------------
oSIST prEN ISO 16181-1:2019
ISO/DIS 16181-1:2019(E)
Contents Page

Foreword ........................................................................................................................................................................................................................................iv

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

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

3 Terms and definitions ..................................................................................................................................................................................... 1

4 Principle ........................................................................................................................................................................................................................ 1

5 Reagents ........................................................................................................................................................................................................................ 2

5.1 Chemicals ..................................................................................................................................................................................................... 2

5.2 Standard solutions ............................................................................................................................................................................... 2

5.2.1 Target Phthalates - stock solution ..................................................................................................................... 2

5.2.2 Internal standard – stock solution .................. .................................................................................................. 2

5.2.3 Calibration solutions .................................................................................................................................................... 2

5.2.4 Extraction solution with internal standard (optional) ................................................................... 3

6 Apparatus ..................................................................................................................................................................................................................... 3

7 Sampling ........................................................................................................................................................................................................................ 3

8 Test procedure ........................................................................................................................................................................................................ 4

8.1 Extraction .................................................................................................................................................................................................... 4

8.1.1 Ultrasonic extraction .................................................................................................................................................... 4

8.1.2 Alternative extraction procedures for PVC materials ...................................................................... 4

8.1.3 Preparation of a method blank ............................................................................................................................ 4

8.2 Determination with GC-MS........................................................................................................................................................... 4

9 Expression of results ........................................................................................................................................................................................ 5

9.1 Calibration curve ................................................................................................................................................................................... 5

9.2 Determination of the phthalates content ......................................................................................................................... 5

10 Test report ................................................................................................................................................................................................................... 6

Annex A (normative) Information for some identified phthalates ....................................................................................... 7

Annex B (informative) Suitable gas chromatography-mass spectrometry (GC-MS) apparatus

and detection limits for determination of phthalates ................................................................................................10

Annex C (informative) Example of total ion chromatogram for phthalates ..............................................................12

Annex D (informative) Extraction of phthalates by using toluene and THF .............................................................13

Bibliography .............................................................................................................................................................................................................................15

© ISO 2019 – All rights reserved iii
---------------------- Page: 5 ----------------------
oSIST prEN ISO 16181-1:2019
ISO/DIS 16181-1:2019(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).

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 Technical Committee ISO/TC 216 Footwear.

This document together with ISO 16181-2 cancels and replaces ISO/TS 16181:2013, which has been

technically revised.
iv © ISO 2019 – All rights reserved
---------------------- Page: 6 ----------------------
oSIST prEN ISO 16181-1:2019
DRAFT INTERNATIONAL STANDARD ISO/DIS 16181-1:2019(E)
Footwear — Critical substances potentially present in
footwear and footwear components —
Part 1:
Determination of phthalate with solvent extraction

WARNING — The use of this document can involve hazardous materials, operations and

equipment. It does not purport to address all of the safety or environmental problems associated

with its use. It is the responsibility of users of this standard to take appropriate measures

to ensure the safety and health of personnel and the environment prior to application of the

standard, and fulfil statutory and regulatory requirements for this purpose.
1 Scope

This part of ISO 16181 specifies a test method to determine the qualitatively and quantitatively

presence of phthalate compounds (Annex A) in footwear and footwear components.
NOTE 1 A list of relevant materials can be found in ISO/TR 16178, Annex A.

NOTE 2 This test method can also be used to determine phthalates other than listed in Annex A subject to

validation.
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 4787, Laboratory glassware — Volumetric instruments — Methods for testing of capacity and for use

ISO/TR 16178, Footwear — Critical substances potentially present in footwear and footwear components

3 Terms and definitions
No terms and definitions are listed in this document.

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

— ISO Online browsing platform: available at http: //www .iso .org/obp
— IEC Electropedia: available at http: //www .electropedia .org/
4 Principle

The test sample is extracted using toluene at 60 °C in an ultrasonic bath for 1 h. An aliquot is then

analysed using a gas chromatograph with mass selective detector.
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5 Reagents
5.1 Chemicals
Unless otherwise specified, use only reagents of recognized analytical grade.
5.1.1 Toluene, CAS number: 108-88-3.
5.1.2 Bis (2-Ethylhexyl) phtalates-3,4,5,6-D4 (CAS number: 93951-87-2)
5.1.3 Phthalates, see Annex 1.
5.1.4 Acetone, CAS number: 67-64-1.
5.1.5 Methanol, CAS number: 67-56-1.
5.1.6 Cyclohexane, CAS number: 110-82-7.
5.1.7 Tetrahydrofurane (THF), CAS number: 109-99-9
5.1.8 n-hexane, CAS number: 110-54-3
5.2 Standard solutions
5.2.1 Target Phthalates - stock solution

Based on its tasks a laboratory shall decide which phthalates out of Table A.1 needs to be determined.

Based on this decision standard stock solution for each phthalate shall be available either as

commercially available certified mixes or individual components in solution or as self-prepared

individual standard stock solutions of each phthalate in toluene (5.1.1).

EXAMPLE For standard stock solutions with concentrations of 1000 µg/ml, weigh 50,0 mg of each phthalate

(Table A.1) into 50 ml volumetric flasks, fill the volumetric flasks up to the mark with toluene (5.1.1) and mix

thoroughly to dissolve completely the substance.
5.2.2 Internal standard – stock solution

Prepare an internal standard stock solution which is in the same concentration range as the standard

stock solutions (5.2.1) by dissolving the internal standard (5.1.2) in toluene (5.1.1) according to the

example in 5.2.1.
5.2.3 Calibration solutions

Prepare at least five appropriate phthalate calibration solutions, each containing an equal amount of

the target phthalates (5.1.3) and an amount of internal standard (5.1.2) in toluene (5.1.1).

Example for calibration solutions, see Table 1.
Table 1 — Example of calibration solutions
Standard L1 L2 L3 L4 L5
Concentration of phthalate (µg/ml) 2,5 25 50 75 100
1) CAS: Chemical Abstract Service.
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Table 1 (continued)
Standard L1 L2 L3 L4 L5
Volume of the phthalate stock solution (µl) (5.2.1) 25 250 500 750 1 000
Volume of the internal standard stock solution (µl) (5.2.2) 500
Concentration of the internal standard (µg/ml) 50
Volume of toluene (µl) (5.1.1) (completed to 10ml) 9 475 9 250 9 000 8 750 8 500
5.2.4 Extraction solution with internal standard (optional)

Prepare the extraction solution with the same concentration of an internal standard as in the calibration

solutions (e.g. 50 µg/ml) by diluting internal standard working solution (5.2.2) with toluene (5.1.1).

6 Apparatus

The usual laboratory apparatus and laboratory glassware, according to ISO 4787, shall be used, in

addition to the following.

Glassware, after washing, should be given an extra rinse with 0,1 N nitric acid and finally with acetone,

acetone/methanol and/or cyclohexane.
6.1 Analytical balance, with a precision of at least 0,1 mg.
6.2 Flask with Teflon stopper, e.g. 20 ml.

6.3 Ultrasonic bath with adjustable temperature, suitable for operation at 60 °C.

6.4 PTFE-membrane filter, pore width 0,45 µm.
6.5 Volumetric flasks of suitable volume.
6.6 GC vials, e.g. 2 ml
6.7 Gas chromatograph with mass-selective
...

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