SIST EN ISO 16181-2:2021
(Main)Footwear - Critical substances potentially present in footwear and footwear components - Part 2: Determination of phthalate without solvent extraction (ISO 16181-2:2021)
Footwear - Critical substances potentially present in footwear and footwear components - Part 2: Determination of phthalate without solvent extraction (ISO 16181-2:2021)
This document specifies a method for the determination of the content of specific phthalates (see Annex
A) by pyrolyzer/thermal desorption gas chromatography-mass spectrometry (Py/TD-GC-MS). This
document is applicable to all types of footwear materials except textiles.
NOTE See also CEN/TR 16417 for a list of the specific phthalates to which this document applies.
Schuhe - Möglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische Substanzen - Teil 2: Bestimmung von Phthalaten ohne Lösemittelextraktion (ISO 16181-2:2021)
Dieses Dokument legt ein Verfahren zur Bestimmung des Gehaltes an spezifischen Phthalaten (siehe Anhang A) mit Gaschromatographie-Massenspektrometrie mit Pyrolyse/thermischer Desorption (Py/TD GC MS) fest. Dieses Dokument gilt für alle Arten von Schuhwerkstoffen mit Ausnahme von Textilien.
ANMERKUNG Siehe auch CEN/TR 16417 für eine Liste von spezifischen Phthalaten, für die dieses Dokument anzuwenden ist.
WARNHINWEIS - Die Anwendung dieses Dokuments kann gefährliche Materialien, Arbeitsabläufe oder Geräte einschließen. Es bezweckt nicht, sämtliche in Zusammenhang mit seiner Anwendung stehenden Sicherheits- oder Umweltprobleme zu behandeln. Es liegt in der Verantwortung der Anwender dieses Dokuments, die geeigneten Maßnahmen zu ergreifen, um den Sicherheits- und Gesundheitsschutz des Personals und der Umwelt vor Anwendung des Dokuments sicherzustellen und die zu diesem Zweck anwendbaren gesetzlichen Beschränkungen zu bestimmen.
Chaussures - Substances critiques potentiellement présentes dans les chaussures et les composants des chaussures - Partie 2: Détermination des phtalates sans extraction par solvant (ISO 16181-2:2021)
Le présent document spécifie une méthode pour la détermination de la teneur en phtalates spécifiques (voir l’Annexe A) par pyrolyse/désorption thermique et chromatographie en phase gazeuse-spectrométrie de masse (Py/TD-GC-MS). Le présent document s’applique à tous les types de matériaux utilisés dans les chaussures, à l’exception des textiles.
NOTE Voir également le CEN/TR 16417, qui comporte une liste des phtalates spécifiques pour lesquels le présent document s’applique.
Obutev - Kritične snovi, ki so lahko v obutvi in sestavnih delih obutve - 2. del: Ugotavljanje ftalatov brez ekstrakcije s topilom (ISO 16181-2:2021)
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN ISO 16181-2:2021
01-september-2021
Nadomešča:
SIST-TS CEN ISO/TS 16181:2011
Obutev - Kritične snovi, ki so lahko v obutvi in sestavnih delih obutve - 2. del:
Ugotavljanje ftalatov brez ekstrakcije s topilom (ISO 16181-2:2021)
Footwear - Critical substances potentially present in footwear and footwear components
- Part 2: Determination of phthalate without solvent extraction (ISO 16181-2:2021)
Schuhe - Möglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische
Substanzen - Teil 2: Bestimmung von Phthalaten ohne Lösemittelextraktion (ISO 16181-
2:2021)
Chaussures - Substances critiques potentiellement présentes dans les chaussures et les
composants des chaussures - Partie 2: Détermination des phtalates sans extraction par
solvant (ISO 16181-2:2021)
Ta slovenski standard je istoveten z: EN ISO 16181-2:2021
ICS:
61.060 Obuvala Footwear
SIST EN ISO 16181-2:2021 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
---------------------- Page: 1 ----------------------
SIST EN ISO 16181-2:2021
---------------------- Page: 2 ----------------------
SIST EN ISO 16181-2:2021
EN ISO 16181-2
EUROPEAN STANDARD
NORME EUROPÉENNE
July 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 2:
Determination of phthalate without solvent extraction
(ISO 16181-2:2021)
Chaussures - Substances critiques potentiellement Schuhe - Möglicherweise in Schuhen und
présentes dans les chaussures et les composants des Schuhbestandteilen vorhandene kritische Substanzen -
chaussures - Partie 2: Détermination des phtalates sans Teil 2: Bestimmung von Phthalaten ohne
extraction par solvant (ISO 16181-2:2021) Lösemittelextraktion (ISO 16181-2:2021)
This European Standard was approved by CEN on 22 May 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 16181-2:2021 E
worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
SIST EN ISO 16181-2:2021
EN ISO 16181-2:2021 (E)
Contents Page
European foreword . 3
2
---------------------- Page: 4 ----------------------
SIST EN ISO 16181-2:2021
EN ISO 16181-2:2021 (E)
European foreword
This document (EN ISO 16181-2:2021) 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 January 2022, and conflicting national standards shall
be withdrawn at the latest by January 2022.
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.
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 websites.
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 16181-2:2021 has been approved by CEN as EN ISO 16181-2:2021 without any
modification.
3
---------------------- Page: 5 ----------------------
SIST EN ISO 16181-2:2021
---------------------- Page: 6 ----------------------
SIST EN ISO 16181-2:2021
INTERNATIONAL ISO
STANDARD 16181-2
First edition
2021-06
Footwear — Critical substances
potentially present in footwear and
footwear components —
Part 2:
Determination of phthalate without
solvent extraction
Chaussures — Substances critiques potentiellement présentes dans les
chaussures et les composants des chaussures —
Partie 2: Détermination des phtalates sans extraction par solvant
Reference number
ISO 16181-2:2021(E)
©
ISO 2021
---------------------- Page: 7 ----------------------
SIST EN ISO 16181-2:2021
ISO 16181-2:2021(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 16181-2:2021
ISO 16181-2:2021(E)
Contents Page
Foreword .iv
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 1
5 Apparatus . 2
6 Reagents and materials . 2
7 Sampling . 3
8 Test procedure . 3
8.1 Test sample preparation . 3
8.2 Calibration . 3
8.3 Chromatographic analysis . 4
8.3.1 The chromatography parameters for gas chromatograph – mass
spectrometer equipped with a pyrolyzer . 4
8.3.2 Qualitative and quantitative analysis by gas chromatograph – mass
spectrometer equipped with a pyrolyzer . 4
9 Calculation of phthalate compounds in the sample . 4
9.1 Calculation of the phthalate compounds in the sample . 4
9.2 Performance of the test method . 5
10 Detection limit . 5
11 Test report . 5
Annex A (informative) List of phthalates specified in CEN/TR 16417 . 6
Annex B (informative) Sampling guidelines . 9
Annex C (informative) Chromatography parameters for gas chromatography mass
spectrometry equipped with a pyrolyzer .12
Annex D (informative) Verification of the evolved gas analysis (EGA) thermal desorption zone .14
Annex E (informative) Examples of chromatogram for phthalate by Py/TD-GC-MS .16
Annex F (informative) Comparative test results of ISO 16181-1 and this document (i.e.
ISO 16181-2) .18
Bibliography .22
© ISO 2021 – All rights reserved iii
---------------------- Page: 9 ----------------------
SIST EN ISO 16181-2:2021
ISO 16181-2:2021(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 16181-2, together with ISO 16181-1, cancels and replaces ISO/TS 16181:2011,
which has been technically revised.
The main changes compared to the previous edition are as follows:
— phthalates were added to the list in Table A.1 (from 7 onwards);
— this document introduces a new technique.
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 16181-2:2021
INTERNATIONAL STANDARD ISO 16181-2:2021(E)
Footwear — Critical substances potentially present in
footwear and footwear components —
Part 2:
Determination of phthalate without 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 method for the determination of the content of specific phthalates (see Annex
A) by pyrolyzer/thermal desorption gas chromatography-mass spectrometry (Py/TD-GC-MS). This
document is applicable to all types of footwear materials except textiles.
NOTE See also CEN/TR 16417 for a list of the specific phthalates to which this document applies.
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 16181-1, Footwear — Critical substances potentially present in footwear and footwear components —
Part 1: Determination of phthalate with solvent extraction
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 sample is directly introduced into a pyrolyzer, the phthalates are thermally extracted under a
specific heat zone and then transferred to the gas chromatograph. Phthalate compounds are separated
by the gas chromatographic capillary column and detected by a mass spectrometer.
When compared to ISO 16181-1, the two analytical methods should present similar trends but at the
same time, not necessarily the same absolute result. Therefore, in case of any dispute, ISO 16181-1 shall
be used in preference.
© ISO 2021 – All rights reserved 1
---------------------- Page: 11 ----------------------
SIST EN ISO 16181-2:2021
ISO 16181-2:2021(E)
5 Apparatus
5.1 Analytical balance, capable of measuring accurately to 0,000 01 g (0,01 mg).
5.2 Cryogenic grinding/milling mill with liquid N cooling.
2
5.3 Nipper (a hand tool for cutting samples).
5.4 Micro spatula.
5.5 Tweezers.
5.6 Cutter.
5.7 File.
5.8 Micro puncher.
5.9 Deactivated glass wool.
5.10 Micro syringes or automated pipettes.
5.11 Sample cup.
5.12 Volumetric flasks, 10 ml and 100 ml.
5.13 Gas chromatograph – mass spectrometer equipped with a pyrolyzer.
— Pyrolyzer/thermal desorption accessory:
A temperature rise of 1 °C to 100 °C per minute should be possible across a temperature range from
40 °C to 500 °C. The sample cup should be treated for chemical stability and should be capable of
accommodating both liquid and solid samples. It should be possible to maintain the interface between
the thermal pyrolysis unit and the gas chromatograph inlet up to 400 °C.
6 Reagents and materials
All reagent chemicals shall be tested for contamination and blank values prior to application as follows.
6.1 n-hexane, for preparing the phthalates standard solution, GC grade or higher.
6.2 Phthalates, see Table A.1.
6.3 Helium, purity greater than a volume fraction of 99,999 %.
6.4 Calibrants: prepare stock solutions containing 100 mg/l of each phthalate (see Annex A) in
n-hexane (6.1).
NOTE A commercially available Certified Reference Materials (CRM) containing specific phthalates could be
used as a calibrant.
2 © ISO 2021 – All rights reserved
---------------------- Page: 12 ----------------------
SIST EN ISO 16181-2:2021
ISO 16181-2:2021(E)
6.4.1 Stock solution of phthalates, 10 000 mg/l.
Weigh accurately 100 mg of each phthalate (6.2) into a 10 ml volumetric flask (5.12) respectively and
dissolve with n-hexane (6.1) and then fill it up to the mark.
6.4.2 Standard solution for calibration curve of phthalates, 100 mg/l.
Add 1 ml of each stock solution of phthalates (6.4.1) to 100-ml volumetric flasks (5.12) and filled up to
the mark with n-hexane (6.1).
6.5 Blank material (no phthalate compounds shall be included).
7 Sampling
In the footwear, all types of footwear materials shall be tested except:
— textiles (without any coating), and
— metallic parts.
Information on sampling are given in Annex B
If the sample consists of homogeneous materials, then the sample shall be cut into small pieces using
a cutting tool (5.6 to 5.8). Place approximately 0,5 mg of the cut sample into a pre-weighed sample cup
using a micro spatula (5.4) or tweezers (5.5). Record the total weight of the cup with the sample in it
to the nearest 0,01 mg and then record the sample weight by subtracting the weight of the sample cup
from the total weight.
If the sample consists of heterogeneous materials (multi-layer materials), the sample shall be ground to
pass through a 500 μm sieve before extraction. Cryogenic grinding/milling with liquid N cooling (5.2)
2
is recommended. Place approximately 0,5 mg of the powdered sample into a pre-weighed sample cup
using a micro spatula (5.4) or tweezers (5.5). Record the total weight of the cup with the sample in it to
the nearest 0,01 mg and record the sample weight by subtracting the weight of the sample cup from the
total weight.
8 Test procedure
8.1 Test sample preparation
Place an appropriate amount of deactivated glass wool into the cup with the sample to ensure that the
sample powder will not spill out. Determine the phthalates by Py/TD-GC-MS (5.13). An example of a
programme and the parameters for the GC-MS analysis of the target phthalates are given in Annex C.
The measure of the sample weight using a balance can be unstable at a digit of 0,01 mg. To check the
accuracy of the weighting sample, it is recommended to check the reproducibility of the weighting
sample. If the reproducibility of weighting one sample five times is below 10 %, it is then possible to use
the average value as the sample weight.
8.2 Calibration
Prepare at least three appropriate phthalate calibration solutions.
Example for calibration solutions, see Table 1. 1, 2, 5 and 10 μl of 100 mg/l phthalates standard solution
(6.4.2) should be put into the sample cups, respectively.
© ISO 2021 – All rights reserved 3
---------------------- Page: 13 ----------------------
SIST EN ISO 16181-2:2021
ISO 16181-2:2021(E)
Table 1
...
SLOVENSKI STANDARD
oSIST prEN ISO 16181-2:2019
01-november-2019
Obutev - Kritične snovi, ki so lahko v obutvi in sestavnih delih obutve - 2. del:
Ugotavljanje ftalatov brez ekstrakcije s topilom (ISO/DIS 16181-2:2019)
Footwear - Critical substances potentially present in footwear and footwear components
- Part 2: Determination of phthalate without solvent extraction (ISO/DIS 16181-2:2019)
Schuhe - Möglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische
Substanzen - Teil 2: Bestimmung von Phthalaten ohne Lösemittelextraktion (ISO/DIS
16181-2:2019)
Chaussures - Substances critiques potentiellement présentes dans les chaussures et les
composants des chaussures - Partie 2: Détermination des phtalates sans extraction par
solvant (ISO/DIS 16181-2:2019)
Ta slovenski standard je istoveten z: prEN ISO 16181-2
ICS:
61.060 Obuvala Footwear
oSIST prEN ISO 16181-2:2019 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
---------------------- Page: 1 ----------------------
oSIST prEN ISO 16181-2:2019
---------------------- Page: 2 ----------------------
oSIST prEN ISO 16181-2:2019
DRAFT INTERNATIONAL STANDARD
ISO/DIS 16181-2
ISO/TC 216 Secretariat: UNE
Voting begins on: Voting terminates on:
2019-09-18 2019-12-11
Footwear — Critical substances potentially present in
footwear and footwear components —
Part 2:
Determination of phthalate without solvent extraction
Chaussures — Substances critiques potentiellement présentes dans les chaussures et les composants des
chaussures -- —
Partie 2: Détermination des phtalates sans 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 16181-2:2019(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 16181-2:2019
ISO/DIS 16181-2:2019(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 16181-2:2019
ISO/DIS 16181-2:2019(E)
Contents Page
Foreword .iv
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 1
5 Apparatus . 1
6 Reagents and materials . 2
7 Sampling . 3
8 Test procedure . 3
8.1 Test sample preparation . 3
8.2 Calibration . 3
8.3 Chromatographic analysis . 3
8.3.1 The chromatography parameters for gas chromatograph — mass
spectrometer equipped with pyrolyzer . 3
8.3.2 Qualitative and quantitative analysis by gas chromatograph — mass
spectrometer equipped with pyrolyzer . 3
9 Calculation of phthalate compounds in the sample . 4
10 Detection limit . 4
11 Test report . 4
Annex A (informative) The list of phthalates specified in CEN/TR 16417 .5
Annex B (informative) Sampling guideline . 7
Annex C (informative) The chromatography parameters for gas chromatography mass
spectrometry equipped with pyrolyzer . . 9
Annex D (informative) Verification of the EGA thermal desorption zone .11
Annex E (informative) Examples of chromatogram for phthalate by Py/TD-GC-MS .13
Bibliography .14
© ISO 2019 – All rights reserved iii
---------------------- Page: 5 ----------------------
oSIST prEN ISO 16181-2:2019
ISO/DIS 16181-2:2019(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 16181-1 cancels and replaces ISO/TS 16181:2013, which has been
technically revised.
iv © ISO 2019 – All rights reserved
---------------------- Page: 6 ----------------------
oSIST prEN ISO 16181-2:2019
DRAFT INTERNATIONAL STANDARD ISO/DIS 16181-2:2019(E)
Footwear — Critical substances potentially present in
footwear and footwear components —
Part 2:
Determination of phthalate without solvent extraction
1 Scope
This international standard specifies a method for the determination of the content of specific
phthalates (Annex A) by pyrolyzer/thermal desorption gas chromatography-mass spectrometry (Py/
TD-GC-MS). This international standard is applicable to all types of footwear materials except textiles.
NOTE ISO/TR 16417:2017 defines which phthalates are concerned by this determination.
2 Normative references
There are no normative references in this document.
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
This test method is designed to specify procedures for qualitative and quantitative of specific phthalates
in footwear materials by pyrolyer/thermal desorption gas chromatography-mass spectrometry(Py/
TD-GC-MS). The sample is directly introduced into pyrolyzer, thermally extract phthalates under a
specific heat zone and then transferred to the gas chromatograph. Phthalate compounds are separated
by gas chromatographic capillary column and detected by mass spectrometer.
5 Apparatus
5.1 Analytical balance capable of measuring accurately to 0,000 01 g (0,01 mg)
5.2 cryogenic grinding/milling mill with liquid N cooling
2
5.3 nipper (a hand tool for cutting samples)
5.4 micro spatula
5.5 tweezers
5.6 cutter
© ISO 2019 – All rights reserved 1
---------------------- Page: 7 ----------------------
oSIST prEN ISO 16181-2:2019
ISO/DIS 16181-2:2019(E)
5.7 file
5.8 micro puncher
5.9 deactivated glass wool
5.10 micro syringe or automated pipettes
5.11 sample cup
5.12 Volumetric flasks 10 mL and 100 mL
5.13 gas chromatograph - mass spectrometer equipped with pyrolyzer:
— Pyrolyzer/thermal desorption accessory:
A temperature rise of 1 °C to 100 °C per minute should be possible across a temperature range from
40 °C to 500 °C. The sample cup should be treated for chemical stability, and should be capable of
accommodating both liquid and solid samples. It should be possible to maintain the interface between
the thermal pyrolysis unit and the gas chromatograph inlet up to 400 °C.
6 Reagents and materials
All reagent chemicals shall be tested for contamination and blank values prior to application as follow:
6.1 n-Hexane for preparing the phthalates standard solution, GC grade or higher
6.2 Phthalates (Annex A)
6.3 Helium (purity greater than a volume fraction of 99,999 %)
6.4 Calibrants:
a) Prepare stock solutions containing 100 mg/L of each phthalate(Annex A) in n-hexane(6.1)
respectively.
NOTE A commercially available CRM is polypropylene resin pellet containing BBP, DBP DEHP and DNOP
(National Metrology Institute of Japan, NMIJ CRM 8151-a), PVC containing BBP, DBP DEHP and DNOP (Korean
Research Institute for Standards and Science, KRISS CRM 113-03-006), or polyethylene containing BBP, DBP, DEHP,
DEP (Diethyl phthalate), DIDP, DINP, DMP (Dimethyl phthalate) and DNOP (SPEX CertiPrep, US, CRM-PE001).
6.4.1 Stock solution of phthalates, 10 000 mg/L
100 mg of the respective phthalate are dissolved in different 10 mL volumetric flasks (5.12) with
n-hexane (6.1) and filled up to the mark.
6.4.2 Standard solution for calibration curve of phthalates, 100 mg/L
Add 1 mL of each stock solution of phthalates (6.4.1) into a 100 mL volumetric flasks (5.12) and filled up
to the mark with n-hexane (6.1).
6.5 Blank material (no phthalate compounds shall be included).
2 © ISO 2019 – All rights reserved
---------------------- Page: 8 ----------------------
oSIST prEN ISO 16181-2:2019
ISO/DIS 16181-2:2019(E)
7 Sampling
Definition of the sampling need to be done.
In the footwear, all types of footwear materials except textiles shall be tested.
If the sample consists of homogeneous materials, the sample can either be cut into small pieces using a
cutting tool(5.6~5.8).
If the sample consists of heterogeneous materials (multi-layer materials), the sample shall be ground to
pass through a 500 μm sieve before extraction. Cryogenic grinding/milling with liquid N2 cooling(5.2)
is strongly recommended. More detail procedure described in annex B.
8 Test procedure
8.1 Test sample preparation
Place approximately 0,5 mg of the cut or powdered sample into a pre-weighed sample cup using a micro
spatula(5.4) or tweezers(5.5). Record the total weight of the cup with the sample in it to the nearest
0,01 mg and record the sample weight by subtracting the weight of the sample cup from the total
weight. Place an appropriate amount of deactivated glass wool into the sample cup to ensure that the
sample powder will not spill out.
NOTE The measure of sample weight using a balance may be unstable at digit of 0.01 mg. To check the
accuracy of weighting sample, it is recommend to check reproducibility of weighting sample. If the reproducibility
of five times weighting of one sample is below 10 %, it is possible to use the average value as the sample weight.
8.2 Calibration
1, 2, 5 and 10 μL of 100 mg/L phthalates standard solution (6.4.2) were put into sample cups,
respectively.
Table 1 — Calibration standard
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.