SIST EN IEC 62321-11:2024
(Main)Determination of certain substances in electrotechnical products - Part 11: Tris (2-chloroethyl) phosphate (TCEP) in plastics by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS)
Determination of certain substances in electrotechnical products - Part 11: Tris (2-chloroethyl) phosphate (TCEP) in plastics by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS)
This part of IEC 62321 specifies two different techniques for the determination of TCEP tris(2-chloroethyl) phosphate (TCEP) in plastics, the GC-MS or LC-MS method; both of which are suitable for quantitative analysis.
These two techniques have been evaluated for use with polyurethane, Polyvinyl chloride and polyethylene materials containing TCEP between 200 mg/kg to 2 000 mg/kg. Use of the methods escribed in International Standard for other polymers and concentration ranges has not been specifically evaluated.
These test methods do not apply to plastics materials having a processing temperature higher than 230 ℃.
NOTE TCEP starts thermal decomposition at approximately 230 ℃. Polymer types which have a processing temperature into shapes of plastics (e.g. pellets, moulded parts, or sheets etc.) not exceeding the decomposition temperature can contain TCEP.
Py-TD-GC-MS is another technique, suitable for the screening of TCEP in plastics (See Annex A).
Določevanje posameznih snovi v elektrotehničnih izdelkih - 11. del: Določevanje ? tris (2-kloroetil) fosfata (TCEP) v plastiki ? polimernih materialih ? s plinsko kromatografijo-masno spektrometrijo (GC-MS) in tekočinsko kromatografijo-masno spektrometrijo (LC-MS)
Détermination de certaines substances dans les produits électrotechniques - Partie 11: Phosphate de tris(2-chloroéthyle) (TCEP) dans les plastiques par chromatographie en phase gazeuse-spectrométrie de masse (GC-MS) et chromatographie en phase liquide-spectrométrie de masse (LC-MS)
L'IEC 62321-11:2023 spécifie deux techniques différentes pour la détermination du phosphate de tris(2‑chloroéthyle) (TCEP) dans les plastiques, à savoir la méthode GC-MS et la méthode LC-MS, qui s'appliquent toutes les deux pour une analyse quantitative. Ces deux techniques s'appliquent aux matériaux en polyuréthane, en polychlorure de vinyle et en polyéthylène qui contiennent entre 200 mg/kg et 2 000 mg/kg de TCEP. Ces méthodes d'essai ne s'appliquent pas aux matières plastiques dont la température de mise en œuvre est supérieure à 230 °C. La technique de GC-MS à l'aide d'un pyrolyseur/accessoire de désorption thermique (Py/TD-GC-MS) est décrite à l'Annexe A et peut être utilisée pour la détection du TCEP dans les plastiques.
Določevanje posameznih snovi v elektrotehničnih izdelkih - 11. del: Določevanje tri(2-kloroetil) fosfata (TCEP) v polimernih materialih s plinsko kromatografijo in masno spektrometrijo (GC-MS) ter tekočinsko kromatografijo in masno spektrometrijo (LC-MS)
Ta del standarda IEC 62321 določa različni tehniki za določevanje tri(2-kloroetil) fosfata (TCEP) v polimernih materialih s plinsko kromatografijo in masno spektrometrijo (GC-MS) ter tekočinsko kromatografijo in masno spektrometrijo (LC-MS), oba postopka pa se uporabljata za kvantitativno analizo.
Obe tehniki se uporabljata s poliuretanskimi, polivinilkloridnimi in polietilenskimi materiali z vsebnostjo tri(2-kloroetil) fosfata med 200 mg/kg in 2000 mg/kg.
Metodi se ne uporabljata za polimerne materiale, ki imajo temperaturo obdelave večjo od 230 °C.
Plinska kromatografija in masna spektrometrija, ki uporablja tehniko za pirolizo/toplotno desorpcijo (Py/TD-GC-MS), je opisana v dodatku A in jo je mogoče uporabiti za presejanje tri(2-kloroetil) fosfata v polimernih materialih.
OPOMBA: Tri(2-kloroetil) fosfat sproži termično razgradnjo pri približno 230 °C. Vrste polimerov, ki imajo temperaturo obdelave v oblike polimernih materialov (npr. kroglice, vliti deli ali pločevina), ki ne presega temperature razgradnje, lahko vsebujejo tri(2-kloroetil) fosfat.
General Information
Standards Content (Sample)
SLOVENSKI STANDARD
01-marec-2024
Določevanje posameznih snovi v elektrotehničnih izdelkih - 11. del: Določevanje
tri(2-kloroetil) fosfata (TCEP) v polimernih materialih s plinsko kromatografijo in
masno spektrometrijo (GC-MS) ter tekočinsko kromatografijo in masno
spektrometrijo (LC-MS)
Determination of certain substances in electrotechnical products - Part 11: Tris (2-
chloroethyl) phosphate (TCEP) in plastics by gas chromatography-mass spectrometry
(GC-MS) and liquid chromatography-mass spectrometry (LC-MS)
Določevanje posameznih snovi v elektrotehničnih izdelkih - 11. del: Določevanje ? tris (2-
kloroetil) fosfata (TCEP) v plastiki ? polimernih materialih ? s plinsko kromatografijo-
masno spektrometrijo (GC-MS) in tekočinsko kromatografijo-masno spektrometrijo (LC-
MS)
Détermination de certaines substances dans les produits électrotechniques - Partie 11:
Phosphate de tris(2-chloroéthyle) (TCEP) dans les plastiques par chromatographie en
phase gazeuse-spectrométrie de masse (GC-MS) et chromatographie en phase liquide-
spectrométrie de masse (LC-MS)
Ta slovenski standard je istoveten z: EN IEC 62321-11:2024
ICS:
29.020 Elektrotehnika na splošno Electrical engineering in
general
31.020 Elektronske komponente na Electronic components in
splošno general
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
EUROPEAN STANDARD EN IEC 62321-11
NORME EUROPÉENNE
EUROPÄISCHE NORM January 2024
ICS 13.020.01; 43.040.10
English Version
Determination of certain substances in electrotechnical products
- Part 11: Tris(2-chloroethyl) phosphate (TCEP) in plastics by
gas chromatography-mass spectrometry (GC-MS) and liquid
chromatography-mass spectrometry (LC-MS)
(IEC 62321-11:2023)
Détermination de certaines substances dans les produits Verfahren zur Bestimmung von bestimmten Substanzen in
électrotechniques - Partie 11: Phosphate de tris(2- Produkten der Elektrotechnik - Teil 11: Tris(2-
chloroéthyle) (TCEP) dans les plastiques par chlorethyl)phosphat (TCEP) in Kunststoffen mit
chromatographie en phase gazeuse-spectrométrie de Gaschromatographie-Massenspektrometrie (GC-MS) und
masse (GC-MS) et chromatographie en phase liquide- Flüssigkeitschromatographie-Massenspektrometrie
spectrométrie de masse (LC-MS) (LC-MS)
(IEC 62321-11:2023) (IEC 62321-11:2023)
This European Standard was approved by CENELEC on 2024-01-19. CENELEC 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 CENELEC 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 CENELEC member into its own language and notified to the CEN-CENELEC Management Centre has the
same status as the official versions.
CENELEC members are the national electrotechnical committees of Austria, Belgium, Bulgaria, Croatia, Cyprus, the Czech Republic,
Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, the
Netherlands, Norway, Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Türkiye and the United Kingdom.
European Committee for Electrotechnical Standardization
Comité Européen de Normalisation Electrotechnique
Europäisches Komitee für Elektrotechnische Normung
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2024 CENELEC All rights of exploitation in any form and by any means reserved worldwide for CENELEC Members.
Ref. No. EN IEC 62321-11:2024 E
European foreword
The text of document 111/723/FDIS, future edition 1 of IEC 62321-11, prepared by IEC/TC 111
"Environmental standardization for electrical and electronic products and systems" was submitted to
the IEC-CENELEC parallel vote and approved by CENELEC as EN IEC 62321-11:2024.
The following dates are fixed:
• latest date by which the document has to be implemented at national (dop) 2024-10-19
level by publication of an identical national standard or by endorsement
• latest date by which the national standards conflicting with the (dow) 2027-01-19
document have to be withdrawn
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CENELEC shall not be held responsible for identifying any or all such patent rights.
Any feedback and questions on this document should be directed to the users’ national committee. A
complete listing of these bodies can be found on the CENELEC website.
Endorsement notice
The text of the International Standard IEC 62321-11:2023 was approved by CENELEC as a European
Standard without any modification.
In the official version, for Bibliography, the following note has to be added for the standard indicated:
ISO 472:2013 NOTE Approved as EN ISO 472:2013 (not modified)
Annex ZA
(normative)
Normative references to international publications
with their corresponding European publications
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.
NOTE 1 Where an International Publication has been modified by common modifications, indicated by (mod), the
relevant EN/HD applies.
NOTE 2 Up-to-date information on the latest versions of the European Standards listed in this annex is available
here: www.cencenelec.eu.
Publication Year Title EN/HD Year
IEC 62321-1 2013 Determination of certain substances in EN 62321-1 2013
electrotechnical products - Part 1:
Introduction and overview
IEC 62321-2 2021 Determination of certain substances in EN IEC 62321-2 2021
electrotechnical products - Part 2:
Disassembly, disjointment and mechanical
sample preparation
IEC 62321-11
Edition 1.0 2023-12
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
Determination of certain substances in electrotechnical products –
Part 11: Tris(2-chloroethyl) phosphate (TCEP) in plastics by gas
chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass
spectrometry (LC-MS)
Détermination de certaines substances dans les produits électrotechniques –
Partie 11: Phosphate de tris(2-chloroéthyle) (TCEP) dans les plastiques par
chromatographie en phase gazeuse-spectrométrie de masse (GC-MS) et
chromatographie en phase liquide-spectrométrie de masse (LC-MS)
INTERNATIONAL
ELECTROTECHNICAL
COMMISSION
COMMISSION
ELECTROTECHNIQUE
INTERNATIONALE
ICS 13.020.01, 43.040.10 ISBN 978-2-8322-7777-50
– 2 – IEC 62321-11:2023 © IEC 2023
CONTENTS
FOREWORD . 4
INTRODUCTION . 6
1 Scope . 7
2 Normative references . 7
3 Terms, definitions and abbreviated terms . 7
3.1 Terms and definitions . 7
3.2 Abbreviated terms . 8
4 Principle . 9
5 Reagents and materials . 9
6 Apparatus . 10
6.1 GC-MS method . 10
6.2 LC-MS method . 11
7 Sampling . 11
8 Procedure . 11
8.1 General instructions for the analysis . 11
8.2 Sample preparation . 11
8.2.1 General . 11
8.2.2 GC-MS method . 12
8.2.3 LC-MS method . 13
8.3 Instrumental parameters . 14
8.3.1 GC-MS method . 14
8.3.2 LC-MS method . 15
8.4 Calibrants . 16
8.5 Calibration . 17
8.5.1 General . 17
8.5.2 TCEP and surrogate (100 μg/ml) stock solution . 17
8.5.3 Internal standard solution (100 μg/ml of anthracene-d ) . 17
8.5.4 Standard solutions . 17
9 Calculation of TCEP concentration . 19
10 Precision . 21
10.1 GC-MS method . 21
10.2 LC-MS method . 21
11 Quality assurance and control . 22
11.1 General . 22
11.2 GC-MS method . 22
11.2.1 Performance . 22
11.2.2 Method detection limit and reporting limit . 23
11.3 LC-MS method . 24
11.3.1 Performance . 24
11.3.2 Method detection limit and reporting limit . 25
12 Test report . 25
Annex A (informative) Tris(2-chloroethyl) phosphate (TCEP) in plastics by gas
chromatography-mass spectrometry using a pyrolyser/thermal desorption accessory
(Py/TD-GC-MS) . 26
A.1 Principle . 26
IEC 62321-11:2023 © IEC 2023 – 3 –
A.2 Reagents and materials . 27
A.3 Apparatus . 27
A.4 Sampling. 28
A.5 Procedure . 28
A.5.1 General instructions for the analysis . 28
A.5.2 Sample preparation . 28
A.5.3 Instrumental parameters . 29
A.5.4 Calibration . 30
A.6 Calculation of TCEP concentration . 31
A.6.1 General . 31
A.6.2 Determination of RF of DEHP . 31
A.6.3 Calculation . 32
Annex B (informative) Examples of chromatograms and mass spectrum by GC-MS . 33
Annex C (informative) Examples of chromatograms and mass spectrum by LC-MS . 34
Annex D (informative) Examples of chromatograms and mass spectrum by
Py-TD-GC-MS . 35
Bibliography . 36
Figure B.1 – Gas chromatogram of TCEP, TCEP-d , and anthracene-d . 33
12 10
Figure B.2 – Mass spectrum of TCEP by GC-MS . 33
Figure B.3 – Mass spectrum of TCEP-d by GC-MS . 33
Figure C.1 – Liquid chromatogram of TCEP and TCEP-d . 34
Figure C.2 – Mass spectrum of TCEP by LC-MS . 34
Figure C.3 – Mass spectrum of TCEP-d by LC-MS . 34
Figure D.1 – Total ion current chromatogram of TCEP by Py-TD-GC-MS . 35
Figure D.2 – Mass spectrum of TCEP by Py-TD-GC-MS . 35
Table 1 – Measurement condition of GC-MS . 14
Table 2 – Reference masses for the quantification of TCEP . 15
Table 3 – Measurement condition of LC-MS . 16
Table 4 – Calibration standard solution of TCEP with internal standard – Estimated
TCEP sample solution concentration 0,1 µg/ml and higher . 18
Table 5 – Calibration standard solution of TCEP with internal standard – Estimated
TCEP sample solution concentration lower than 0,1 µg/ml . 18
Table 6 – IIS 11 repeatability and reproducibility (GC-MS) . 21
Table 7 – IIS 11 repeatability and reproducibility (LC-MS) . 22
Table A.1 – Measurement conditions of Py/TD-GC-MS . 29
– 4 – IEC 62321-11:2023 © IEC 2023
INTERNATIONAL ELECTROTECHNICAL COMMISSION
____________
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –
Part 11: Tris(2-chloroethyl) phosphate (TCEP) in plastics by gas
chromatography-mass spectrometry (GC-MS) and liquid
chromatography-mass spectrometry (LC-MS)
FOREWORD
1) The International Electrotechnical Commission (IEC) is a worldwide organization for standardization comprising
all national electrotechnical committees (IEC National Committees). The object of IEC is to promote international
co-operation on all questions concerning standardization in the electrical and electronic fields. To this end and
in addition to other activities, IEC publishes International Standards, Technical Specifications, Technical Reports,
Publicly Available Specifications (PAS) and Guides (hereafter referred to as “IEC Publication(s)”). Their
preparation is entrusted to technical committees; any IEC National Committee interested in the subject dealt with
may participate in this preparatory work. International, governmental and non-governmental organizations liaising
with the IEC also participate in this preparation. IEC collaborates closely with the International Organization for
Standardization (ISO) in accordance with conditions determined by agreement between the two organizations.
2) The formal decisions or agreements of IEC on technical matters express, as nearly as possible, an international
consensus of opinion on the relevant subjects since each technical committee has representation from all
interested IEC National Committees.
3) IEC Publications have the form of recommendations for international use and are accepted by IEC National
Committees in that sense. While all reasonable efforts are made to ensure that the technical content of IEC
Publications is accurate, IEC cannot be held responsible for the way in which they are used or for any
misinterpretation by any end user.
4) In order to promote international uniformity, IEC National Committees undertake to apply IEC Publications
transparently to the maximum extent possible in their national and regional publications. Any divergence between
any IEC Publication and the corresponding national or regional publication shall be clearly indicated in the latter.
5) IEC itself does not provide any attestation of conformity. Independent certification bodies provide conformity
assessment services and, in some areas, access to IEC marks of conformity. IEC is not responsible for any
services carried out by independent certification bodies.
6) All users should ensure that they have the latest edition of this publication.
7) No liability shall attach to IEC or its directors, employees, servants or agents including individual experts and
members of its technical committees and IEC National Committees for any personal injury, property damage or
other damage of any nature whatsoever, whether direct or indirect, or for costs (including legal fees) and
expenses arising out of the publication, use of, or reliance upon, this IEC Publication or any other IEC
Publications.
8) Attention is drawn to the Normative references cited in this publication. Use of the referenced publications is
indispensable for the correct application of this publication.
9) IEC draws attention to the possibility that the implementation of this document may involve the use of (a)
patent(s). IEC 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, IEC 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 https://patents.iec.ch. IEC
shall not be held responsible for identifying any or all such patent rights.
IEC 62321-11 has been prepared by IEC technical committee 111: Environmental
standardization for electrical and electronic products and systems, in collaboration with
ISO subcommittee SC 5: Physical-chemical properties of ISO technical committee 61: Plastics.
It is an International Standard.
It is published as a double logo standard.
IEC 62321-11:2023 © IEC 2023 – 5 –
The text of this International Standard is based on the following documents:
Draft Report on voting
111/723/FDIS 111/735A/RVD
Full information on the voting for its approval can be found in the report on voting indicated in
the above table.
The language used for the development of this International Standard is English.
This document was drafted in accordance with ISO/IEC Directives, Part 2, and developed in
accordance with ISO/IEC Directives, Part 1 and ISO/IEC Directives, IEC Supplement, available
at www.iec.ch/members_experts/refdocs. The main document types developed by IEC are
described in greater detail at www.iec.ch/publications.
A list of all parts in the IEC 62321 series, published under the general title Determination of
certain substances in electrotechnical products, can be found on the IEC website.
The committee has decided that the contents of this document will remain unchanged until the
stability date indicated on the IEC website under webstore.iec.ch in the data related to the
specific document. At this date, the document will be
• reconfirmed,
• withdrawn, or
• revised.
– 6 – IEC 62321-11:2023 © IEC 2023
INTRODUCTION
The widespread use of electrotechnical products has drawn increased attention to their impact
on the environment. In many countries, this has resulted in the adoption of regulations affecting
wastes, substances, and energy use of electrotechnical products.
The use of certain substances (e.g. lead (Pb), cadmium (Cd), and polybrominated diphenyl
ethers (PBDEs)) in electrotechnical products is a source of concern in current and proposed
regional legislation.
The purpose of the IEC 62321 series is therefore to provide test methods that will allow the
electrotechnical industry to determine the levels of certain substances of concern in
electrotechnical products on a consistent global basis.
This first edition of IEC 62321-11 introduces a new subject covering tris(2-chloroethyl)
phosphate (TCEP) in the IEC 62321 series.
TCEP is a halogenated phosphorus-based flame retardant that is disclosable as a substance
of very high concern (SVHC) as it is classified as toxic to reproduction category 2 (R60) and
was included in the candidate list for authorization on 13 January 2010, following ECHA’s
decision ED/68/2009 [1] and in regulation (EC) No 1907/2006 ANNEX XVI [2].
TCEP is used as a flame retardant in plastics such as polyester and polyurethane foam and as
a plasticizer in polyvinyl chloride. Additionally, TCEP is used as an alternative for brominated
flame retardants that have been restricted. No applicable testing standard exists for TCEP
analysis in plastics.
As a result, analysis criteria have been established by an IEC TC 111 and ISO/TC 61/SC 5 joint
working group for the joint development of an IEC and ISO double logo International Standard,
to provide a test method that will allow the industry to determine the concentrations of TCEP in
plastics.
WARNING – Persons using this document should be familiar with normal laboratory practice.
This document does not purport to address all of the safety problems, if any, associated with
its use. It is the responsibility of the user to establish appropriate safety and health practices
and to ensure compliance with any national regulatory conditions.
___________
Numbers in square brackets refer to the Bibliography.
IEC 62321-11:2023 © IEC 2023 – 7 –
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –
Part 11: Tris(2-chloroethyl) phosphate (TCEP) in plastics by gas
chromatography-mass spectrometry (GC-MS) and liquid
chromatography-mass spectrometry (LC-MS)
1 Scope
This part of IEC 62321 specifies two different techniques for the determination of
tris(2-chloroethyl) phosphate (TCEP) in plastics, the GC-MS or LC-MS method, both of which
are applicable to quantitative analysis.
These two techniques are applicable to use with polyurethane, polyvinylchloride, and
polyethylene materials containing TCEP between 200 mg/kg to 2 000 mg/kg.
These test methods do not apply to plastic materials having a processing temperature higher
than 230 °C.
GC-MS using a pyrolyser/thermal desorption accessory (Py/TD-GC-MS) technique is described
in Annex A and can be used for the screening of TCEP in plastics.
NOTE TCEP starts thermal decomposition at approximately 230 °C. Polymer types that have a processing
temperature into shapes of plastics (e.g. pellets, moulded parts or sheets) not exceeding the decomposition
temperature can contain TCEP.
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.
IEC 62321-1:2013, Determination of certain substances in electrotechnical products – Part 1:
Introduction and overview
IEC 62321-2:2021, Determination of certain substances in electrotechnical products – Part 2:
Disassembly, disjointment and mechanical sample preparation
3 Terms, definitions and abbreviated terms
3.1 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminology databases for use in standardization at the following
addresses:
• IEC Electropedia: available at https://www.electropedia.org
• ISO Online browsing platform: available at https://www.iso.org/obp
– 8 – IEC 62321-11:2023 © IEC 2023
3.1.1
screening
analytical procedure to determine the presence or absence of substances in the representative
part or section of a product, relative to the value or values chosen as the criterion for presence,
absence, or further testing
Note 1 to entry: If the screening method produces values that are not conclusive, then additional analysis or other
follow-up actions can be necessary to make a final presence or absence decision.
3.1.2
plastic
material that contains as an essential ingredient a high polymer and which, at some stage in its
processing into finished products, can be shaped by flow
Note 1 to entry: Elastomeric materials, which are also shaped by flow, are not considered to be plastics.
Note 2 to entry: In some countries, particularly the United Kingdom, the term "plastics" is used as the singular form
as well as the plural form.
[SOURCE: ISO 472:2013 [3], 2.702]
3.1.3
polymer
substance composed of molecules characterized by the multiple repetition of one or more
species of atoms or groups of atoms (constitutional units) linked to each other in amounts
sufficient to provide a set of properties that do not vary markedly with the addition or removal
of one or a few of the constitutional units
[SOURCE: ISO 1382:2020 [4], 3.369]
3.1.4
blank
test that follows the same procedures and conditions as the sample test without a sample, which
enables quantification of the contamination in the test
3.2 Abbreviated terms
ACN acetonitrile
API-ES atmospheric pressure ionization-electrostatic
BSA N,O-bis(trimethylsilyl)acetamide
BSTFA N,O-bis(trimethylsilyl)trifluoroacetamide
CCC continuing calibration check standard
D dilution factor
DEHP di-(2-ethylhexyl) phthalate
DMDCS dimethyldichlorosilane
EI electron ionization
GC-MS gas chromatography-mass spectrometry
HPLC high-performance liquid chromatography
ID internal diameter
IIS international interlaboratory study
IS internal standard
LC-MS liquid chromatography-mass spectrometry
LOD limit of detection
MDL method detection limit
IEC 62321-11:2023 © IEC 2023 – 9 –
MS mass spectrometry
PBB polybrominated biphenyl
PBDE polybrominated diphenyl ether
PE polyethylene
PS polystyrene
PTFE polytetrafluoroethylene
PUR polyurethane
PVC polyvinyl chloride
Py/TD-GC-MS gas chromatography-mass spectrometry using a pyrolyser/thermal desorption
accessory
QC quality control
RF response factor
RRF relative response factor
RSD relative standard deviation
SIM single (or "selected") ion monitoring
TCEP tris(2-chloroethyl) phosphate
TD thermal desorption
THF tetrahydrofuran
TICS tentatively identified compounds
4 Principle
The samples are dissolved in THF and the matrix polymer is separated by precipitation with
methanol, TCEP is determined qualitatively and quantitatively using GC-MS or LC-MS.
5 Reagents and materials
Use chemicals of analytical grade, unless otherwise indicated.
a) TCEP (tris(2-chloroethyl) phosphate): CAS No. 115-96-8 (purity of greater than a mass
fraction of 98 %);
b) THF (GC grade or higher, higher than 99,9 %);
c) n-Hexane (GC grade or higher, higher than 98,5 %);
d) methanol (GC grade or higher, higher than 99,9 %);
e) mixed solvent (THF mixed with methanol, the volume ratio of THF/methanol is 1/4);
f) helium (purity of greater than a volume fraction of 99,999 %);
g) calibrants; reference materials of TCEP (purity of greater than a mass fraction of 98 %);
h) surrogate and internal standards:
– surrogate standard is used to monitor analytes recovery according to 8.2.2.1 and 8.2.3.1,
for example TCEP-d ;
– internal standard is used to correct injection errors, according to 8.2.2.1 and 8.2.3.1, for
example anthracene-d .
The standards are acceptable when using a quadruple-type mass spectrometer.
A high-resolution mass spectrometer will require the use of other suitable standard substances
having a mass and elution time similar to that of the analyte.
– 10 – IEC 62321-11:2023 © IEC 2023
6 Apparatus
6.1 GC-MS method
The following items shall be used for the analysis:
a) analytical balance capable of measuring accurately to 0,000 1 g;
b) cryogenic grinding mill with liquid N cooling;
c) ultrasonic bath;
d) 1 ml, 5 ml, 10 ml, 50 ml, and 100 ml volumetric flasks;
e) Soxhlet extractors:
– 30 ml Soxhlet extractors;
– 250 ml round-bottomed flask;
– ground-in stopper NS 29/32;
– Dimroth condenser NS 29/32;
– boiling stones (e.g. glass pearls or Raschig rings);
f) 30 ml cellulose extraction thimble with ID 22 mm, height 80 mm;
g) glass wool for extraction thimble;
h) heating jackets for 250 ml round-bottomed flask;
i) glass funnels;
j) aluminium foil;
k) cork rings;
l) 0,45 µm PTFE syringe filter;
m) microlitre syringe or automatic pipettes;
n) Pasteur pipettes;
o) 2 ml sample vials and a screw cap with a PTFE gasket or, depending on the analytical
system, a comparable sample receptacle;
p) mini-shaker known as vortexer or vortex mixer;
q) deactivated injector liner for GC-MS;
r) gas chromatograph-mass spectrometer, split/splitless inlet, and a programmable
temperature-controlled oven. The mass spectrometer shall be able to perform selected ion
monitoring (SIM) and total ion current ("full scan"). The ionization box shall be treated for
chemical stability and controlled at 230 °C. The kinetic energy of 70 eV shall be applied in
electron ionization (EI) mode;
s) capillary column;
A liquid phase of 100 % dimethyl polysiloxane or 5 % diphenyl, 95 % dimethyl polysiloxane
has been found suitable. The preferred column dimension length is 30 m, internal diameter
is 0,25 mm, and the film thickness is 0,25 µm;
t) 50 ml amber vial;
u) vacuum rotary evaporator;
v) auto-sampler.
.
The use of an auto-sampler is recommended to ensure repeatability
IEC 62321-11:2023 © IEC 2023 – 11 –
6.2 LC-MS method
Items a) to p) in 6.1 and the following items shall be used for the analysis:
a) high-performance liquid chromatography (HPLC) system equipped with a mass
spectrometer detector;
The use of an auto-sampler is recommended to ensure repeatability.
b) pump;
c) column oven;
d) stationary phase: C , 150 mm × 2,1 mm, 5 µm or equivalent film thickness.
7 Sampling
Manual cutting or cryogenic grinding or milling with liquid nitrogen cooling is recommended to
be performed in accordance with IEC 62321-2:2021.
The sample shall be ground as small as 500 µm in diameter. Cryogenic grinding with liquid N
cooling is strongly recommended. Reference polymer materials shall also be ground in the same
way.
If the grinder cannot be used, the sample shall be cut to around 2 mm × 2 mm.
NOTE For a composite plastic that is made from more than one material, but cannot be separated mechanically,
the concentration of TCEP can be determined for the composite material, as it cannot be confirmed which of the
constituent plastics is the source of the TCEP.
8 Procedure
8.1 General instructions for the analysis
The validation of the instrumentation should include testing of potential cross-contaminations
between sequential samples. Additional blanks or an inverted sequence of testing will help to
identify cross-contamination.
In order to reduce blank values, ensure the cleanliness of all glass equipment and deactivate
glass wool (see 6.1 g)) by subjecting it to 450 °C for at least 30 min. To avoid the decomposition
of TCEP by UV light during extraction and analysis, glass equipment made from brown or amber
glass shall be used.
If the amount of TCEP in the sample is considerably above the 0,1 % range, it will be necessary
to carry out the analysis using an adjusted sample size or by repeating the analysis using an
extract that has been appropriately diluted prior to internal standard addition.
After analysis of test samples with high analyte concentration, blank samples shall be analysed,
until the background level is decreased to lower than 30 mg/kg. In order to reduce blank values,
ensure the cleanliness of all tools used in sample preparation.
A blank polymer material or blank sample cup is used for blank-sample analysis.
8.2 Sample preparation
8.2.1 General
The sample preparation requires clean glassware (e.g. single-use items) to avoid cross-
contamination. The extraction method is chosen by the solubility of the sample polymer in THF.
– 12 – IEC 62321-11:2023 © IEC 2023
8.2.2 GC-MS method
8.2.2.1 Stock solution
The following stock solution shall be prepared:
a) surrogate standard to monitor analyte recovery (e.g. TCEP-d ): 1 000 μg/ml in a solvent;
NOTE 1 The solvent is THF or n-hexane, which is decided by the extraction method.
b) internal standard to correct for injection error (e.g. anthracene-d ): 10 μg/ml or 100 μg/ml
in a solvent.
NOTE 2 The solvent is methanol or n-hexane, which is decided by the extraction method.
8.2.2.2 Extraction by sonication for soluble polymer
For a soluble polymer sample like PUR or PVC, the following procedure shall be applied:
a) Weigh 200 mg ± 10 mg of the sample and transfer it into a 50 ml vial (6.1 t)). Record the
weight to the nearest 0,1 mg. Other sample amounts may be used for samples with
potentially very low or very high TCEP concentrations but the maximum sample amount is
500 mg. Transfer 10 ml of THF and 10 μl of surrogate standard (8.2.2.1 a)) to the 50 ml vial
(6.1 t)).
b) Tightly cap the sample 50 ml vial (6.1 t)). A small piece of adhesive tape may be used to
prevent the cap from loosening due to vibration.
c) Place the 50 ml vial (6.1 t)) in an ultrasonic bath (6.1 c)) at 60 °C and sonicate for 60 min.
d) Allow the 50 ml vial (6.1 t)) to cool to ambient temperature, (20 ± 5) °C.
e) Add 40 ml of methanol (Clause 5 d)) dropwise into the 50 ml vial (6.1 t)) and mix well to
precipitate the sample matrix. The resulting extracted solution should stand at room
temperature for 30 min.
f) Filter the solution through a 0,45 µm PTFE membrane filter.
g) Transfer 1 ml of the filtrate into a 2 ml vial (6.1 o)) and add 10 μl of internal standard (8.2.2.1
b)) into the 2 ml vial (6.1 o)).
h) Cap the 2 ml vial (6.1 o)) with a PTFE-coated seal and stir well.
8.2.2.3 Soxhlet extraction for insoluble polymer
The following steps shall be applied for samples other than PUR and PVC:
a) To clean the Soxhlet extractors (6.1 e)), a 2 h pre-extraction is carried out with 100 ml of
n-hexane (Clause 5 c)). The washing solvent is discarded after cleaning.
b) Transfer 200 mg ± 10 mg of the sample into cellulose extraction thimbles (6.1 f)) for Soxhlet
extraction. Record the mass to the nearest 0,1 mg. Other sample amounts may be used for
samples with potentially very low or very high TCEP concentrations but the maximum
sample amount is 500 mg.
c) Allow the sample to be transferred through a funnel (6.1 i)) into the extraction thimble
(6.1 f)). In order to ensure a quantitative transfer, the funnel (6.1 i)) should be rinsed with
approximately 10 ml of n-hexane (Clause 5 c)).
d) 10 μl of surrogate standard (8.2.2.1 a) is added.
e) Cover the thimble (6.1 f)) with glass wool (6.1 g)) to prevent the sample from floating.
f) 100 ml of n-hexane (Clause 5 c)) is used for extraction under reflux. Allow the sample to be
extracted for at least 6 h with 6 cycles/h to 8 cycles/h. Cover the flask with aluminium foil
during extraction. The evaporation temperature is recommended to be controlled under
68 °C.
g) After 6 h of reflux, concentrate the extract to less than 40 ml using a vacuum rotary
evaporator (6.1 u)), or a similar process.
IEC 62321-11:2023 © IEC 2023 – 13 –
h) Transfer the concentrated solution into a 50 ml volumetric flask (6.1 d)). Rinse the
evaporator flask with a small amount of n-hexane (Clause 5 c)) and add to the 50 ml
volumetric flask (6.1 d)). Dilute with n-hexane (Clause 5 c)) to 50 ml.
i) Filter the solution through a 0,45 µm PTFE syringe filter (6.1 l)).
j) Transfer 1 ml of the filtrate into a 2 ml vial (6.1 o)) and add 10 μl of internal standard
(8.2.2.1 b)) into the vial (6.1 o)).
k) Cap the vial (6.1 o)) with a PTFE-coated seal and stir well.
8.2.3 LC-MS method
8.2.3.1 Stock solution
The following stock solution shall be prepared:
a) surrogate standard to monitor analyte recovery (e.g. TCEP-d ): 1 000 μg/ml in a solvent.
NOTE The solvent is THF or n-hexane, which is decided by the extraction method.
8.2.3.2 Extraction by sonication for soluble polymer
For a soluble polymer sample like PUR or PVC, the following procedure shall be applied:
a) Weigh 200 mg ± 10 mg of the sample and transfer it into a 50 ml vial (6.1 t)). Record the
weight to the nearest 0,1 mg. Other sample amounts may be used for samples with
potentially very low or very high TCEP concentrations but the maximum sample amount is
500 mg.
b) Transfer 10 ml of THF and 10 μl of surrogate standard (8.2.2.1 a)) to the 50 ml vial (6.1 t)).
c) Tightly cap the sample 50 ml vial (6.1 t)). A small piece of adhesive tape may be used to
prevent the cap from loosening due to vibration.
d) Place the 50 ml vial (6.1 t)) in a 60 °C ultrasonic bath and sonicate it for 60 min.
e) Allow the 50 ml vial (6.1 t)) to cool to ambient temperature, (20 ± 5) °C.
f) Add 40 ml of methanol (Clause 5 d)) dropwise into the 50 ml vial (6.1 t)) and mix well to
precipitate the sample matrix. The resulting extracted solution stands at room temperature
for 30 min.
g) Filter the solution through a 0,45 µm PTFE membrane filter.
h) Transfer 1 ml of the filtrate into a 2 ml vial (6.1 o)).
i) Cap the 2 ml vial (6.1 o)) with a PTFE-coated seal and stir well.
8.2.3.3 Soxhlet extraction for insoluble polymer
The following steps shall be applied for samples other than PUR and PVC:
a) To clean the Soxhlet extractors (6.1 e), a 2 h pre-extraction is carried out with 100 ml of
n-hexane (Clause 5 c)). The washing solvent is discarded after cleaning.
b) Transfer 200 mg ± 10 mg of the sample into cellulose extraction thimbles (6.1 f)) for Soxhlet
extraction. Record the mass to the nearest 0,1 mg. Other sample amounts may be used for
samples with potentially very low or very high TCEP concentrations but the maximum
sample amount is 500 mg.
c) Allow the sample to be transferred through a funnel (6.1 i)) into the extraction thimble
(6.1 f)). In order to ensure a quantitative transfer, the funnel (6.1 i)) should be rinsed with
approximately 10 ml of n-hexane (Clause 5 c)).
d) 10 μl of surrogate standard (8.2.3.1 a) is added.
e) Cover the thimble (6.1 f)) with glass wool (6.1 g)) to prevent the sample from floating.
f) 100 ml of n-hexane (Clause 5 c)) is used for extraction under reflux. Allow the sample to be
extracted for at least 6 h with 6 cycles/h to 8 cycles/h. Cover the flask with aluminium foil
during extraction.
– 14 – IEC 62321-11:2023 © IEC 2023
g) After 6 h of reflux, concentrate the extract to less than 5 ml using a vacuum rotary evaporator
(6.1 u)), or a similar process.
h) Transfer the concentrated solution into a 50 ml volumetric flask (6.1 d)). Rinse the
evaporator flask with a small amount of methanol (Clause 5 d)) and add to the 50 ml
volumetric flask (6.1 d)). Dilute with methanol (Clause 5 d)) to 50 ml. The solvent shall be
changed to methanol by dilution so that the solvent is the same as for the mobile phase of
LC-MS.
i) Filter the solution through a 0,45 µm PTFE membrane filter.
j) Transfer 1 ml of the filtrate into a 2 ml vial (6.1 o)).
k) Cap the vial (6.1 o)) with a PTFE-coated seal and stir well.
8.3 Instrumental parameters
8.3.1 GC-MS method
Different conditions can be necessary to optimize a specific GC-MS system to achieve effective
separation of TCEP and meet the QC and LOD requirements.
The parameters given in Table 1 and Table 2 have been found suitable and are provided as an
example.
Table 1 – Measurement condition of GC-MS
GC
Injection volume 1,0 μl
Non-polar (Phenyl-arylene polymer equivalent to 5 % diphenyl-dimethylpolysiloxane)
Column
Length 30 m; internal diameter 0,25 mm; film thickness 0,25 µm
Injector liner 4 mm single bottom taper glass liner with glass wool at bottom (deactivated)
Injection port
270 °C
temperature
110 °C for 2 min, then increase at a rate of 15 K/min up to 15
...
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