EN IEC 62321-3-3:2021

SLOVENSKI STANDARD
01-december-2021
Določevanje posameznih snovi v elektrotehničnih izdelkih - 3-3. del: Preséjanje
polibromiranih bifenilov, polibromiranih difenil etrov in ftalatov v polimerih s
pirolizo (Py-GC-MS) ali s termodesorpcijsko plinsko kromatografijo z masno
spektrometrijo (TD-GC-MS)
Determination of certain substances in electrotechnical products  Part 3-3: Screening of
polybrominated biphenyls, polybrominated diphenyl ethers and phthalates in polymers by
pyrolysis (Py-GC-MS) or thermal desorption (TD-GC-MS) gas chromatography-mass
spectrometry
Ta slovenski standard je istoveten z: EN IEC 62321-3-3:2021
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 62321-3-3

NORME EUROPÉENNE
EUROPÄISCHE NORM
October 2021
ICS 13.020.01; 43.040.10
English Version
Determination of certain substances in electrotechnical products
- Part 3-3: Screening - Polybrominated biphenyls,
polybrominated diphenyl ethers and phthalates in polymers by
gas chromatography-mass spectrometry using a
pyrolyser/thermal desorption accessory (Py/TD-GC-MS)
(IEC 62321-3-3:2021)
Détermination de certaines substances dans les produits Verfahren zur Bestimmung von bestimmten Substanzen in
électrotechniques - Partie 3-3: Détection - Diphényles Produkten der Elektrotechnik - Teil 3-3: Screening der
polybromés, diphényléthers polybromés et phtalates dans polybromierten Biphenyle, polybromierten Diphenylether
les polymères par chromatographie en phase gazeuse- und Phthalate in Polymeren durch Pyrolyse (Py-GC-MS)
spectrométrie de masse par pyrolyse/thermodésorption oder Thermodesorption-Gaschromatographie-
(Py/TD-GC-MS) Massenspektrometrie (TD-GC-MS)
(IEC 62321-3-3:2021) (IEC 62321-3-3:2021)
This European Standard was approved by CENELEC on 19 October 2021. CEN and 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 CEN and 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 CEN and CENELEC member into its own language and notified to the CEN-CENELEC Management Centre
has the same status as the official versions.
CEN and CENELEC members are the national standards bodies and national electrotechnical committees 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 Electrotechnical Standardization
Comité Européen de Normalisation Electrotechnique
Europäisches Komitee für Elektrotechnische Normung
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2021 All rights of exploitation in any form and by any means reserved worldwide for CEN national Members and for
CEN/CENELEC CENELEC Members.
Ref. No. EN IEC 62321-3-3:2021 E

European foreword
The text of document 111/626/FDIS, future edition 1 of IEC 62321-3-3, 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 62321-3-3:2021.
The following dates are fixed:
• latest date by which the document has to be implemented at national (dop) 2022–07–19
level by publication of an identical national standard or by endorsement
• latest date by which the national standards conflicting with the (dow) 2024–10–19
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 62321-3-3:2021 was approved by CENELEC as a
European Standard without any modification.
In the official version, for Bibliography, the following notes have to be added for the standards
indicated:
IEC 62321-1:2013 NOTE Harmonized as EN 62321-1:2013 (not modified)
IEC 62321-2:2013 NOTE Harmonized as EN 62321-2:2014 (not modified)
IEC 62321-8:2017 NOTE Harmonized as EN 62321-8:2017 (not modified)
IEC 62321-3-1:2013 NOTE Harmonized as EN 62321-3-1:2014 (not modified)
IEC 62321-3-2:2020 NOTE Harmonized as EN IEC 62321-3-2:2020 (not modified)
2 3
IEC 62321:2008 NOTE Harmonized as EN 62321:2009 (not modified)
ISO 3696 NOTE Harmonized as EN ISO 3696
ISO/IEC 17025 NOTE Harmonized as EN ISO/IEC 17025

To be published. Stage at time of publication: prEN IEC 62321-3-2:2020.
Withdrawn.
Withdrawn.
IEC 62321-3-3 ®
Edition 1.0 2021-09
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
HORIZONTAL PUBLICATION
PUBLICATION HORIZONTALE
Determination of certain substances in electrotechnical products –

Part 3-3: Screening – Polybrominated biphenyls, polybrominated diphenyl ethers

and phthalates in polymers by gas chromatography-mass spectrometry using a

pyrolyser/thermal desorption accessory (Py/TD‑GC‑MS)

Détermination de certaines substances dans les produits électrotechniques –

Partie 3-3: Détection – Diphényles polybromés, diphényléthers polybromés et

phtalates dans les polymères par chromatographie en phase gazeuse-

spectrométrie de masse par pyrolyse/thermodésorption (Py/TD‑GC‑MS)

INTERNATIONAL
ELECTROTECHNICAL
COMMISSION
COMMISSION
ELECTROTECHNIQUE
INTERNATIONALE
ICS 13.020.01; 43.040.10 ISBN 978-2-8322-1011-6

– 2 – IEC 62321-3-3:2021 © IEC 2021
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 . 9
4 Principle . 10
4.1 Overview. 10
4.2 Principle of test . 11
5 Reagents and materials . 11
6 Apparatus . 12
7 Sampling . 12
8 Procedure . 12
8.1 General instructions for the analysis . 12
8.2 Sample preparation . 13
8.2.1 General . 13
8.2.2 Polymer sample . 13
8.2.3 Stock solution or polymer reference material . 13
8.3 Instrumental parameters . 13
8.4 Calibration . 15
8.4.1 General . 15
8.4.2 Determination of RRFs . 15
9 Calculation of PBBs, PBDEs and phthalates concentration . 16
9.1 General . 16
9.2 Determination of RF of DEHP . 17
9.3 Calculation . 17
9.3.1 Calculation of RF . 17
9.3.2 Calculation of concentration. 17
10 Precision . 18
10.1 Screening judgement . 18
10.2 Repeatability and reproducibility . 20
11 Quality assurance and control . 23
11.1 General . 23
11.2 Quality control . 23
11.2.1 Sensitivity test . 23
11.2.2 Blank test . 23
11.2.3 System stability test . 24
11.2.4 Degradation test . 24
11.2.5 RRF test . 24
11.3 Method detection limit (MDL) and limit of quantification (LOQ) . 25
12 Test report . 25
Annex A (informative) Flow chart of screening and verification test method . 26
Annex B (informative) Principle of Py/TD-GC-MS instruments . 28
Annex C (informative) Other test methods . 29

IEC 62321-3-3:2021 © IEC 2021 – 3 –
Annex D (informative) Commercially available reference solutions and materials . 30
D.1 Reference solution . 30
D.2 Polymer reference materials . 31
Annex E (informative) Sampling procedure . 33
E.1 Sample preparation using cutting tools. 33
E.2 Sample preparation using cryogenic grinding mill . 33
E.3 Accurate weighing of sample . 33
E.4 Method of sample injection . 33
Annex F (informative) Verification of the EGA thermal desorption zone . 34
Annex G (informative) Example of chromatograms . 36
Annex H (informative) Examples of RRFs . 37
Annex I (informative) Sample analysis sequence . 38
Annex J (informative) Results of international inter-laboratory study 3-3 . 39
Bibliography . 42

Figure A.1 – Flow chart for screening step and verification test step for PBDEs, PBBs
and phthalates . 26
Figure B.1 – Example of Py/TD-GC-MS instrument . 28
Figure D.1 – Sample preparation of reference materials. 32
Figure F.1 – Example of EGA thermogram of a PVC sample containing phthalates . 34
Figure F.2 – Example of EGA thermogram of a polystyrene sample containing PBDEs . 35
Figure G.1 – Total ion current chromatogram of 0,1 µg of PBBs, PBDEs and phthalates
mixture by Py/TD-GC-MS . 36

Table 1 – Measurement conditions of Py/TD-GC-MS . 14
Table 2 – IIS3-3 Screening and threshold judgement . 18
Table 3 – IIS3-3 Repeatability and reproducibility (phthalate) . 20
Table 4 – IIS3-3 Repeatability and reproducibility (PBB) . 21
Table 5 – IIS3-3 Repeatability and reproducibility (PBDE) . 22
Table A.1 – Screening methods for phthalate esters, PBBs and PBDEs in the
IEC 62321 series . 27
Table C.1 – Other test methods . 29
Table D.1 – Example list of commercially available reference solutions of PBBs and
PBDEs . 30
Table D.2 – Example list of commercially available reference solutions of phthalates . 31
Table D.3 – Example list of commercially available reference materials of PBBs,
PBDEs and PS considered suitable for Py/TD-GC-MS . 31
Table D.4 – Example list of commercially available reference materials of phthalates
considered suitable for Py/TD-GC-MS. 32
Table E.1 – Example of variation of weighting samples . 33
Table H.1 – RRFs of analytes . 37
Table I.1 – Sample analysis sequence for Py/TD-GC-MS analysis . 38
Table J.1 – Statistical data for phthalates . 39
Table J.2 – Statistical data for polybrominated biphenyls . 40
Table J.3 – Statistical data for polybrominated diphenyl ethers . 41

– 4 – IEC 62321-3-3:2021 © IEC 2021
INTERNATIONAL ELECTROTECHNICAL COMMISSION
____________
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 3-3: Screening – Polybrominated biphenyls,
polybrominated diphenyl ethers and phthalates in polymers
by gas chromatography-mass spectrometry using a
pyrolyser/thermal desorption accessory (Py/TD‑GC‑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,
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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) Attention is drawn to the possibility that some of the elements of this IEC Publication may be the subject of patent
rights. IEC shall not be held responsible for identifying any or all such patent rights.
IEC 62321-3-3 has been prepared by IEC technical committee 111: Environmental
standardization for electrical and electronic products and systems. It is an International
Standard.
The text of this International Standard is based on the following documents:
FDIS Report on voting
111/626/FDIS 111/632/RVD
Full information on the voting for its approval can be found in the report on voting indicated in
the above table.
IEC 62321-3-3:2021 © IEC 2021 – 5 –
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/standardsdev/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,
• replaced by a revised edition, or
• amended.
– 6 – IEC 62321-3-3:2021 © IEC 2021
INTRODUCTION
The widespread use of electrotechnical products has drawn increased attention to their impact
on the environment. In many countries all over the world, this has resulted in the adaptation of
regulations affecting wastes, substances and energy use of electrotechnical products.
The use of polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs) and
certain phthalates in electrotechnical products is of concern in many regions of the world.
The purpose of this document is therefore to provide a test method that will allow the
electrotechnical industry to determine the levels of polybrominated biphenyls (PBBs),
polybrominated diphenyl ethers (PBDEs), di-isobutyl phthalate (DIBP), di-n-butyl phthalate
(DBP), benzylbutyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate
(DNOP), di-isononyl phthalate (DINP) and di-isodecyl phthalate (DIDP) in electrotechnical
products on a consistent global basis.
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.

IEC 62321-3-3:2021 © IEC 2021 – 7 –
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 3-3: Screening – Polybrominated biphenyls,
polybrominated diphenyl ethers and phthalates in polymers
by gas chromatography-mass spectrometry using a
pyrolyser/thermal desorption accessory (Py/TD‑GC‑MS)

1 Scope
This part of IEC 62321 specifies the screening analysis of polybrominated biphenyls (PBBs),
polybrominated diphenyl ethers (PBDEs), di-isobutyl phthalate (DIBP), di-n-butyl phthalate
(DBP), benzylbutyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate
(DNOP), di-isononyl phthalate (DINP), and di-isodecyl phthalate (DIDP) in polymers of
electrotechnical products using the analytical technique of gas chromatography-mass
spectrometry using a pyrolyser/thermal desorption accessory (Py/TD-GC-MS).
This test method has been evaluated through the analysis of PP (polypropylene), PS
(polystyrene), and PVC (polyvinyl chloride) materials containing deca-BDE between 100 mg/kg
and 1 000 mg/kg and individual phthalates between 100 mg/kg to 4 000 mg/kg as depicted in
Annex J. Use of the methods described in this document for other polymer types, PBBs
(mono-deca), PBDEs (mono-deca) and phthalates or concentration ranges other than those
specified above has not been specifically evaluated.
This document has the status of a horizontal standard in accordance with IEC Guide 108 [1] .
2 Normative references
There are no normative references in this document.
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 terminological databases for use in standardization at the following
addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
_____________
Numbers in square brackets refer to the bibliography.

– 8 – IEC 62321-3-3:2021 © IEC 2021
3.1.1
reference material
material, sufficiently homogeneous and stable with reference to specified properties, which has
been established to be fit for its intended use in measurement or in examination of nominal
properties
[SOURCE: IEC 62321-1:2013, 3.1.7 [2]]
3.1.2
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 may be necessary to make a final presence/absence decision.
[SOURCE: IEC 62321-1:2013, 3.1.10]
3.1.3
calibrant
calibration standard
substance in solid or liquid form with known and stable concentration(s) of the analyte(s) of
interest used to establish instrument response with respect to analyte(s) concentration(s) or
mass
3.1.4
response factor
RF
ratio between the mass of the compound being analysed and the peak area of that compound
in Equation (1)
RF = A / m (1)
where
RF is the response factor;
A is the peak area of a compound;
m is the mass of a compound
3.1.5
relative response factor
RRF
ratio between the RFs of two compounds – compound A and compound B – in Equation (2)
RRF = RF / RF (2)
A/B A B
where
RRF is the relative response factor of compound A to compound B;
A/B
RF is the response factor of compound A;
A
RF is the response factor of compound B
B
IEC 62321-3-3:2021 © IEC 2021 – 9 –
3.1.6
substitute compound
compound used to calculate RRFs of each analyte
Note 1 to entry: More than one compound can be selected as a substitute compound. The RRF of the analyte is the
ratio of the RF of the analyte to this compound. In Equation (3), compound B corresponds to this. The role is the
same as internal standards to correct the response factor. However, this is not included in test samples and is
analysed before analysis of test samples. From the RF of the substitute compound and the RRF of the analyte, the
RF of each analyte is calculated.
RF = RRF × RF (3)
A A/B B
where
RF is the response factor of compound A;
A
RF is the response factor of compound B; substitute compound
B
3.2 Abbreviated terms
BB-003 4-bromobiphenyl
BB-015 4,4'-dibromobiphenyl
BB-029 2,4,5-tribromobiphenyl
BB-049 2,2',4,5'-tetrabromobiphenyl
BB-103 2,2',4,5',6-pentabromobiphenyl
BB-153 2,2',4,4',5,5'-hexabromobiphenyl
BB-189 2,3,3',4,4',5,5'-heptabromobiphenyl
BB-194 2,2',3,3’,4,4',5,5'-octabromobiphenyl
BB-206 2,2’,3,3’,4,4’,5,5’,6- nonabromobiphenyl
BB-209 decabromo biphenyl
BBP benzyl butyl phthalate
BDE-003 4-bromodiphenyl ether
BDE-015 4,4'-dibromodiphenyl ether
BDE-028 2,4,4'-tribromodihenyl ether
BDE-047 2,2',4,4'-tetrabromodiphenyl ether
BDE-099 2,2',4,4',5-pentabromodiphenyl ether
BDE-153 2,2',4,4',5,5'-hexabromodiphenyl ether
BDE-183 2,2',3,4,4',5',6-heptabromodiphenyl ether
BDE-203 2,2',3,4,4',5,5',6-octabromodiphenyl ether
BDE-206 2,2',3,3',4,4',5,5',6-nonabromodiphenyl ether
BDE-209 decabromodiphenyl ether
CRM certified reference material
DBP di-n-butyl phthalate
DEHP di-(2-ethylhexyl) phthalate
DIBP di-isobutyl phthalate
DIDP di-isodecyl phthalate
DINP di-isononyl phthalate
DNOP di-n-octyl phthalate
EGA evolved gas analysis
EI electron ionization
– 10 – IEC 62321-3-3:2021 © IEC 2021
GC gas chromatography
LOQ limit of quantification
MDL method detection limit
MS mass spectrometry
PBB polybrominated biphenyl
PBDE polybrominated diphenyl ether
PBMS performance-based measurement system
PE polyethylene
PP polypropylene
PS polystyrene
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
SIM selected ion monitoring
THF tetrahydrofuran
4 Principle
4.1 Overview
The concept of 'screening' has been developed to reduce the amount of testing. Executed as a
predecessor to any other test analysis, the main objective of screening is to quickly determine
whether the screened part or section of a product:
– contains a certain substance at a concentration significantly higher than its value or values
chosen as criterion, and therefore may be deemed unacceptable;
– contains a certain substance at a concentration significantly lower than its value or values
chosen as criterion, and therefore may be deemed acceptable;
– contains a certain substance at a concentration so close to the value or values chosen as
criterion that when all possible errors of measurement and safety factors are considered,
no conclusive decision can be made about the acceptable absence or presence of a certain
substance and, therefore, a follow-up action may be required, including further analysis
using verification testing procedures.
This test method is designed specifically to screen for PBBs, PBDEs, DIBP, DBP, BBP, DEHP,
DNOP, DINP, and DIDP in polymers in electrotechnical products by using the analytical
technique of Py/TD-GC-MS. Annex A provides a flow chart as an example of how this method
can be used for screening.
IEC 62321-3-3:2021 © IEC 2021 – 11 –
4.2 Principle of test
Py/TD-GC-MS uses gas chromatography-mass spectrometry coupled with a pyrolyser/thermal
desorption accessory (see Annex B, Figure B.1) to screen the presence of PBBs, PBDEs, DIBP,
DBP, BBP, DEHP, DNOP, DINP and DIDP in polymers in electrotechnical products. Since
Py/TD-GC-MS does not require any prolonged solvent extraction process, a fast screening of
PBBs, PBDEs and phthalates is available. The polymer sample is directly introduced into the
pyrolyser, which thermally extracts PBBs, PBDEs and phthalates from a polymer under a
specific heat zone. Thermally desorbed PBBs, PBDEs and phthalates are then transferred to
the gas chromatograph. PBBs, PBDEs and phthalates are separated by a gas chromatographic
capillary column and detected by a mass spectrometer. The respective PBBs, PBDEs and
phthalates are identified based on the retention times, m/z (quantification and confirmation ions),
and ion ratio as a result of standard specimen analysis. The selected ion monitoring (SIM) mode
is used as the measuring mode of MS to improve detection limits. Calculation of the PBBs,
PBDEs and phthalates concentration in the original sample is achieved by using response
factors (RFs) and relative response factors (RRFs) normalized by RF of the substitute
compound. RRFs can be continuously used by verifying the accuracy. Moreover, when the
accuracy satisfies the recovery rate between 70 % and 130 % by the test in 11.2.5, the RRFs
which are determined by a different Py/TD-GC-MS system can be applied.
NOTE 1 Additionally, scan measurement of MS is suitable to check negative matrix interference from other additives
in the polymer. Negative matrix interference causes ion suppression which provides lower concentration results.
Scan/SIM measurement (simultaneous measurements) is also applicable.
NOTE 2 Annex C provides the potential alternative test methods for the screening.
NOTE 3 Since IEC 62321 (all parts) employs PBMS, test methods that provide equivalent performance criteria
required in this document do not prevent its use.
5 Reagents and materials
All reagent chemicals shall be tested for contamination and blank values prior to application as
follows.
When measuring PBBs and/or PBDEs, low degradable materials (such as PP and PS) shall be
used as a standard sample for the determination of response factors, refer to Annex D:
NOTE 1 Deca-BB and deca-BDE are known to become highly degradable in some types of polymers.
a) blank polymer material from a pure source which does not contain the specific analytes and
other compounds that may interfere with the analysis by peak overlapping or ion
suppression: refer to Annex D;
b) helium (purity greater than a volume fraction of 99,999 %);
NOTE 2 The nitrogen gas can be used if it is confirmed that the required performance is satisfied.
c) calibrants: refer to Annex D;
d) polymer reference materials: One contains approximately 100 mg/kg of analytes (PBBs,
PBDEs and/or phthalates) and the other 1 000 mg/kg;
The following reagent chemicals, when used for preparing the polymer sample, shall be similarly
tested as the above:
e) toluene for preparing the PBBs, PBDEs and phthalates standard solution, GC grade or
higher;
f) THF for preparing the polymer solution, GC grade or higher.

– 12 – IEC 62321-3-3:2021 © IEC 2021
6 Apparatus
The following items shall be used for the analysis:
a) analytical balance capable of measuring accurately to 0,000 01 g (0,01 mg);
b) deactivated glass wool;
c) deactivated sample cup; if a sample cup is re-used, analyte carry-over shall be confirmed
by analysing without a sample;
NOTE 1 Before a sample cup is re-used, it is baked out to prevent cross contamination. However, if a re-used
sample cup causes certain PBDE and PBB decomposition, the sample cup is not re-used.
d) gas chromatograph – mass spectrometer equipped with a pyrolyser/thermal desorption
accessory, a split/splitless inlet and a programmable temperature controlled oven. The mass
spectrometer shall be able to perform selected ion monitoring (SIM) and a total ion
monitoring ("full scan");
NOTE 2 An auto-sampler is used to ensure repeatability.
e) pyrolyser/thermal desorption accessory;
f) capillary column;
The following items should be used for sample preparation as necessary:
g) cryogenic grinding mill with liquid nitrogen cooling;
h) polymer sample preparation tools to cut or file polymer such as nipper, micro spatula,
tweezers, cutter, file, and micro puncher;
i) micro syringe or automated pipettes;
j) glass equipment; made from brown or amber glass for long-term storage of PBDEs.
NOTE 3 To avoid decomposition and/or debromination of PBDEs by UV light during long-term sample storage,
glass equipment made from brown or amber glass is used.
7 Sampling
The sample can either be cut into small pieces using a cutter or filed off.
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 contaminations.
The following general instructions should be followed:
a) After analysis of test samples with high analyte concentration, blank samples should be
analysed until the background level of PBBs, PBDEs and phthalates is decreased to a value
equivalent to 100 mg/kg or even lower.
NOTE A blank polymer material or blank sample cup is used for blank-sample analysis.
b) In order to reduce blank values, ensure the cleanliness of all tools used in the sample
preparation.
IEC 62321-3-3:2021 © IEC 2021 – 13 –
8.2 Sample preparation
8.2.1 General
The sample preparation requires clean labware (e.g. cutter, tweezers) to avoid cross
contamination.
NOTE If the distribution of the analyte is not uniform and a sample mass of 0,5 mg is not guaranteed to represent
the degree of concentration, the sample is taken from several locations and mixed well using a cryogenic mill or
completely dissolved using an optimal solvent such as THF. Refer to IEC 62321-2 [3].
8.2.2 Polymer sample
a) Place approximately 0,5 mg of the cut or powdered sample into a pre-weighed sample cup
using a micro spatula or tweezers.
b) 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.
c) Place an appropriate amount of deactivated glass wool into the sample cup to ensure that
the sample powder will not spill out.
NOTE Refer to Annex E.
8.2.3 Stock solution or polymer reference material
The PS solution and standard mixture solution are available for the calibration and sensitivity
check. When polymer reference materials are available, they shall be used for the calibration
and sensitivity check. A thinly stretched polymer reference sheet or film would also be available
(see Annex D).
NOTE 1 The following solution concentrations and solvent types are examples and can be changed.
a) PS solution: 50 mg/ml in THF solvent;
NOTE 2 The other type of base polymer is available if it is dissolved completely by a suitable solvent.
NOTE 3 When measuring PBBs and/or PBDEs, deca-BDE is known to become highly degradable in some types
of polymers and a PS solution is used as a standard sample for the determination of response factors; refer
Annex D.
b) PBB solution: 50 μg/ml mono to deca-BB in toluene;
c) PBDE solution: 50 μg/ml mono to deca-BDE in toluene;
d) phthalate solution: 100 μg/ml in organic solvent such as hexane or toluene; the phthalate
solution should contain all phthalates necessary for analysis of DIBP, DBP, BBP, DEHP,
DNOP, DINP and DIDP;
e) stock solution of substitute compound such as DEHP: 100 µg/ml in organics solvent such
as hexane or toluene.
NOTE 4 When more than one compound is used as a substitute compound, each stock solution or mixture
solution is prepared.
8.3 Instrumental parameters
Different conditions may be necessary to optimize a specific Py/TD-GC-MS system to achieve
effective separation of each substance and meet the quality control (QC) and method detection
limits (MDL) requirements. The following parameters have been found suitable and are provided
as an example (see Table 1). The total ion current chromatogram and mass chromatogram is
shown in Annex G (see Figure G.1).

– 14 – IEC 62321-3-3:2021 © IEC 2021
Table 1 – Measurement conditions of Py/TD-GC-MS
Pyrolyser
Furnace temperature 200 °C → (20 °C/min) → 300 °C → (5 °C/min) → 340°C (1 min)
Interface temperature 300 °C (interface temperature control mode: manual)
GC
Column 100 % dimethyl polysiloxane, length 15 m; internal diameter 0,25 mm; film
thickness 0,05 µm
Injection port temperature 320 °C
Column oven temperature 80 °C → (20 °C /min) → 300 °C (5 min)
Injection mode Split (split ratio: 1/50)
Carrier gas Helium, 1,5 ml/min, constant linear velocity
MS
Ion source temperature 230 °C
Ionization method Electron ionization (EI), 70 eV.
Compound name Quantification ion Confirmation ion-1 Confirmation ion-2
BB-003 231,9 233,9 -
BB-015 311,8 309,8 313,8
BB-029 389,8 387,8 391,8
BB-049 309,8 307,8 467,7
BB-103 387,7 385,7 545,6
BB-153 467,6 465,6 627,5
BB-189 545,6 543,6 705,4
BB-194 625,5 623,5 627,5
BB-206 703,4 701,4 705,4 (863,4)
785,3 (943,1;
BB-209 783,3 781,3 215,8; 382,6;
384,5)
BDE-003 247,9 249,9
BDE-015 327,8 325,8 329,8
Monitoring mass ion (m/z)
BDE-028 405,8 403,8 407,8
BDE-047 325,8 323,8 483,7
BDE-099 403,7 401,7 561,6
BDE-153 483,6 481,6 643,5
BDE-183 561,6 559,6 721,4
BDE-203 641,5 639,5 643,5 (801,3)
BDE-206 719,4 717,4 721,4 (879,2)
BDE-209 799,3 797,3 959,1
DIBP 223 205 149
DBP 223 205 149
BBP 206 91 149
DEHP 279 167 149
DNOP 279 167 149
DINP 293 167 149
DIDP 307 167 149
Scan range m/z 50 to 1 000
IEC 62321-3-3:2021 © IEC 2021 – 15 –
NOTE 1 Additionally, scan measurement of MS is available to check negative matrix interference from other
additives in the polymer. Negative matrix interference causes ion suppression which provides a wrong quantitation
result. Simultaneous scan and SIM measurement are also acceptable.
NOTE 2 Scan measuring of MS is available for the detection of other additives.
NOTE 3 DIDP and DINP have multiple chromatogram peaks. The areas of these peaks above the baseline are
integrated.
NOTE 4 See Annex F for an optimization of furnace temperature.
NOTE 5 To prevent decomposition of PBDEs and PBBs, an inert or a thermally treated ion source box is available.

8.4 Calibration
8.4.1 General
The RRF for each analyte shall be calculated from the RF of each analyte and that of the
substitute compound. Selection of the substitute compound is critical in this method. DEHP is
a preferred compound because it is thermally and chemically stable especially in the process
of Py/TD-GC-MS analysis. Substitute compounds can be selected for each group of analytes
such as PBDEs, PBBs and phthalates, which have close physical and chemical properties.
The following describes the case where DEHP is used as the substitute compound.
8.4.2 Determination of RRFs
RRFs are determined for six phthalates (DIBP, DBP, BBP, DNOP, DINP, DIDP), mono- to
decabrominated biphenyl (PBB) and mono- to decabrominated diphenyl ether (PBDE). For
PBBs and PBDEs, the RRFs are determined for each congener. If DEHP is used as a substitute
compound, the RRF of DEHP becomes one.
RRFs can be continuously used by verifying the accuracy. Moreover, when the accuracy
satisfies the recovery rate between 70 % and 130 % by the test in 11.2.5, the RRFs which are
determined by a different Py/TD-GC-MS system can be applied.
NOTE 1 The accuracy required for RRFs is described in 11.2.3 and 11.2.4.
The procedure for the determination of RRF using a solution is as follows:
a) Prepare 0,5 mg of sample (e.g. PS polymer) containing analytes at a concentration of
1 000 mg/kg.
– Inject 10 μl of PS solution (50 mg/ml) into the sample cup.
– Inject 10 μl of PBB solution (50 μg/ml), 10 μl of PBDE solution (50 μg/ml) and 5 μl of
phthalate stock solution (100 μg/ml) into the same sample cup.
– Dry the sol
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