IEC 62321-3-3:2021

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 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.

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)

L'IEC 62321-3-3:2021 spécifie l’analyse de détection de diphényles polybromés (PBB), de diphényléthers polybromés (PBDE), de phtalate de diisobutyle (DIBP), de phtalate de dibutyle (DBP), de phtalate de benzyle et de butyle (BBP), de phtalate de bis(2-éthylhexyle) (DEHP), de phtalate de di-n-octyle (DNOP), de phtalate de di-isononyle (DINP) et de phtalate de di-isodécyle (DIDP) dans les polymères des produits électrotechniques en utilisant la méthode analytique de la chromatographie en phase gazeuse-spectrométrie de masse par pyrolyse/thermodésorption (Py/TD-GC-MS).
Cette méthode d’essai a été évaluée à l'aide de l’analyse de matériaux de PP (polypropylène), de PS (polystyrène) et de PVC (polychlorure de vinyle) qui contiennent du déca-BDE à des concentrations allant de 100 mg/kg à 1 000 mg/kg ainsi que des phtalates individuels à des concentrations comprises entre 100 mg/kg et 4 000 mg/kg, comme cela est décrit dans l’Annexe J. L'utilisation des méthodes décrites dans le présent document pour d’autres types de polymères, de PBB (mono à déca), de PBDE (mono à déca) et pour des phtalates ou des plages de concentration autres que ceux spécifiés ci-dessus n’a pas été évaluée spécifiquement.
Le présent document a le statut d'une norme horizontale conformément au Guide 108 de l'IEC.

General Information

• Status: Published
• Publication Date: 13-Sep-2021
• ICS: 13.020.01 - Environment and environmental protection in general
• ICS: 43.040.10 - Electrical and electronic equipment
• Technical Committee: TC 111 - Environmental standardization for electrical and electronic products and systems
• Drafting Committee: WG 3 - TC 111/WG 3
• Current Stage: PPUB - Publication issued
• Start Date: 14-Sep-2021
• Completion Date: 10-Sep-2021

Overview

IEC 62321-3-3:2021 is an internationally recognized standard developed by the International Electrotechnical Commission (IEC) that specifies screening methods for detecting hazardous substances in electrotechnical products. This part, titled "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)", focuses on analyzing specific brominated flame retardants and phthalates in polymer materials.

The standard defines analytical procedures using Py/TD-GC-MS technology to screen for:

• Polybrominated biphenyls (PBBs)
• Polybrominated diphenyl ethers (PBDEs)
• Several types of phthalates including DIBP, DBP, BBP, DEHP, DNOP, DINP, and DIDP

It provides a reliable and harmonized method mainly applicable to polypropylene (PP), polystyrene (PS), and polyvinyl chloride (PVC) polymers within defined concentration ranges, ensuring accurate chemical safety assessments in electrical and electronic components.

Key Topics

• Analytical Technique: Uses gas chromatography-mass spectrometry combined with pyrolyser/thermal desorption, enabling effective extraction and measurement of PBBs, PBDEs, and phthalates in polymers.
• Scope and Application Range: Targets polymers commonly used in electrotechnical products containing concentrations of specific substances in mg/kg concentrations, with emphasis on screening rather than full quantification.
• Sample Preparation: Involves careful sampling procedures like cutting or cryogenic grinding to ensure representative polymer sample analysis.
• Calibration and Quality Control: Describes calibration methods including determination of relative response factors (RRFs), plus rigorous quality control steps such as blank tests, sensitivity and stability checks, ensuring dependable screening results.
• Screening Results Evaluation: Provides criteria for screening judgements based on detection limits, repeatability, and reproducibility data validated through international inter-laboratory studies.
• Horizontal Standard Status: Functions as a horizontal standard supporting a broad range of electrotechnical applications and passing quality benchmarks in line with IEC Guide 108.

Applications

The IEC 62321-3-3:2021 standard is essential for:

• Regulatory Compliance: Assisting manufacturers and testing labs to meet international hazardous substance regulations such as RoHS (Restriction of Hazardous Substances) by screening for banned or restricted additives in polymeric components.
• Quality Assurance in Manufacturing: Enabling quality control during the production of electrotechnical materials by identifying polybrominated flame retardants and phthalates that may impact environmental safety.
• Environmental Health and Safety: Supporting safer design and recycling of electrical and electronic devices through early detection of substances with potential environmental or health risks.
• Research and Development: Providing a validated method for formulation scientists and chemists to evaluate polymer additive compositions during product development.

Related Standards

IEC 62321-3-3:2021 is part of the IEC 62321 series, which covers determination of various restricted substances in electrical and electronic products. Related standards include:

• IEC 62321-1: Introduction and overview of procedures for determination of certain substances.
• IEC 62321-4: Determination of mercury in electrotechnical products.
• IEC 62321-5: Determination of cadmium, lead, and other heavy metals.
• IEC 62321-6: Methods for hexavalent chromium detection.
• IEC 62321-7 series: Covers additional substances like phthalates and flame retardants with alternative analysis methods.

These standards collectively provide a comprehensive framework for chemical safety testing, ensuring global harmonization in hazardous substance screening and compliance for the electronics industry.

---

Keywords: IEC 62321-3-3, electrotechnical products, polybrominated biphenyls, polybrominated diphenyl ethers, phthalates, Py/TD-GC-MS, gas chromatography-mass spectrometry, polymers, screening method, hazardous substances, electrical and electronic equipment, RoHS compliance, polymer analysis, quality assurance.

Standards Content (Sample)

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)

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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

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
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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.
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.

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
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.
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.
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
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 solution at room temperature.
b) Analyse the samples.
c) Record the peak area.
d) Calculate the RF of DEHP and that of each analyte using Equations (4) and (5), respectively.
e) Calculate the RRFs of each analyte using Equation (8).
Polymer reference materials, such as those containing these analytes at a concentration of
1 000 mg/kg, can be used as well as DEHP at the concentration of 1 000 mg/kg as a substitute
compound sample.
f) Analyse polymer reference materials (8.2.1).
g) Record peak area.
h) Calculate the RF of DEHP and that of each analyte using Equations (4) and (5).
i) Calculate the RRFs of each analyte using Equation (8).

– 16 – IEC 62321-3-3:2021 © IEC 2021
RF = A / m (4)
DEHP DEHP DEHP
RF = A / m (5)
A A A
where
−1
RF and RF are the response factors of DEHP and of the analyte, respectively (mg );
DEHP A
A and A
...