IEC 62321-10:2020

Determination of certain substances in electrotechnical products - Part 10: Polycyclic aromatic hydrocarbons (PAHs) in polymers and electronics by gas chromatography-mass spectrometry (GC-MS)

IEC 62321-10:2020 specifies one normative technique for the determination of polycyclic aromatic hydrocarbons (PAHs) in polymers of electrotechnical products. These PAHs can especially be found in the plastic and rubber parts of a wide range of consumer articles. They are present as impurities in some of the raw materials used in the production of such articles, in particular in extender oils and in carbon black. They are not added intentionally to the articles and do not perform any specific function as constituents of the plastic or rubber parts.
The gas chromatography-mass spectrometry (GC MS) test method is suitable for the determination of polycyclic aromatic hydrocarbons (PAHs).
These test methods have been evaluated for use with plastics and rubbers. These test methods have been evaluated for use with ABS (acrylonitrile butadiene styrene) containing individual PAHs ranging from 37,2 mg;kg to 119 mg;kg and rubbers containing individual PAHs ranging from 1 mg;kg to 221,2 mg;kg.
WARNING – This document does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this document to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
This horizontal standard is primarily intended for use by technical committees in the preparation of standards in accordance with the principles laid down in IEC Guide 108.
One of the responsibilities of a technical committee is, wherever applicable, to make use of horizontal standards in the preparation of its publications. The contents of this horizontal standard will not apply unless specifically referred to or included in the relevant publications.

Détermination de certaines substances dans les produits électrotechniques - Partie 10: Hydrocarbures aromatiques polycycliques (HAP) dans les polymères et les produits électroniques par chromatographie en phase gazeuse-spectrométrie de masse (GC-MS)

L'62321-10:20220 spécifie une méthode normative de détermination des hydrocarbures aromatiques polycycliques (HAP) dans les polymères des produits électrotechniques. Ces HAP se trouvent surtout dans les éléments en plastique et en caoutchouc de nombreux articles grand public. Ils sont présents sous forme d’impuretés dans certaines des matières premières entrant dans la fabrication de ces articles, notamment dans les huiles de dilution et le noir de carbone. Les HAP ne sont pas ajoutés intentionnellement aux articles et ne remplissent aucune fonction spécifique en tant que composants des éléments en plastique ou en caoutchouc.
La méthode d’essai chromatographie en phase gazeuse-spectrométrie de masse (GC MS - gas chromatography-mass spectrometry) convient à la détermination des hydrocarbures aromatiques polycycliques (HAP).
Ces méthodes d’essai ont été évaluées pour utilisation sur des plastiques et des caoutchoucs. Elles ont en outre été évaluées pour l’ABS (acrylonitrile butadiène styrène) allant de 37,2 mg/kg à 119 mg/kg de HAP spécifiques et pour des caoutchoucs allant de 1 mg/kg à 221,2 mg/kg de HAP spécifiques.
AVERTISSEMENT – Le présent document n’a pas pour but de traiter tous les problèmes éventuels de sécurité liés à son utilisation. Il incombe à l’utilisateur du présent document d’établir, avant de l’utiliser, des pratiques d’hygiène et de sécurité appropriées et de déterminer l’applicabilité des restrictions réglementaires.
Cette norme horizontale est essentiellement destinée à l'usage des comités d'études dans l'élaboration des normes, conformément aux principes établis dans le Guide IEC 108.
Une des responsabilités d'un comité d'études est, partout où cela est possible, de se servir des normes horizontales lors de l'élaboration de ses publications. Le contenu de cette norme horizontale ne s'applique pas, à moins qu'il ne soit spécifiquement désigné ou inclus dans les publications concernées.

General Information

• Status: Published
• Publication Date: 23-Jun-2020
• ICS: 13.020.01 - Environment and environmental protection in general
• ICS: 13.260 - Protection against electric shock. Live working
• ICS: 29.020 - Electrical engineering 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: 24-Jun-2020
• Completion Date: 26-Jun-2020

Standards Content (Sample)

IEC 62321-10 ®
Edition 1.0 2020-06
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
HORIZONTAL STANDARD
NORME HORIZONTALE
Determination of certain substances in electrotechnical products –
Part 10: Polycyclic aromatic hydrocarbons (PAHs) in polymers and electronics
by gas chromatography-mass spectrometry (GC-MS)

Détermination de certaines substances dans les produits électrotechniques –
Partie 10: Hydrocarbures aromatiques polycycliques (HAP) dans les polymères
et les produits électroniques par chromatographie en phase gazeuse-
spectrométrie de masse (GC MS)

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IEC 62321-10 ®
Edition 1.0 2020-06
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
HORIZONTAL STANDARD
NORME HORIZONTALE
Determination of certain substances in electrotechnical products –

Part 10: Polycyclic aromatic hydrocarbons (PAHs) in polymers and electronics

by gas chromatography-mass spectrometry (GC-MS)

Détermination de certaines substances dans les produits électrotechniques –

Partie 10: Hydrocarbures aromatiques polycycliques (HAP) dans les polymères

et les produits électroniques par chromatographie en phase gazeuse-

spectrométrie de masse (GC MS)

INTERNATIONAL
ELECTROTECHNICAL
COMMISSION
COMMISSION
ELECTROTECHNIQUE
INTERNATIONALE
ICS 13.020.01; 43.040.10 ISBN 978-2-8322-8441-4

– 2 – IEC 62321-10:2020 © IEC 2020
CONTENTS
FOREWORD . 4
INTRODUCTION . 6
1 Scope . 7
2 Normative references . 7
3 Terms, definitions and abbreviated terms . 8
3.1 Terms and definitions . 8
3.2 Abbreviated terms . 8
4 Principle . 8
5 Reagents and materials . 8
6 Apparatus . 9
7 Sampling . 10
8 Procedure . 10
8.1 General instructions for the analysis . 10
8.2 Sample preparation . 11
8.2.1 Ultrasonic extraction . 11
8.2.2 Soxhlet extraction . 11
8.2.3 Sample clean-up . 11
8.3 Instrumental parameters . 12
8.4 Calibrants . 13
8.4.1 General . 13
8.4.2 Stock solution . 13
8.4.3 Preparation of calibration standard . 13
8.4.4 Internal standard . 15
8.4.5 Surrogate standard . 15
8.5 Calibration . 15
8.5.1 General . 15
8.5.2 Calibration standard solutions of PAHs . 16
9 Calculation of PAH concentration . 17
9.1 General . 17
9.2 Calculation . 17
10 Precision: repeatability and reproducibility . 18
11 Quality assurance and control . 20
11.1 Performance . 20
11.2 Limit of detection (LOD) or method detection limit (MDL) and limit of
quantification (LOQ) . 20
12 Test report . 21
Annex A (informative) Additional GC-MS conditions . 22
A.1 Instrumental parameters for GC-MS . 22
A.2 Examples of suitable column and its separation results for PAHs . 23
Annex B (informative) Results of international interlaboratory study of PAHs
(IIS10-PAHs) . 26
Annex C (informative) Labware cleaning procedure for PAH testing . 28
C.1 With the use of furnace (non-volumetric glassware only) . 28
C.2 Without the use of furnace (glassware and plastic-ware) . 28
C.3 Estimation of cleanness of the inner areas of volumetric glassware . 29

Bibliography . 30

Figure A.1 – Examples of total ion chromatograms of PAHs for each suitable PAH
column, naphthalene to benzo[ghi]perylene . 25

Table 1 – List of reference masses for the quantification of PAHs . 12
Table 2 – Example list of commercially available calibration chemicals considered
suitable for this analysis . 13
Table 3 – Preparation of low concentrations of the calibration standard solution for
GC-MS analysis . 16
Table 4 – Preparation of high concentrations of the calibration standard solution for
GC-MS analysis . 16
Table 5 – IIS10-PAHs repeatability and reproducibility . 18
Table A.1 – Instrument parameters for GC-MS . 22
Table A.2 – Examples of suitable column and its separation results for PAHs . 23
Table A.3 – Information of each PAH substance and numbers of aromatic rings . 25
Table B.1 – Statistical data for GC-MS . 26

– 4 – IEC 62321-10:2020 © IEC 2020
INTERNATIONAL ELECTROTECHNICAL COMMISSION
____________
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 10: Polycyclic aromatic hydrocarbons (PAHs) in polymers and
electronics by gas chromatography-mass spectrometry (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
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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.
International Standard IEC 62321-10 has been prepared by IEC technical committee 111:
Environmental standardization for electrical and electronic products and systems.
The text of this International Standard is based on the following documents:
FDIS Report on voting
111/575/FDIS 111/580/RVD
Full information on the voting for the approval of this International Standard can be found in the
report on voting indicated in the above table.
This document has been drafted in accordance with the ISO/IEC Directives, Part 2.
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 "http://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 62321-10:2020 © IEC 2020
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 62321-10 introduces a new subject covering polycyclic aromatic
hydrocarbons (PAHs) in the IEC 62321 series.
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 10: Polycyclic aromatic hydrocarbons (PAHs) in polymers and
electronics by gas chromatography-mass spectrometry (GC-MS)

1 Scope
This part of IEC 62321 specifies one normative technique for the determination of polycyclic
aromatic hydrocarbons (PAHs) in polymers of electrotechnical products. These PAHs can
especially be found in the plastic and rubber parts of a wide range of consumer articles. They
are present as impurities in some of the raw materials used in the production of such articles,
in particular in extender oils and in carbon black. They are not added intentionally to the articles
and do not perform any specific function as constituents of the plastic or rubber parts.
The gas chromatography-mass spectrometry (GC-MS) test method is suitable for the
determination of polycyclic aromatic hydrocarbons (PAHs).
These test methods have been evaluated for use with plastics and rubbers. These test methods
have been evaluated for use with ABS (acrylonitrile butadiene styrene) containing individual
PAHs ranging from 37,2 mg/kg to 119 mg/kg and rubbers containing individual PAHs ranging
from 1 mg/kg to 221,2 mg/kg.
WARNING – This document does not purport to address all of the safety concerns, if any,
associated with its use. It is the responsibility of the user of this document to establish
appropriate safety and health practices and determine the applicability of regulatory limitations
prior to use.
This horizontal standard is primarily intended for use by technical committees in the preparation
of standards in accordance with the principles laid down in IEC Guide 108.
One of the responsibilities of a technical committee is, wherever applicable, to make use of
horizontal standards in the preparation of its publications. The contents of this horizontal
standard will not apply unless specifically referred to or included in the relevant publications.
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, Determination of certain substances in electrotechnical products – Part 2:
Disassembly, disjointment and mechanical sample preparation
ISO 3696, Water for analytical laboratory use – Specification and test methods

– 8 – IEC 62321-10:2020 © IEC 2020
3 Terms, definitions and abbreviated terms
3.1 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following
addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
3.2 Abbreviated terms
ABS acrylonitrile butadiene styrene
CCC continuing calibration check standard
EI electron ionization
GC-MS gas chromatography-mass spectrometry
IS internal standard
IUPAC International Union of Pure and Applied Chemistry
LOD limit of detection
LOQ limit of quantification
MDL method detection limit
PAH polycyclic aromatic hydrocarbon
PBDE polybrominated diphenyl ether
QC quality control
RSD relative standard deviation
SIM selected ion monitoring
TICS tentatively identified compounds
US EPA United States Environmental Protection Agency

4 Principle
PAH compounds are quantitatively determined using ultrasonic extraction or Soxhlet extraction
followed by gas chromatography-mass spectrometry (GC-MS) using single (or "selected") ion
monitoring (SIM).
5 Reagents and materials
Use, as far as available, reagents of analytical quality, or better. Use only reagents with
negligibly low concentrations of PAH and verify by blank determinations and, if necessary, apply
additional cleaning steps (for calibrants, see 8.4):
a) Dichloromethane (GC grade or higher).
b) Helium (purity of greater than a volume fraction of 99,999 %).
c) Silica gel (purity of greater than a mass fraction of 99 %).
d) Toluene (GC grade or higher).

NOTE 1 The standards are acceptable when using a quadrupole-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 (see 8.4). Other stock solution concentrations can be utilized providing the standard solution
concentrations given in 8.5.2 can be achieved.
e) Sodium sulphate (purity of greater than a mass fraction of 99 %).
f) Surrogate and internal standards:
– internal standard (to correct for injection errors, according to 8.4.2 a)),
(e.g. naphthalene-d8, pyrene-d10, anthracene-d10, phenanthrene-d10,
benzo(a)pyrene-d12, perylene-d12 or triphenylbenzene);
NOTE 2 At least three internal standards are preferably used to be mixed with toluene as extraction agent.
– surrogate standard (to monitor analyte recovery according to 8.4.2 b),
(e.g. chrysene-d12 or p-terphenyl-d14).
g) Petroleum ether (purity of greater than a mass fraction of 99 %).
h) Water (Grade 1 specified in ISO 3696 used for preparation of labware and others).
6 Apparatus
The following items shall be used for the analysis:
a) 0,45 μm PTFE filter membrane.
b) 1 ml, 5 ml, 10 ml, 100 ml volumetric flasks.
c) Aluminium foil.
d) Analytical balance capable of measuring accurately to 0,000 1 g.
e) 40 ml brown or amber vessel.
f) Cryogenic grinding with liquid N cooling.
g) Dry oven.
h) Furnace.
i) Extraction thimble (cellulose 30 ml, ID 22 mm, height 80 mm).
j) Funnel.
k) Glass column (size: 220 mm × 15 mm).
l) Glass wool (for extraction thimble).
m) Heating jackets.
n) Microlitre syringe or automatic pipettes.
o) Mini-shaker (also known as vortexer or vortex mixer).
p) Pasteur pipette.
q) Rotary evaporator.
r) Soxhlet extractors:
– 30 ml Soxhlet extractors,
– 250 ml round-bottomed flasks,
– ground-in stopper NS 29/32,
– Dimroth condenser NS 29/32,
– boiling stones (e.g. glass pearls or Raschig rings).
s) Ultrasonic extractors:
Ultrasonic bath with a minimum power of 200 W and a bath area of 706 cm , corresponding
to 0,28 W/cm , without a basket and with an internal or external thermostat.

– 10 – IEC 62321-10:2020 © IEC 2020
t) Vial for GC-MS:
2 ml sample vials with 100 μl glass insert and a screw cap with polytetrafluoroethylene
(PTFE) gasket or depending on the analytical system, a comparable sample receptacle.
Brown or amber vessels shall be used as indicated in the text of the procedure.
u) GC-MS:
A gas chromatograph with a capillary column coupled to a mass spectrometric detector
(electron ionization, EI) is used for the analysis. The mass spectrometric detector shall be
able to perform selective ion monitoring and have an upper mass range of at least 550 m/z.
The use of an autosampler is strongly recommended to ensure repeatability. Ferrules used
shall not contain more than 40 % graphite (a suitable ferrule is made of 60 % polyimide and
40 % graphite) to decrease the risk that PAHs are absorbed.
v) GC column for PAH analysis:
A column length of 20 m or longer has sufficient separation efficiency for PAH compounds.
An example of suitable column and its separation results is given in Annex A, see Table A.2,
Table A.3 and Figure A.1.
For the capillary column, 5 % phenyl, 95 % methyl polysiloxane (e.g. such as HT8,
DB-EUPAH and ZB-PAH) is recommended. The preferred dimensions are 20 m in length,
0,25 mm or 0,18 mm in internal diameter, and 0,25 μm or 0,14 μm in film thickness.
NOTE Based on the AfPS-GS-2014-01-PAK method, a nonpolar DB-5MS column is not suited for a separation of
the different benzofluoranthenes listed in Table 1.
7 Sampling
As described in IEC 62321-2, unless indicated otherwise (e.g. "using a knife"), cryogenic
grinding with liquid nitrogen cooling is recommended and the samples shall be ground to pass
through a 500 μm sieve before extraction.
If samples are not tested immediately, they shall be stored in tightly sealed glass vessels and
in a cool and dark place.
It shall be confirmed that glassware is thoroughly cleaned and that all new materials that may
come into contact with the sample are checked by blank analysis that they give no interference.
NOTE Interferences which can affect the results can occur due to contaminations from glassware, solvents and
other materials that can come into contact with the sample. Such interferences will form an artifact or will increase
the detector baseline. Interferences can also come from components in samples that co-elute with the specific PAHs
of interest.
8 Procedure
8.1 General instructions for the analysis
The following general instructions shall be followed:
The validation of the instrumentation shall include testing of potential cross contaminations
between sequential samples. Additional blanks or an inverted sequence of testing will help to
identify cross contaminations.
See Annex C for guidance regarding labware cleaning procedures for PAH testing.
To avoid decomposition of PAHs by UV light during extraction and analysis, glass equipment
made from brown or amber glass shall be used.
NOTE If no brown or amber glass is available, aluminium foil can be used for protection from light.

8.2 Sample preparation
8.2.1 Ultrasonic extraction
The following steps shall be followed for sample extraction:
The samples shall be pre-cut less than 5 mm × 5 mm and/or milled by cryogenic grinding with
liquid N cooling or cut sample materials to 2 mm to 3 mm. Quantitatively transfer
500 mg ± 10 mg of the sample into the vessel (Clause 6 e)).
a) Weigh 500 mg ± 10 mg of the sample into a 40 ml amber vessel (Clause 6 e)). Record the
mass to the nearest 0,1 mg.
b) Add 20 μl of the surrogate standard (Clause 5 f)) (100 μg/ml) into the 40 ml amber vessel.
c) Transfer 20 ml of toluene (Clause 5 d)) and 20 μl of internal standard (8.4.4 c)) (100 μg/ml)
to the 40 ml amber vessels (Clause 6 e)).
d) Place it in an ultrasonic extractor (Clause 6 s)) and sonicate it for about 1 h at 60 °C and
then allow to cool at room temperature after the extraction of the sample.
e) Allow the polymer to settle or filter the mixture through a 0,45 μm PTFE membrane.
8.2.2 Soxhlet extraction
For the Soxhlet extraction step the following procedure is applied:
a) Quantitatively transfer 500 mg ± 10 mg of the sample into a cellulose extraction thimble for
Soxhlet extraction. Record the mass to the nearest 0,1 mg.
b) Allow the sample to be transferred through a funnel into the extraction thimble. To ensure a
quantitative transfer, the funnel should be rinsed with approximately 10 ml of toluene.
c) 10 μl of the surrogate standard (8.4.5 d)) (50 μg/ml) is added.
d) Cover the thimble with glass wool to prevent the sample from floating.
e) Approximately 120 ml of toluene is used for extraction under reflux. Allow the sample to be
extracted for at least 6 h with 6 to 8 cycles per hour. Shorter extraction times may result in
lower recoveries of the analyses.
f) After six hours of reflux, the extract is concentrated to about 2 ml using a vacuum rotary
evaporator. 10 μl of the internal standard (8.4.4 d)) (50 μg/ml) is then added and the extract
is diluted with toluene to 5 ml.
g) The diluted sample is transferred into a 2 ml GC sample/auto sample vial with a PTFE
coated seal.
8.2.3 Sample clean-up
If the interference is caused by relatively polar compounds of the same boiling range as the
analytes, then multiple column or cartridge clean-ups may be required.
a) The silica gel (Clause 5 c)) is deactivated beforehand by adding 10 % water (the
corresponding volume of water is added to the silica gel in a glass flask, and the mixture is
homogenized on the rotary evaporator for 1 h at standard pressure and room temperature.
The silica gel can then be stored in the sealed glass flask at room temperature).
b) The packed column is conditioned with 10 ml of petroleum ether (Clause 5 g)).
c) The aliquot of toluene extract is then evaporated to a volume of approximately 1 ml on the
rotary evaporator and poured into the column.
d) The pointed flask is rinsed out with approximately 20 ml of eluent, which is then also
transferred to the clean-up column.
e) Elution is performed with 50 ml of petroleum ether.
f) The collected petroleum ether eluent is amended with 1 ml of toluene and evaporated to a
volume of approximately 1 ml under a nitrogen stream (e.g. on the TurboVap).
g) This is then made up to a defined volume with toluene, and the extract is analysed by GC-MS.

– 12 – IEC 62321-10:2020 © IEC 2020
8.3 Instrumental parameters
Different conditions might be necessary to optimize a specific GC-MS system to achieve
effective separation of all calibration congeners and meet the QC and limits of detection (LOD)
requirements. The following parameters have been found suitable and are provided as an
example:
a) GC column: a column length of approximately 20 m or longer has sufficient separation
efficiency for PAH compounds (see Clause A.2 for an example of suitable column and its
separation results). For the capillary column, 5 % phenyl, 95 % methyl polysiloxane (e.g.
such as HT8, DB-EUPAH and ZB-PAH) is recommended. The preferred dimensions are
length 20 m, internal diameter 0,25 mm or 0,18 mm, and film thickness 0,25 μm or 0,14 μm.
b) Carrier: helium (see Clause 5 b)), 1,0 ml/min, constant flow.
c) Oven: 50 °C (initial temperature), 300 °C (final temperature), 10 °C/min ramp to 300 °C.
d) Injection temperature: 280 °C.
e) Injection volume: 1 μl.
A full scan run using a total ion current ("full scan") MS method for each sample is also
recommended for checking for the existence of peaks/congeners not present in the calibration
(tentatively identified compounds or "TICS") or not seen in the SIM window. If present, identify
the peak and determine the class of compound (e.g. benzo[e]pyrene, benzo[a]pyrene) by
evaluation of the total ion spectra.
Table 1 lists GC-MS parameters related to reference masses for the quantification of PAHs.
Additional detailed GC-MS instrument parameters are described in Table A.1.
Table 1 – List of reference masses for the quantification of PAHs
Type of PAHs Ions (m/z) monitored in the extract
Target ions (m/z) Qualifier ions (m/z)
Internal standard
Naphthalene-d8 136 108 137
Anthracene-d10 188 178 187
Benzo[a]pyrene-d12 264 260 265
Substances
Naphthalene 128 102 129
Acenaphthylene 152 76 151
Acenaphthene 154 76 153
Fluorene 166 83 165
Phenanthrene 178 76 179
Anthracene 178 89 176
Fluoranthene 202 101 200
Pyrene 202 101 200
Benzo[a]anthracene 228 114 226
Chrysene 228 114 226
Benzo[b]fluoranthene 252 126 253
Benzo[j]fluoranthene 252 126 253
Benzo[k]fluoranthene 252 126 253
Benzo[e]pyrene 252 126 253
Benzo[a]pyrene 252 126 253
Indeno[1,2,3cd]pyrene 276 138 274
Dibenzo[a,h]anthracene 278 139 276
Benzo[ghi]perylene 276 138 274

8.4 Calibrants
8.4.1 General
All PAH species from naphthalene- to benzo(g,h,i)perylene shall be included in the calibration.
The availability of calibration standards for a particular PAH (e.g. benzo(a)pyrene) may vary
from region to region. The following Table 2 is an example list of typically available calibration
chemicals which are suitable for this analysis.
8.4.2 Stock solution
The following stock solutions shall be prepared:
a) Internal standard (to correct for injection error): 50 μg/ml, 100 μg/ml in toluene
(e.g. naphthalene-d8, anthracene-d10 and benzo[a]pyrene-d12).
b) Surrogate standard (to monitor analyte recovery): 50 μg/ml, 100 μg/ml in toluene
(e.g. chrysene-d12).
c) A PAH solution can be utilized providing the standard solution concentrations given in
8.5.2 can be achieved.
8.4.3 Preparation of calibration standard
Table 2 – Example list of commercially available calibration chemicals
considered suitable for this analysis
Abbreviation Compound name CAS number Formula Molecular mass
(g/mol)
C H
ACE Acenaphthene 83-32-9 154,20
12 10
C H
ACY Acenaphthylene 208-96-8 152,20
12 8
C H
ANT Anthracene 120-12-7 178,24
14 10
C H
BaA Benzo[a]anthracene 56-55-3 228,30
18 12
C H
BaP Benzo[a]pyrene 50-32-8 252,32
20 12
C H
BeP Benzo[e]pyrene 192-97-2 252,32
20 12
C H
BbF Benzo[b]fluoranthene 205-99-2 252,32
20 12
C H
BjF Benzo[j]fluoranthene 205-82-3 252,32
20 12
C H
BkF Benzo[k]fluoranthene 207-08-9 252,32
20 12
C H
BghiP Benzo[ghi]perylene 191-24-2 276,34
22 12
C H
CHR Chrysene 218-01-9 228,30
18 12
C H
DBahA Dibenzo[a,h]anthracene 53-70-3 278,35
22 14
C H
FLU Fluoranthene 206-44-0 202,26
16 10
C H
FLN Fluorene 86-73-7 166,23
13 10
C H
IcdP Indeno[1,2,3cd]pyrene 193-39-5 276,34
22 12
C H
NP Naphthalene 91-20-3 128,18
10 8
C H
PHE Phenanthrene 85-01-8 178,24
14 10
C H
PYR Pyrene 129-00-0 202,26
16 10
– 14 – IEC 62321-10:2020 © IEC 2020
a) 1 000 mg/l each standard mixed stock solution:
The standards of Table 2 are respectively weighed to 0,1 g (100 mg) with an accuracy of
0,001 g, then placed in a 100 ml beaker, dissolved in a small amount of dichloromethane
(Clause 5 a)), and measuring the volume of 100 ml after they are filled up with
dichloromethane graduated to the mark and transferred to a flask (Clause 6 b)) in order to
well shake the mix. (If necessary, it may be shaked ultrasonically.)
b) Intermediate standard mixed solution of 20 mg/l for GC-MS analysis:
Pipet 2 ml from each stock standard solution (8.4.3 a)) and 2 ml surrogate standard solution
(8.4.5 b)) into a 100 ml volumetric flask and fill with dichloromethane up to the mark.
c) Intermediate standard mixed solution of 10 mg/l for GC-MS analysis:
Pipet 1 ml from each stock standard solution (8.4.3 a)) and 1 ml surrogate standard solution
(8.4.5 b)) into a 100 ml volumetric flask and fill with dichloromethane up to the mark.
d) For low concentration samples, test standard solutions for GC-MS analysis:
For the preparation of low concentrations of the calibration standard solution (8.4.3 e) to
8.4.3 h)), PAH standard solutions are prepared for GC-MS analysis as shown in Table 3.
These standard solutions each contain (20, 50, 100, 200) μg/l of one of the 18 PAH
compounds. Internal standards each contain 50 μg/l of substance (such as naphthalene-
d8, anthracene-d10 and benzo[a]pyrene-d12).
e) 20 μg/l calibration standard solution:
Pipet 0,02 ml from the 10 mg/l standard solution and 0,1 ml from the 5 mg/l working internal
standard solution into a 10 ml volumetric flask and fill with dichloromethane up to the mark.
f) 50 μg/l calibration standard solution:
Pipet 0,05 ml from the 10 mg/l standard solution and 0,1 ml from the 5 mg/l working internal
standard solution into a 10 ml volumetric flask and fill with dichloromethane up to the mark.
g) 100 μg/l calibration standard solution:
Pipet 0,1 ml from the 10 mg/l standard solution and 0,1 ml from the 5 mg/l working internal
standard solution into a 10 ml volumetric flask and fill with dichloromethane up to the mark.
h) 200 μg/l calibration standard solution:
Pipet 0,2 ml from the 10 mg/l standard solution and 0,1 ml from the 5 mg/l working internal
standard solution into a 10 ml volumetric flask and fill with dichloromethane up to the mark.
i) For high concentration samples, test standard solutions for GC-MS analysis:
For the preparation of high concentrations of the calibration standard solution (8.4.3 e) to
8.4.3 h)), PAH standard solutions are prepared for GC-MS analysis as shown in Table 4.
These standard solutions each contain (0,5, 1, 2, 4, 10) mg/l of one of the 18 PAH
compounds. Internal standards each contain 2 mg/l of substance (such as naphthalene-d8,
anthracene-d10 and benzo[a]pyrene-d12).
j) 0,5 mg/l calibration standard solution:
Pipet 0,25 ml from the 20 mg/l standard solution and 1 ml from the 20 mg/l working internal
standard solution into a 10 ml volumetric flask and fill with dichloromethane up to the mark.
k) 1 mg/l calibration standard solution:
Pipet 0,5 ml from the 20 mg/l standard solution and 1 ml from the 20 mg/l working internal
standard solution into a 10 ml volumetric flask and fill with dichloromethane up to the mark.
l) 2 mg/l calibration standard solution:
Pipet 1 ml from the 20 mg/l standard solution and 1 ml from the 20 mg/l working internal
standard solution into a 10 ml volumetric flask and fill with dichloromethane up to the mark.
m) 4 mg/l calibration standard solution:
Pipet 2 ml from the 20 mg/l standard solution and 1 ml from the 20 mg/l working internal
standard solution into a 10 ml volumetric flask and fill with dichloromethane up to the mark.

n) 10 mg/l calibration standard solution:
Pipet 5 ml from the 20 mg/l standard solution and 1 ml from the 20 mg/l working internal
standard solution into a 10 ml volumetric flask and fill with dichloromethane up to the mark.
8.4.4 Internal standard
a) Working internal standard mixed solution:
To analyse by GC-MS methods, using a naphthalene-d8, anthracene-d10 and
benzo[a]pyrene-d12 as an internal standard.
b) 1 000 mg/l working internal standard mixed solution:
Put 0,1 g (100 mg) of three internal standards (naphthalene-d8, anthracene-d10 and
benzo[a]pyrene-d12) into a 100 ml volumetric flask and fill with dichloromethane up to the
mark. (If necessary, ultrasonic shaking may be used).
c) 100 mg/l working internal standard mixed solution:
Pipet 10 ml from the 1 000 mg/l working internal standard mixed solution into a 100 ml
volumetric flask and fill with dichloromethane up to the mark.
d) 50 mg/l working internal standard mixed solution:
Pipet 5 ml from the 1 000 mg/l working internal standard mixed solution into a 100 ml
volumetric flask and fill with dichloromethane up to the mark.
8.4.5 Surrogate standard
a) Working surrogate standard solution:
To monitor analyte recovery, using a chrysene-d12 as a surrogate standard.
b) 1 000 mg/l working internal standard mixed solution:
A quantity of 0,1 g (100 mg) of surrogate standard (chrysene-d12) is placed in a 100 ml
beaker and dissolved in a small amount of dichloromethane (Clause 5 a)), and then filled
with dichloromethane (Clause 5 a)) up to the mark of the 100 ml volumetric flask. (If
necessary, ultrasonic extraction may be used).
c) 100 mg/l working surrogate standard solution:
10 ml of a 1 000 mg/l of working surrogate standard solution (8.4.5 b)) is taken , and placed
in a 100 ml volumetric flask for measurement, then filled with dichloromethane (Clause 5 a))
up to the mark.
d) 50 mg/l working surrogate standard solution:
5 ml of a 1 000 mg/l of working surrogate standard solution (8.4.5 b)) is taken and placed in
a 100 ml volumetric flask for measurement, then filled with dichloromethane (Clause 5 a))
up to the mark.
8.5 Calibration
8.5.1 General
Wherever possible, the solvent used for the sample and standard solutions shall be the same
to avoid any potential solvent effects. A calibration curve shall be developed for quantitative
analysis. At least five calibration solutions shall be prepared in equidistant concentration steps.
Quantification is made on the basis of the measurement of the specified peak areas taken from
the GC chromatogram. The linear regression fit of each calibration curve is required to have a
relative standard deviation (RSD) of less than or equal to 15 % of the linear calibration function.
NOTE If the limiting value of the RSD of 15 % is exceeded, from the point of view of quality assurance, second-
order curve fitting does not guarantee any significantly better adjustment. Only statistical tests such as the F-test
nd
fulfil these requirements by comparing linear/2 order. That means that although the RSD value is exceeded, the
calibration is linear.
– 16 – IEC 62321-10:2020 © IEC 2020
8.5.2 Calibration standard solutions of PAHs
A PAH standard solution (20 μg/ml of ea
...