oSIST prEN 17937:2023

SLOVENSKI STANDARD
oSIST prEN 17937:2023
01-marec-2023
Regulirane kemikalije v izdelkih - Določanje vsebnosti policikličnih aromatskih
ogljikovodikov (PAH) z metodo plinske kromatografije z masno spektrometrijo v
polimernih materialih in gumi v izdelkih, namenjenih širši javnosti, ki prihajajo v
neposredni stik s človeško kožo in ustno votlino
Regulated chemicals in products - Determination of the content of polycyclic aromatic
hydrocarbons (PAHs) by gas chromatography coupled to mass-spectrometry in plastic
and rubber in articles supplied to the general public that come into direct contact with
human skin and oral cavity
Reglementierte Chemikalien in Erzeugnissen - Bestimmung des Gehalts von
polyzyklischen aromatischen Kohlenwasserstoffen (PAK) mittels Gaschromatographie in
Kunststoff und Gummi in Gegenständen für die breite Öffentlichkeit, die in direkten
Kontakt mit der menschlichen Haut und der Mundhöhle kommen
Substances chimiques règlementées dans les produits - Détermination de la teneur en
hydrocarbures aromatiques polycycliques (HAP) par chromatographie en phase gazeuse
couplée à la spectrométrie de masse dans les articles en plastique et en caoutchouc
fournis au grand public entrant en contact direct avec la peau humaine et la cavité
buccale
Ta slovenski standard je istoveten z: prEN 17937
ICS:
71.080.15 Aromatski ogljikovodiki Aromatic hydrocarbons
83.140.01 Izdelki iz gume in polimernih Rubber and plastics products
materialov na splošno in general
oSIST prEN 17937:2023 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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oSIST prEN 17937:2023


DRAFT
EUROPEAN STANDARD
prEN 17937
NORME EUROPÉENNE

EUROPÄISCHE NORM

January 2023
ICS 71.080.15; 83.140.01
English Version

Regulated chemicals in products - Determination of the
content of polycyclic aromatic hydrocarbons (PAHs) by gas
chromatography coupled to mass-spectrometry in plastic
and rubber in articles supplied to the general public that
come into direct contact with human skin and oral cavity
Substances chimiques règlementées dans les produits - Reglementierte Chemikalien in Erzeugnissen -
Détermination de la teneur en hydrocarbures Bestimmung des Gehalts von polyzyklischen
aromatiques polycycliques (HAP) par chromatographie aromatischen Kohlenwasserstoffen (PAK) mittels
en phase gazeuse couplée à la spectrométrie de masse Gaschromatographie in Kunststoff und Gummi in
dans les articles en plastique et en caoutchouc fournis Gegenständen für die breite Öffentlichkeit, die in
au grand public entrant en contact direct avec la peau direkten Kontakt mit der menschlichen Haut und der
humaine et la cavité buccale Mundhöhle kommen
This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee
CEN/TC 462.

If this draft becomes a European Standard, CEN members are bound to comply with the CEN/CENELEC Internal Regulations
which stipulate the conditions for giving this European Standard the status of a national standard without any alteration.

This draft European Standard was established by CEN in three official versions (English, French, German). A version in any other
language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC
Management Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Türkiye and
United Kingdom.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are
aware and to provide supporting documentation.

Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without
notice and shall not be referred to as a European Standard.


EUROPEAN COMMITTEE FOR STANDARDIZATION

COMITÉ EUROPÉEN DE NORMALISATIO N
E UROPÄISCHES KOMITEE FÜR NORMUN G

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2023 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 17937:2023 E
worldwide for CEN national Members.

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Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative references . 5
3 Terms and definitions . 5
4 Principle . 6
5 Reagents . 6
6 Apparatus and materials . 7
7 Sample preparation and storage . 8
7.1 Sample preparation . 8
7.2 Preparation of standard solutions. 8
7.3 Sample storage . 9
8 Procedure . 9
8.1 Extraction . 9
8.2 Sample clean-up . 11
8.3 Determination by GC-MS . 11
8.4 Calibration using an internal standard . 12
8.5 Measurement . 13
8.6 Identification . 13
9 Calculation . 13
10 Test report . 13
Bibliography . 14

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European foreword
This document (prEN 17937:2023) has been prepared by Technical Committee CEN/TC 462 “Regulated
chemicals in products”, the secretariat of which is held by AFNOR.
This document is currently submitted to the CEN Enquiry.
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Introduction
In December 2013, based on a report established in 2010 by the German authorities, the European
Commission amended the REACH Annex XVII through the Regulation (EU) No. 1272/2013, with amend
entry 50, with the addition of paragraphs 5 and 6. This Regulation addresses and restricts the use of
eight PAHs (Polycyclic Aromatic Hydrocarbons) in rubber and plastic articles supplied to the general
public that come into direct as well as prolonged contact or short-term repetitive contact with human
skin or the oral cavity, under normal or reasonably foreseeable conditions of use.
To support the enforcement of this restriction the European Commission requested the European
Committee for Standardization (CEN) and the European Committee for Electrotechnical Standardization
(CENELEC) to draft harmonized standards for the analytical determination of the individual
concentrations of the 8 carcinogenic PAHs, listed in entry 50 of Annex XVII to Regulation (EC) No.
1907/2006 (REACH), in plastic and rubber components (see standardization request M/556).
A Technical Board Working Group 13 "PAHs" (CEN-CLC/BT/WG 13) established by CEN-CENELEC had
to investigate that request through a scoping study which had to identify if any existing methods to
determine the total content for PAHs in rubber and plastic articles exist but also if any spectroscopic
methods could assist Market Surveillance Authorities in performing non-destructive screening tests.
The result of the scoping study based on an up to date literature review concluded the need to develop
a harmonized standard to support (EU) No. 1272/2013 legislation, which is developed hereafter.

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1 Scope
This document specifies a method to determine the total content of the 8 regulated polycyclic aromatic
hydrocarbons (PAHs), see Table 1, in plastic and rubber articles by using GC-MS allowing detection at
0,1 mg PAHs/kg for plastic and 0,2 mg PAHs/kg for rubber material.
Table 1 — List of PAHs
PAHs CAS number
Benzo[a]pyrene (BaP) CAS No 50-32-8
Benzo[e]pyrene (BeP) CAS No 192-97-2
Benzo[a]anthracene (BaA) CAS No 56-55-3
Chrysene (CHR) CAS No 218-01-9
Benzo[b]fluoranthene (BbFA) CAS No 205-99-2
Benzo[j]fluoranthene (BjFA) CAS No 205-82-3
Benzo[k]fluoranthene (BkFA) CAS No 207-08-9
Dibenzo[a,h]anthracene (DBahA) CAS No 53-70-3
NOTE Other PAHs compounds can also be analysed with this method, provided suitability has been proven.
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.
EN ISO 22892:2011, Soil quality — Guidelines for the identification of target compounds by gas
chromatography and mass spectrometry (ISO 22892:2006)
ISO 1407:2011, Rubber — Determination of solvent extract
ISO 21461:2012, Rubber — Determination of the aromaticity of oil in vulcanized rubber compounds
3 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminology databases for use in standardization at the following addresses:
— IEC Electropedia: available at https://www.electropedia.org/
— ISO Online browsing platform: available at https://www.iso.org/obp
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4 Principle
The test specimen is extracted using toluene (or n-heptane) using a Soxhlet or Randall (automated
Soxhlet) extraction or ultrasonic bath extraction method. The extract is concentrated and interfering
compounds are removed by a clean-up method. An aliquot is then analysed using a gas chromatograph
with mass selective detector (GC-MS).
PAHs are identified and quantified with GC-MS by comparison of relative retention times and relative
peak heights (or peak areas) with respect to internal standards added.
5 Reagents
WARNING — Polycyclic Aromatic Hydrocarbons can cause cancer, are suspected of damaging an
unborn child, can cause damage to organs through prolonged or repeated exposure, and can be
fatal if swallowed and/or enter airways. Appropriate measures shall be taken to ensure safety.
All reagents shall be of recognized analytical grade unless specified in a different way.
— Toluene, CAS number: 108-88-3. or n-heptane, CAS number: 142-82-5
— Ethanol, CAS number: 64-17-5
— Cyclohexane, CAS number: 110-82-7
— PAHs standard solutions
The standards shall be chosen so that they behave in the same way as the corresponding analytes and
that they can be readily quantified (see Table 2).
All purchased PAHs standard materials shall be 98 % pure or better and certified in respect of their
purity, concentration level, and authenticity by the manufacturer. PAH standards diluted in cyclohexane
can be accepted.
Standard solutions and extracts should be stored in a dark place (e.g. in amber glassware) at about
(5+/- 3) °C. These standard solutions and extracts shall not be used after 1 year.
— Internal standards
At least 3 internal standards shall be used, using one of each ring system family as shown in Table 2. The
internal standards given in Table 2 are examples. Others may be used, as long as they represent at least
the 3+, the 4+ and the 5+ ring systems
Table 2 — Native (calibration standards) and deuterated (internal standards) PAHs
compounds
Calibration standard Ring system Internal standard
benzo[a]anthracene 3+ benzo[a]anthracene-d12
chrysene 3+ benzo[a]anthracene-d12
benzo[k]fluoranthene 4+ benzo[b]fluoranthene-d12
benzo[b]fluoranthene 4+ benzo[b]fluoranthene-d12
benzo[j]fluoranthene 4+ benzo[b]fluoranthene-d12
benzo[a]pyrene 5+ benzo[a]pyrene-d12
benzo[e]pyrene 5+ benzo[a]pyrene-d12
dibenzo[a,h]anthracene 5+ benzo[a]pyrene-d12
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6 Apparatus and materials
To prevent any interference, it is recommended to avoid plastic and other organic materials.
It is recommended to use the usual equipment and laboratory glassware according to EN ISO 4787:2021
and the following:
— Analytical balance, with a precision of at least 0,1 mg to weigh the samples;
Analytical balance, with precision of at least 0,01 mg shall be used by labs which are preparing their
stock solutions from pure chemicals.
— Micropipettes, 50 μl and 100 μl;
— Pipette, 0,5 ml to 5 ml capacity;
— Glass vials (amber);
— Gas chromatograph coupled to a mass-spectrometer (MS) with electron ionisation (EI) capability
and single ion monitoring (SIM) mode or MS/MS with multiple reaction monitoring (MRM) mode.
GC Capillary Column: it is strongly recommended to use a GC column specifically dedicated for PAHs
analysis, with column length of at least 30 m, internal diameter 0,25 mm to 0,32 mm, film thickness
0,17 μm to 0,25 μm.
Deactivated straight borosilicate liner with small piece of deactivated glass wool - this liner may be used
as long as peak resolution is satisfactory.
An alternative liner is a split/splitless not deactivated liner with glass wool (4-mm internal diameter,
straight liner).
Liners shall be deactivated with a silanizing agent before use. Another alternative is a split/splitless liner
with fluorocarbon liner seals. Such a liner will already contain conditioned silanized glass wool.
Other liners can be used if they produce acceptable results.
It is recommended to use a gold-plated seal for GC injector port or similar nonreactive seal.
GC/MS amber autosampler vials with polytetrafluoroethylene (PTFE)-coated caps.
Crimping tool.
— Extraction apparatus:
2
— Ultrasonic bath: Minimum power 200W wi
...