Textiles and textile products - Organic fluorine - Part 1: Determination of non-volatile compounds by extraction method using liquid chromatography

This document specifies a test method (using liquid chromatography, LC) for detection and quantification of selected extractable perfluorinated and polyfluorinated substances in textile materials (fibres, yarns, fabrics) and coated fabrics.
NOTE 1 CEN/TR 16741 defines which materials are applicable to this determination.
A test method (using gas chromatography, GC) for detection and quantification of selected extractable perfluorinated and polyfluorinated substances is specified in EN 17681-2.
NOTE 2 Both this document and EN 17681-2 are needed for the determination and totalization of the PFOA related substances.
Classes of regulated compounds are listed in Table 2. Classes of other non-regulated compounds that can be determined by this document are defined in Annex C, Table C.1. This document is also applicable for further PFAS substances provided that the method is validated with the additional compounds.
NOTE 3 Commission Delegated Regulation (EU) 2020/784 amending Annex I to the POP Regulation (EU) 2019/1021 as regards the listing of perfluorooctanoic acid (PFOA), its salts and PFOA-related compounds defines among other that “’…PFOA-related compounds’ means the following: … any substances that degrade to PFOA, including any substances (including salts and polymers) having a linear or branched perfluoroheptyl group with the moiety (C7F15)C as one of the structural elements.” To determine whether these are intentionally present it could be necessary to introduce an alkaline hydrolysis method to remove the side-chain from the polymer. According to Commission Regulation (EU) 2021/1297 [7], this applies similarly to C9-C14 PFCAs-related compounds. A future revision of this document will address this aspect.

Textilien und textile Erzeugnisse - Organisches Fluor - Teil 1: Bestimmung des Gehaltes an nichtflüchtigen Verbindungen durch Extraktionsverfahren mittels Flüssigkeitschromatographie

Dieses Dokument legt ein Prüfverfahren (unter Anwendung von Flüssigkeitschromatographie, LC (en: liquid chromatography)) zum Nachweis und zur quantitativen Bestimmung von ausgewählten extrahierbaren perfluorierten und polyfluorierten Verbindungen in textilen Materialien (Fasern, Garne, textile Flächengebilde) und beschichteten textilen Flächengebilden fest.
ANMERKUNG 1 CEN/TR 16741 legt fest, welche Materialien für diese Bestimmung anzuwenden sind.
Ein Prüfverfahren (unter Anwendung von Gaschromatographie, GC (en: gas chromatography)) zum Nachweis und zur quantitativen Bestimmung von ausgewählten extrahierbaren perfluorierten und polyfluorierten Verbindungen ist in EN 17681-2 festgelegt.
ANMERKUNG 2 Sowohl dieses Dokument als auch EN 17681-2 werden für die Bestimmung und Totalisierung der PFOA verwandten Verbindungen benötigt.
Die Klassen regulierter Verbindungen sind in Tabelle 2 aufgeführt. Klassen anderer, nichtregulierter Verbindungen, die nach diesem Dokument bestimmt werden können, sind in Anhang C, Tabelle C.1, festgelegt. Dieses Dokument ist auch anzuwenden für weitere PFAS Verbindungen, vorausgesetzt, dass das Verfahren mit den zusätzlichen Verbindungen validiert wird.
ANMERKUNG 3 Die delegierte Verordnung (EU) 2020/784 der Kommission zur Änderung des Anhangs I der Verordnung (EU) 2019/1021 des Europäischen Parlaments und des Rates hinsichtlich der Aufnahme von Perfluoroctansäure (PFOA), ihrer Salze und von PFOA-verwandten Verbindungen legt u. a. fest, dass „PFOA verwandte Verbindungen umfasst: ...alle Stoffe (...), die zu PFOA abgebaut werden, einschließlich aller Stoffe (auch Salze und Polymere), die eine lineare oder verzweigte Perfluorheptylgruppe mit dem Bestandteil (C7F15)C als Strukturelement aufweisen.“ Um festzustellen, ob ihre Anwesenheit beabsichtigt ist, könnte die Aufnahme eines alkalischen Hydrolyseverfahrens zur Entfernung der Seitenkette des Polymers erforderlich sein. Nach Verordnung (EU) 2021/1297 der Kommission [7] trifft dies gleichermaßen auf C9-C14 PFCA-verwandte Stoffe zu. Eine zukünftige Überarbeitung dieses Dokumentes wird diesen Gesichtspunkt berücksichtigen.

Textiles et produits textiles - Fluor organique - Partie 1 : Détermination de composés non volatils par une méthode d’extraction utilisant la chromatographie en phase liquide

Le présent document spécifie une méthode d'essai (par chromatographie en phase liquide, LC) pour la détection et la quantification, dans des matières textiles (fibres, fils, étoffes) et des supports textiles revêtus, de substances perfluorées et polyfluorées extractibles sélectionnées.
NOTE 1 Le CEN/TR 16741 définit les matériaux auxquels s'applique cette détermination.
Une méthode d'essai (par chromatographie en phase gazeuse, GC) pour la détection et la quantification de substances perfluorées et polyfluorées extractibles sélectionnées est spécifiée dans l'EN 17681-2.
NOTE 2 Le présent document et l'EN 17681-2 sont tous les deux nécessaires pour les substances apparentées au PFOA.
Les classes de composés réglementés sont répertoriées dans le Tableau 2. Les classes d'autres composés, non réglementés, qui peuvent être déterminés en appliquant le présent document sont définies dans le Tableau C.1 (Annexe C). Le présent document est également applicable à d'autres PFAS, à condition que la méthode soit validée avec les composés additionnels.
NOTE 3 Le règlement délégué (UE) 2020/784 de la Commission modifiant l'annexe I du règlement (UE) 2019/1021 concernant les polluants organiques persistants aux fins d’y inscrire l’acide perfluorooctanoïque (PFOA), ses sels et les composés apparentés au PFOA stipule, entre autres, ce qui suit : « par " composés apparentés au PFOA ", il est entendu : … toutes les substances qui se dégradent en PFOA, y compris les substances (sels et polymères compris) qui comportent, parmi leurs éléments structurels, un groupe fonctionnel perfluoroheptyle (C7F15)C linéaire ou ramifié. » Pour déterminer si leur présence est intentionnelle, il pourrait s'avérer nécessaire d'introduire une méthode d'hydrolyse alcaline pour supprimer la chaîne latérale du polymère. Conformément au règlement (UE) 2021/1297[7] de la Commission, ceci s'applique de manière similaire aux composés apparentés aux PFCA en C9-C14. Le sujet sera abordé dans une future révision du présent document.

Tekstil in tekstilni izdelki - Organski fluor - 1. del: Določevanje nehlapnih spojin z ekstrakcijsko metodo s tekočinsko kromatografijo

General Information

Status
Published
Publication Date
27-Sep-2022
Current Stage
6060 - Definitive text made available (DAV) - Publishing
Start Date
28-Sep-2022
Due Date
24-Dec-2021
Completion Date
28-Sep-2022

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SLOVENSKI STANDARD
01-december-2022
Tekstil in tekstilni izdelki - Organski fluor - 1. del: Določevanje nehlapnih spojin z
ekstrakcijsko metodo s tekočinsko kromatografijo
Textiles and textile products - Organic fluorine - Part 1: Determination of non-volatile
compounds by extraction method using liquid chromatography
Textilien und textile Erzeugnisse - Organisches Fluor - Teil 1: Bestimmung des Gehaltes
an nichtflüchtigen Verbindungen durch Extraktionsverfahren mittels
Flüssigkeitschromatographie
Textiles et produits textiles - Fluor organique - Partie 1 : Détermination de composés non
volatils par une méthode d’extraction utilisant la chromatographie en phase liquide
Ta slovenski standard je istoveten z: EN 17681-1:2022
ICS:
59.080.01 Tekstilije na splošno Textiles in 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.

EN 17681-1
EUROPEAN STANDARD
NORME EUROPÉENNE
September 2022
EUROPÄISCHE NORM
ICS 59.080.01
English Version
Textiles and textile products - Organic fluorine - Part 1:
Determination of non-volatile compounds by extraction
method using liquid chromatography
Textiles et produits textiles - Fluor organique - Partie 1 Textilien und textile Erzeugnisse - Organisches Fluor -
: Détermination de composés non volatils par une Teil 1: Bestimmung des Gehaltes an nichtflüchtigen
méthode d'extraction utilisant la chromatographie en Verbindungen durch Extraktionsverfahren mittels
phase liquide Flüssigkeitschromatographie
This European Standard was approved by CEN on 24 July 2022.

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. 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
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 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.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2022 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 17681-1:2022 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
Introduction . 4
1 Scope .11
2 Normative references .11
3 Terms and definitions .11
4 Principle of method .12
5 Reagents .12
6 Equipment .12
7 Sampling .13
7.1 General .13
7.2 Sampling based on area .13
7.3 Sampling based on mass .13
7.4 Preparation of test specimen .13
8 Procedure.14
8.1 Preparation of stock solutions .14
8.2 Preparation of the check solution .14
8.3 Preparation of calibration solutions .14
8.4 Extraction .14
8.5 Analysis .14
9 Expression of results .15
9.1 Calibration .15
9.2 Calculation of the results .15
9.3 Calculation of the sums of certain PFAS .16
9.4 Limit of detection (LoD) and limit of quantification (LoQ) .16
9.5 Reliability of the method .16
10 Test report .18
Annex A (normative) Usable ions and reachable quantification limits for PFAS analysis by
LC/MS/MS .19
Annex B (informative) Interferences with LC/MS/MS .21
Annex C (informative) Non-regulated PFAS .22
Annex D (informative) Chromatographic conditions .23
D.1 General .23
D.2 Chromatographic conditions .23
D.3 LC/MS/MS conditions .23
Bibliography .24

European foreword
This document (EN 17681-1:2022) has been prepared by Technical Committee CEN/TC 248 “Textiles
and textile products”, the secretariat of which is held by BSI.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by March 2023, and conflicting national standards shall be
withdrawn at the latest by March 2023.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN 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 standards body.
A complete listing of these bodies can be found on the CEN website.
According to the CEN-CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to implement this European Standard: 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 the United
Kingdom.
Introduction
In the European Union, according to Regulation (EU) 2019/1021 on persistent organic pollutants (POP),
Article 3, Clause 1, in connection with Annex I, amended by Commission Delegated Regulation
(EU) 2020/784, the manufacturing, placing on the market and use of perfluorooctanoic acid (PFOA), its
salts and PFOA-related compounds, whether on their own, in mixtures or in articles, is prohibited. This
is in addition to the existing prohibition of perfluorooctane sulfonic acid and its derivatives (PFOS).
According to Article 4 Clause 1. (b) this does not apply in the case of a substance present as an
unintentional trace contaminant, as specified in the relevant entries of Annex I in substances, mixtures
or articles.
Annex I Part A, describing perfluorooctane sulfonic acid and its derivatives (PFOS), contains the specific
exemption (Point 2) to concentrations of PFOS in semi-finished products or articles, or parts thereof, if
the concentration of PFOS is lower than 0,1 % mass fraction calculated with reference to the mass of
structurally or micro-structurally distinct parts that contain PFOS or, for textiles or other coated
materials, if the amount of PFOS is lower than 1 μg/m of the coated material. PFOS compounds have the
+
formula C F SO X where X = OH, Metal salt (O-M ), halide, amide and other derivatives, including
8 17 2
polymers.
In Annex I Part A, describing perfluorooctanoic acid (PFOA), its salts and PFOA-related compounds,
contains the specific exemption (Point 1) to concentrations of PFOA or any of its salts equal to or below
0,025 mg/kg (0,000 002 5 % mass fraction), where they are present in substances, mixtures or articles.
In addition, (Point 2) Article 4(1) applies to concentrations of any individual PFOA-related compound or
a combination of PFOA-related compounds equal to or below 1 mg/kg (0,000 1 % mass fraction) where
they are present in substances, mixtures or articles.
PFOA, its salts and PFOA-related compounds means the following:
i) perfluorooctanoic acid, including any of its branched isomers;
ii) its salts;
iii) PFOA-related compounds which, for the purposes of the Convention, are any substances that degrade
to PFOA, including any substances (including salts and polymers) having a linear or branched
perfluoroheptyl group with the moiety (C F )C as one of the structural elements.
7 15
The following compounds are not included as PFOA-related compounds:
iv) C F -X, where X = F, Cl, Br;
8 17
v) fluoropolymers that are covered by CF [CF ] -R’, where R’ = any group, n > 16;
3 2 n
vi) perfluoroalkyl carboxylic acids (including their salts, esters, halides and anhydrides) with ≥ 8
perfluorinated carbons;
vii) perfluoroalkane sulfonic acids and perfluoro phosphonic acids (including their salts, esters, halides
and anhydrides) with ≥ 9 perfluorinated carbons;
viii) perfluorooctane sulfonic acid and its derivatives (PFOS), as listed in Annex I.
As a further exemption in Annex I Part A (Point 5 c) the manufacturing, placing on the market and use of
PFOA, its salts and PFOA-related compounds is allowed in textiles for oil and water repellency for the
protection of workers from dangerous liquids that comprise risks to their health and safety, until 4 July
2023.
Commission Regulation (EU) 2021/1297 amending Regulation (EC) No 1907/2006 (REACH), Annex
XVII [7] restricts perfluorocarboxylic acids containing 9 to 14 carbon atoms in the chain (C9-C14 PFCAs),
their salts and C9-C14 PFCA-related substances from 25 February 2023.
This restriction concerns the following substances:
Linear and branched perfluorocarboxylic acids of the formula C F -C(= O)OH where n = 8, 9, 10, 11,
n 2n+1
12, or 13 (C9-C14 PFCAs), including their salts, and any combinations thereof;
Any C9-C14 PFCA-related substance having a perfluoro group with the formula C F - directly attached
n 2n+1
to another carbon atom, where n = 8, 9, 10, 11, 12, or 13, including their salts and any combinations
thereof;
Any C9-C14 PFCA-related substance having a perfluoro group with the formula C F - that it is not
n 2n+1
directly attached to another carbon atom, where n = 9, 10, 11, 12, 13 or 14 as one of the structural
elements, including their salts and any combinations thereof.
The following substances are excluded from this designation:
C F -X, where X = F, Cl, or Br
n 2n+1
where n = 9, 10, 11, 12, 13 or 14, including any combinations thereof,
C F -C(= O)OX' where n > 13 and X' = any group, including salts.
n 2n+1
Several per- and poly-fluorinated alkylated substances (PFAS), which are not restricted under the POP
Regulation have been added as Substances of Very High Concern (SVHC) to the Candidate List according
to Regulation (E
...

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