EN 17681-1:2025

Textiles and textile products - Per- and polyfluoroalkyl substances (PFAS) - Part 1: Analysis of an alkaline extract using liquid chromatography and tandem mass spectrometry

This document specifies a test method, including the degradation of certain side-chain fluorinated polymers during the extraction with simultaneous alkaline hydrolysis, and using liquid chromatography (LC) and tandem mass spectrometry (MS/MS) for identification and quantification of certain per- and polyfluoroalkyl substances (PFAS). The document is applicable to all materials of textile products.
Table 2 indicates a list of target PFAS which can be analysed with this document. PFAS of Table 2 marked with the footnote e) and footnote f) undergo alkaline hydrolysis and only their per- or polyfluorinated degradation products such as PFOA or n:2 fluorotelomer alcohols (n:2 FTOHs, n = 4, 6, 8, 10) can be determined.
Through the methods outlined in the informative Annex E and Annex F, free n:2 FTOHs, PFOA and non-polymeric PFAS of Table 2 marked with the footnote e) and footnote f), that are not stable to alkaline hydrolysis, can be identified and quantified.
Certain side-chain fluorinated polymers release n:2 FTOHs (n = 4, 6, 8, 10) under the described extraction conditions. Since these side-chain fluorinated polymers can be PFOA or C9-C14 PFCA-related substances restricted by the EU-POPs [1] or EU-REACH [2] regulations, the amounts of released n:2 FTOHs can be used to indirectly assess whether the concentration of the aforementioned side-chain fluorinated polymers exceed limits for PFOA or C9-C14 PFCA-related substances.
This document is also applicable to the determination of further PFAS, provided that the method is validated with the additional substances and that these PFAS are stable to alkaline hydrolysis and dehydrofluorination.

Textilien und textile Erzeugnisse - Per- und polyfluorierte Alkylverbindungen (PFAS) - Teil 1: Untersuchung eines alkalischen Extraktes mittels Flüssigkeitschromatographie und Tandem-Massenspektrometrie

Dieses Dokument legt ein Prüfverfahren, einschließlich des Abbaus bestimmter seitenkettenfluorierter Polymere während der Extraktion mit gleichzeitiger alkalischer Hydrolyse, unter Verwendung von Flüssigkeitschromatographie (LC, en: liquid chromatography) und Tandem-Massenspektrometrie (MS/MS, en: tandem mass spectrometry) zur Identifizierung und quantitativen Bestimmung bestimmter per- und polyfluorierter Alkylverbindungen (PFAS) fest. Das Dokument ist für alle Materialien textiler Erzeugnisse anwendbar.
In Tabelle 2 ist eine Liste der Ziel-PFAS angegeben, die nach diesem Dokument analysiert werden können. PFAS in Tabelle 2, die mit der Fußnote e) und der Fußnote f) gekennzeichnet sind, werden einer alkalischen Hydrolyse unterzogen, und nur ihre per- oder polyfluorierten Abbauprodukte wie beispielsweise PFOA oder n:2 Fluortelomeralkohole (n:2 FTOHs, n = 4, 6, 8, 10) können bestimmt werden.
Durch die im informativen Anhang E und Anhang F beschriebenen Verfahren können freie n:2 FTOHs, PFOA und nichtpolymere PFAS in Tabelle 2, die mit der Fußnote e) und der Fußnote f) gekennzeichnet und nicht stabil gegenüber alkalischer Hydrolyse sind, identifiziert und quantitativ bestimmt werden.
Bestimmte seitenkettenfluorierte Polymere setzen unter den beschriebenen Extraktionsbedingungen n:2 FTOHs (n = 4, 6, 8, 10) frei. Da diese seitenkettenfluorierten Polymere PFOA oder C9-C14-PFCA-verwandte Verbindungen sein können, die nach der EU-POPs-Verordnung [1] oder der EU-REACH-Verordnung [2] beschränkt sind, können die Mengen der freigesetzten n:2 FTOHs indirekt verwendet werden, um zu bewerten, ob die Konzentration der vorstehend genannten seitenkettenfluorierten Polymere die Grenzwerte für PFOA oder C9-C14-PFCA-verwandte Verbindungen überschreitet.
Dieses Dokument ist auch für die Bestimmung weiterer PFAS anwendbar, vorausgesetzt, dass das Verfahren mit den zusätzlichen Verbindungen validiert ist und dass diese PFAS gegenüber alkalischer Hydrolyse und Dehydrofluorierung stabil sind.

Textiles et produits textiles - Substances perfluoroalkylées et polyfluoroalkylées (PFAS) - Partie 1 : Analyse d’un extrait alcalin par chromatographie en phase liquide et spectrométrie de masse en tandem

Le présent document spécifie une méthode d’essai incluant la dégradation de certains polymères fluorés à chaîne latérale pendant l’extraction avec hydrolyse alcaline simultanée et en utilisant la chromatographie en phase liquide (LC) et la spectrométrie de masse en tandem (MS/MS) pour l’identification et la quantification de certaines substances perfluoroalkylées et polyfluoroalkylées (PFAS). Le document est applicable à tous les matériaux de produits textiles.
Le Tableau 2 donne une liste des PFAS cibles qui peuvent être analysées à l’aide du présent document. Les PFAS du Tableau 2 repérées par les notes de bas de tableau e) et f) subissent une hydrolyse alcaline et seuls leurs produits de dégradation perfluorés et polyfluorés tels que le PFOA ou les n:2 alcools fluorotélomères (n:2 FTOH, n = 4, 6, 8, 10) peuvent être déterminés.
Grâce aux méthodes décrites aux Annexes E et F informatives, les n:2 FTOH libres, le PFOA et les PFAS non polymères du Tableau 2 repérées par les notes de bas de tableau e) et f), qui ne sont pas stables à l’hydrolyse alcaline, peuvent être identifiés et quantifiés.
Certains polymères fluorés à chaîne latérale libèrent des n:2 FTOH (n = 4, 6, 8, 10) dans les conditions d’extraction décrites. Dans la mesure où ces polymères fluorés à chaîne latérale peuvent être des substances apparentées au PFOA ou au PFCA en C9-C14 soumises à restriction par le Règlement UE concernant les POP [1] ou le Règlement UE REACH [2], les quantités de n:2 FTOH libérés peuvent être utilisées pour évaluer indirectement si la concentration des polymères fluorés à chaîne latérale susmentionnés dépasse les limites relatives aux substances apparentées au PFOA ou au PFCA en C9-C14.
Le présent document est également applicable à la détermination d’autres PFAS, sous réserve que la méthode soit validée avec les substances supplémentaires et que ces PFAS soient stables à l’hydrolyse alcaline et à la déshydrofluoration.

Tekstilije in tekstilni izdelki - Per- in polifluoroalkilne snovi (PFAS) - 1. del: Analiza alkalnega ekstrakta s tekočinsko kromatografijo in tandemsko masno spektrometrijo

General Information

• Status: Published
• Publication Date: 29-Apr-2025
• ICS: 59.080.01 - Textiles in general
• Technical Committee: CEN/TC 248 - Textiles and textile products
• Drafting Committee: CEN/TC 248/WG 26 - Methods of test for phthalates
• Current Stage: 6060 - Definitive text made available (DAV) - Publishing
• Start Date: 30-Apr-2025
• Due Date: 16-May-2025
• Completion Date: 30-Apr-2025
• Directive: 1907/2006 - Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 18 December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), establishing a European Chemicals Agency, amending Directive 1999/45/EC and repealing Council Regulation (EEC) No 793/93 and Commission Regulation (EC) No 1488/94 as well as Council Directive 76/769/EEC and Commission Directives 91/155/EEC, 93/67/EEC, 93/105/EC and 2000/21/EC
• Ref Project: SIST EN 17681-1:2025 - Textiles and textile products - Per- and polyfluoroalkyl substances (PFAS) - Part 1: Analysis of an alkaline extract using liquid chromatography and tandem mass spectrometry

Relations

• Replaces: EN 17681-1:2022 - Textiles and textile products - Organic fluorine - Part 1: Determination of non-volatile compounds by extraction method using liquid chromatography
• Effective Date: 08-Feb-2023

Standards Content (Sample)

SLOVENSKI STANDARD
01-julij-2025
Tekstilije in tekstilni izdelki - Per- in polifluoroalkilne snovi (PFAS) - 1. del: Analiza
alkalnega ekstrakta s tekočinsko kromatografijo in tandemsko masno
spektrometrijo
Textiles and textile products - Per- and polyfluoroalkyl substances (PFAS) - Part 1:
Analysis of an alkaline extract using liquid chromatography and tandem mass
spectrometry
Textilien und textile Erzeugnisse - Per- und polyfluorierte Alkylverbindungen (PFAS) -
Teil 1: Untersuchung eines alkalischen Extraktes mittels Flüssigkeitschromatographie
und Tandem-Massenspektrometrie
Textiles et produits textiles - Substances perfluoroalkylées et polyfluoroalkylées (PFAS) -
Partie 1 : Analyse d’un extrait alcalin par chromatographie en phase liquide et
spectrométrie de masse en tandem
Ta slovenski standard je istoveten z: EN 17681-1:2025
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
April 2025
EUROPÄISCHE NORM
ICS 59.080.01 Supersedes EN 17681-1:2022
English Version
Textiles and textile products - Per- and polyfluoroalkyl
substances (PFAS) - Part 1: Analysis of an alkaline extract
using liquid chromatography and tandem mass
spectrometry
Textiles et produits textiles - Substances Textilien und textile Erzeugnisse - Per- und
perfluoroalkylées et polyfluoroalkylées (PFAS) - Partie polyfluorierte Alkylverbindungen (PFAS) - Teil 1:
1 : Analyse d'un extrait alcalin par chromatographie en Untersuchung eines alkalischen Extraktes mittels
phase liquide et spectrométrie de masse en tandem Flüssigkeitschromatographie und Tandem-
Massenspektrometrie
This European Standard was approved by CEN on 14 March 2025.

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
© 2025 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 17681-1:2025 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
Introduction . 5
1 Scope . 14
2 Normative references . 14
3 Terms and definitions . 14
4 Principle . 15
5 Reagents . 15
6 Apparatus . 16
7 Sampling . 16
7.1 General . 16
7.2 Sampling based on area . 16
7.3 Sampling based on mass . 17
8 Procedure. 17
8.1 Preparation of stock solutions . 17
8.2 Preparation of the check solution for recovery rate . 17
8.3 Preparation of calibration solutions . 17
8.4 Extraction and alkaline hydrolysis . 17
8.5 Analysis . 18
9 Expression of results . 19
9.1 Calibration . 19
9.2 Calculation of the results of individual PFAS . 19
9.3 Calculation of the sums of certain PFAS . 20
9.4 Limits of quantitation of the test method . 20
9.5 Reliability of the test method . 20
10 Test report . 20
Annex A (normative) Usable ions and limits of quantification for PFAS analysis of sample matrix
by LC-MS/MS . 21
Annex B (informative) Interferences with LC-MS/MS . 24
Annex C (informative) Instrumental conditions . 25
Annex D (informative) Reliability of the test method . 27
Annex E (informative) Extraction with methanol . 30
Annex F (informative) Analysis with GC-MSD . 31
Bibliography . 40

European foreword
This document (EN 17681-1:2025) 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 October 2025, and conflicting national standards shall
be withdrawn at the latest by October 2025.
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.
This document supersedes EN 17681-1:2022.
This document includes the following significant technical changes with respect to EN 17681-1:2022:
— the title has been changed;
— the introduction has been amended;
— Table 1 has been revised;
— Table 2 has been reordered and updated with regard to new EU regulations; the majority of the
substance names has been aligned with EN 17892:2024 [8]; 10:2 fluorotelomer methacrylate has
been added;
— Clause 1: the scope has been changed considering extraction with simultaneous alkaline hydrolysis;
— Clause 2: EN 17681-2 has been deleted;
— 3.1, 3.2 and 3.3 have been added;
— Clause 4 has been changed, describing the extraction with simultaneous alkaline hydrolysis;
— Clause 5 and Clause 6 have been amended and reorganised;
— 7.1: the note has been deleted;
— 8.4 has been technically revised, describing the extraction with simultaneous hydrolysis;
— 9.3 and 9.4 have been rephrased and amended;
— 9.5 has been deleted, statistical data on the reliability are shown in Annex D;
— Clause 10 has been rephrased;
— Table A.1: the majority of the substance names has been aligned with EN 17892:2024 [8];
— Table C.1 has been integrated into Table 2 and former Annex C has been deleted;
— former Annex D has become Annex C;
— Annex D on the reliability of the test method has been added;
— Annex E describing the methanol extraction has been added;
— Annex F describing the analysis of certain PFAS with gas chromatography with mass selective
detector (GC-MSD) based on EN 17681-2:2022 [9] has been added;
— Bibliography: further references have been added.
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, several groups of per- and polyfluoroalkyl substances (PFAS) are restricted
whether on their own, in mixtures or in articles.
Regulation (EU) 2019/1021 on persistent organic pollutants (POPs) [1] restricts:
— perfluorooctane sulfonic acid and its derivatives (PFOS);
— perfluorooctanoic acid (PFOA), its salts and PFOA-related compounds;
— perfluorohexane sulfonic acid (PFHxS), its salts and PFHxS-related compounds (status September
2024).
Regulation (EC) No 1907/2006 (REACH), Annex XVII, Entry 68 [2] restricts:
— perfluorocarboxylic acids containing 9 to 14 carbon atoms in the chain (C9-C14 PFCAs), their salts
and C9-C14 PFCA-related substances;
— perfluorohexanoic acid (PFHxA), its salts and PFHxA-related substances, in textiles in clothing and
related accessories for the general public from 10 October 2026, in textiles other than in clothing and
related accessories for the general public from 10 October 2027 [3] (status September 2024).
Restrictions of other groups of PFAS are subject to the REACH restriction process [4].
Additionally, several per- and poly-fluorinated alkyl substances (PFAS), which are not restricted under
the EU-POPs or EU-REACH regulations have been added as substances of very high concern (SVHC) to the
candidate list according to Regulation (EC) No 1907/2006 (REACH), Article 59 [2].
Some of the aforementioned restrictions can also concern side-chain fluorinated polymers if they are
PFOA or C9-C14 PFCA-related substances. By using methanol as extraction solvent as described in
EN 17681-1:2022 and EN 17681-2:2022, the presence of side-chain fluorinated polymers cannot be
determined.
This document describes a method that will result in alkaline hydrolysis of certain side-chain fluorinated
polymers during the extraction process by using a mixture of methanol and aqueous sodium hydroxide
solution as extraction solvent. This extraction solvent cannot only extract residual PFAS from the sample,
but also cleaves the polymers that are esters of polymerized hydrocarbon acids, such as acrylic acid, and
n:2 fluorotelomer alcohols (n:2 FTOHs) to release n:2 FTOHs as a consequence. By quantifying the
amount of n:2 FTOHs, one can indirectly assess whether the amount of side-chain fluorinated polymers
consisting of polymerised hydrocarbon acids and n:2 FTOHs exceeds the limits for polymers that are
related substances to perfluorocarboxylic acids, which are restricted under the relevant EU-POPs or EU-
REACH regulations.
Since the group of PFAS consist of several thousand substances it is not possible to test for all of them in
targeted testing, e.g. for many PFAS reference standards are not available. Therefore,
CEN/TC 248/WG 26 “Textiles — Test methods for analysis of EC restricted substances”,
CEN/TC 289/WG 1 “Chemical test methods”, CEN/TC 309/WG 2 “Footwear and environmental aspects“
and ISO/TC 216/WG 2 “C
...