prEN 17681-1

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   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 prEN 17681-2.
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.

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) zum Nachweis und zur quantitativen Bestimmung von ausgewählten extrahierbaren perfluorierten und polyfluorierten Substanzen in textilen Materialien (Fasern, Garne, textile Flächengebilde) und beschichteten textilen Flächengebilden fest.
ANMERKUNG   CEN/TR 16741 legt fest, welche Materialien für diese Bestimmung geeignet sind.
Ein Prüfverfahren (unter Anwendung von Gaschromatographie, GC) zum Nachweis und zur quantitativen Bestimmung von ausgewählten extrahierbaren perfluorierten und polyfluorierten Substanzen ist in prEN 17681-2 festgelegt.
Die Klassen regulierter Verbindungen sind in Tabelle 2 aufgeführt. Klassen anderer, nicht regulierter Verbindungen, die nach diesem Dokument bestimmt werden können, sind in Anhang C, Tabelle C.1, festgelegt. Dieses Dokument ist auch anzuwenden für weitere PFAS Substanzen, vorausgesetzt, dass das Verfahren mit den zusätzlichen Verbindungen validiert wird.

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   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 le prEN 17681-2.
Les classes de composés réglementés sont répertoriées dans le Tableau 2. Les classes d'autres composés, non réglementés, qui peuvent être déterminés par le présent document sont définies dans le Tableau C.1 de l'Annexe C. Le présent document est également applicable à d'autres PFAS, à condition que la méthode soit validée avec les composés additionnels.

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

General Information

• Status: Not Published
• 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: 4599 - Dispatch of FV draft to CMC - Finalization for Vote
• Due Date: 09-Feb-2022
• Completion Date: 09-Feb-2022
• Ref Project: oSIST prEN 17681-1:2021 - Textiles and textile products - Organic fluorine - Part 1: Determination of non-volatile compounds by extraction method using liquid chromatography

Standards Content (sample)

SLOVENSKI STANDARD
oSIST prEN 17681-1:2021
01-junij-2021

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
Ta slovenski standard je istoveten z: prEN 17681-1
ICS:
59.080.01 Tekstilije na splošno Textiles in general
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
oSIST prEN 17681-1:2021 en

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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oSIST prEN 17681-1:2021
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oSIST prEN 17681-1:2021
DRAFT
EUROPEAN STANDARD
prEN 17681-1
NORME EUROPÉENNE
EUROPÄISCHE NORM
June 2021
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
Textilien und textile Erzeugnisse - Organisches Fluor -
Teil 1: Bestimmung des Gehaltes an nichtflüchtigen
Verbindungen durch Extraktionsverfahren mittels
Flüssigkeitschromatographie

This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee

CEN/TC 248.

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, Turkey 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 NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels

© 2021 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 17681-1:2021 E

worldwide for CEN national Members.
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oSIST prEN 17681-1:2021
prEN 17681-1:2021 (E)
Contents Page

European foreword ....................................................................................................................................................... 3

Introduction .................................................................................................................................................................... 4

1 Scope .................................................................................................................................................................... 9

2 Normative references .................................................................................................................................... 9

3 Terms and definitions ................................................................................................................................... 9

4 Principle of method ........................................................................................................................................ 9

5 Reagents ............................................................................................................................................................. 9

5.4 Selected PFAS listed in Table 2 and Table C.1 .................................................................................... 10

6 Equipment ...................................................................................................................................................... 10

7 Sampling .......................................................................................................................................................... 10

7.1 General ............................................................................................................................................................. 10

7.2 Sampling based on area ............................................................................................................................. 10

7.3 Sampling based on mass ............................................................................................................................ 11

7.4 Preparation .................................................................................................................................................... 11

7.4.1 Preparation of test specimen ................................................................................................................... 11

8 Procedure........................................................................................................................................................ 11

8.1 Preparation of stock solutions ................................................................................................................ 11

8.2 Preparation of the check solution .......................................................................................................... 11

8.3 Preparation of calibration solutions ..................................................................................................... 11

8.4 Extraction ........................................................................................................................................................ 11

8.5 Analysis ............................................................................................................................................................ 12

9 Expression of results ................................................................................................................................... 12

9.1 Calibration ...................................................................................................................................................... 12

9.2 Calculation of the results ........................................................................................................................... 12

9.3 Calculation of the results of a sum ......................................................................................................... 13

9.4 Limit of detection (LoD) and limit of quantification (LoQ) ........................................................... 13

10 Test report ...................................................................................................................................................... 13

Annex A (normative) Usable ions and LOQ for PFAS analysis by LC/MS/MS ....................................... 14

Annex B (informative) Interferences with LC/MS/MS ................................................................................. 16

Annex C (informative) Non-regulated PFAS .................................................................................................... 17

Annex D (informative) Chromatographic conditions ................................................................................... 19

D.1 General ............................................................................................................................................................. 19

D.2 Chromatographic conditions ................................................................................................................... 19

D.3 LC/MS/MS conditions ................................................................................................................................. 19

Bibliography ................................................................................................................................................................. 20

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oSIST prEN 17681-1:2021
prEN 17681-1:2021 (E)
European foreword

This document (prEN 17681-1:2021) has been prepared by Technical Committee CEN/TC 248 “Textiles and

textile products”, the secretariat of which is held by BSI.
This document is currently submitted to the CEN Enquiry.
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oSIST prEN 17681-1:2021
prEN 17681-1:2021 (E)
Introduction

In the European Union, according to Regulation (EU) 2019/1021 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, shall be 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 shall 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 % by weight 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

8 17 2

X = OH, Metal salt (O-M ), halide, amide and other derivatives, including polymers.

Annex I also states (point 5) that once standards are adopted by the European Committee for Standardization

(CEN) they shall be used as the analytical test methods for demonstrating the conformity of articles to point

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 % by weight) where they are present in substances, mixtures or articles. In addition, (Point 2)

Article 4(1) shall apply 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 % by weight) 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:
(i) C F -X, where X = F, Cl, Br;
8 17

(ii) fluoropolymers that are covered by CF [CF ]n-R’, where R’ = any group, n > 16;

3 2

(iii) perfluoroalkyl carboxylic acids (including their salts, esters, halides and anhydrides) with ≥ 8

perfluorinated carbons;

(iv) perfluoroalkane sulfonic acids and perfluoro phosphonic acids (including their salts, esters, halides and

anhydrides) with ≥ 9 perfluorinated carbons;

(v) 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 shall be 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.

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 (EC) No 1907/2006 (REACH), Article 59.
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oSIST prEN 17681-1:2021
prEN 17681-1:2021 (E)

Per- and poly-fluorinated compounds from C4 – C14 (PFAS) occur, for example, in soil and water repellent

finishes within textiles or can be introduced as contaminants (e.g. from water sources). Categories of PFAS

are shown in Table 1. Table 2 lists classes of regulated compounds (i.e. listed in regulation) including acids,

telomers, sulfonates and sulfonamidalcohols. Compounds of concern (i.e. not listed yet in regulation) are

shown in the informative Annex C.
Table 1 — Categories of PFAS
Applications
Type of PFAS Sub-group Category
Sources of contamination
Use
Surfactant in fire-fighting
foam, emulsifier in floor
+ +
K , Li ,
polish mist, suppressant
diethanolamine
Surfactant for alkaline for metal plating baths,
(DEA) salt
cleaners surfactant for etching acids
for circuit boards, pesticide
Analysed as acids
active ingredient for ant
bait traps
PFAS salts
Mist suppressant for metal
Amines B
plating baths
Ammonium salts
Emulsifier for
C
fluoropolymer production
Analysed as acids
Water/solvent
Amphoterics repellence for D
leather/paper
Antistatic agent in
Carboxylates E
photographic paper
PFAS substances Amides Pesticide active ingredient F
Waterproofing casts
Oxazolidinones G
(electronics)
Alcohols, silanes,
alkoxylates, fatty Soil/water repellence
acid esters, for carpets,
H
adipates, fabric/upholstery,
urethanes, apparel, leather,
polyesters, metal/glass
PFAS
acrylates
polymers/oligomers
Soil/oil/water repellence
Water repellence for
for plates, food containers,
carpet,
Copolymers, bags, wraps, folding
fabric/upholstery, I
phosphate esters cartons, containers,
apparel, leather,
carbonless forms, masking
metal/glass
papers

These substances are not relevant in the manufacturing process of textiles but it is possible to find them as contaminants.

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oSIST prEN 17681-1:2021
prEN 17681-1:2021 (E)
Table 2 — Regulated PFAS
PFAS
No Chemicals CAS No. LC GC category
law (§)
(Table 1)
Perfluorinated carboxylic acids
under
1 PFHxA Perfluoro-n-hexanoic acid 307-24-4 x evaluation A and C
(REACh)
2 PFOA Perfluoro-n-octanoic acid 335-67-1 x POP A and C
Perfluoro-n-octanoic salts
APFO C
- Ammonium pentadecafluorooctanoate
3825-26-1
Na-PFO A
- Sodium perfluorooctanoate
335-95-5
2.2 x POP
- Potassium perfluorooctanoate
K-PFO 2395-00-8 A
- Silver perfluorooctanoate
335-93-3
Ag-PFO A
- Perfluorooctanoyl fluoride
335-60-0
F-PFO A
3 8:2 FTS 1H,1H,2H,2H-Perfluorodecanesulfonic acid 39108-34-4 x POP A
4 Me-PFOA Methyl perfluorooctanoate 376-27-2 x POP H
5 Et-PFOA Ethyl perfluorooctanoate 3108-24-5 x POP H
Reach
6 PFNA Perfluoro-n-nonanoic acid 375-95-1 x
(SVHC)
Reach
7 PFDA Perfluoro-n-decanoic acid 335-76-2 x
(SVHC)
Reach
8 PFUnA Perfluoroundecanoic acid 2058-94-8 x
(SVHC)
Reach
9 PFDoA Perfluorododecanoic acid 307-55-1 x
(SVHC)
Reach
10 PFTrA Perfluorotridecanoic acid 72629-94-8 x
(SVHC)
Reach
11 PFTeA Perfluorotetradecanoic acid 376-06-7 x
(SVHC)
12 PF-3,7-DMOA Perfluoro(3,7-dimethyloctanoic acid) 172155-07-6 x POP
2H,2H,3H,3H-Heptadecafluoroundecanoic
13 4HPFUnA 34598-33-9 x POP
Acid
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oSIST prEN 17681-1:2021
prEN 17681-1:2021 (E)
PFAS
No Chemicals CAS No. LC GC category
law (§)
(Table 1)
Perfluorinated sulfonic acids
Reach
14 PFBS Perfluorobutanesulfonic acid 375-73-5 x A
(SVHC)
Reach
15 PFHxS Perfluorohexanesulfonic acid 355-46-4 x H
(SVHC)
16 PFOS Perfluoro octanesulfonic acid 1763-23-1 x POP H
Perfluorooctane sulfonic acid salts
C8F17SO2X
- potassium Perfluorooctane sulfonate
2795-39-3
- lithium Perfluorooctane sulfonate
29457-72-5
16.2 PFOS-X - ammonium Perfluorooctane sulfonate x POP
29081-56-9 A
- bis2(hydroxyethyl)ammonium
70225-14-8
Perfluorooctane sulfonate
56773-42-3
- tetraethyl ammonium
heptadecafluorooctane sulfonate
Perfluoro-octanesulfonamides (FOSA)
17 PFOSA Perfluorooctane sulfonamide 754-91-6 x POP F
18 N-MeFOSA N-Methylperfluoro-1-octanesulfonamide 31506-32-8 x POP F
19 N-EtFOSA N-Ethylperfluoro-1-octanesulfonamide 4151-50-2 x POP F
Perfluoro-octanesulfonamido ethanol (FOSE)
2-(N-methylperlfuoro-1-
20 N-MeFOSE 24448-09-7 x x POP H
octanesulfonamideo)-ethanol
2-(N-Ethylperfluoro-1-
21 N-EtFOSE 1691-99-2 x x POP H
octanesulfonamido)-ethanol
Fluorinated telomer alcohols (FTOH)
b
22 8:2 FTOH 2-Perfluorooctylethanol 678-39-7 x POP H
Fluorinated telomer acrylate (FTA)
b
23 8:2 FTA 1H,1H,2H,2H-Perfluorodecyl acrylate 27905-45-9 x POP H
Other
24 PFOSF Heptadecafluorooctanesulfonyl fluoride 307-35-7 x POP
1H,1H,2H,2H-
25 8:2 FTMA 1996-88-9 x POP
heptadecafluorodecylmethacrylate
1-decanaminium, N-decyl-N, N dimethyl-
0,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-
26 251099-16-8 x POP A
heptadecafluoro-1-
octanesulfonate
Reach
2,3,3,3-tetrafluoro-2-
27 HPFO-DA 13252-13-6 x A and C
(heptafluoropropoxy)propionic acid
(SVHC)
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oSIST prEN 17681-1:2021
prEN 17681-1:2021 (E)
PFAS
No Chemicals CAS No. LC GC category
law (§)
(Table 1)
2,3,3,3-tetrafluoro-2-
(heptafluoropropoxy)propionic acid salts
and acyl halides
Reach
27.2 HPFO-DA -X 21062-98-8 x A and C
X = F
(SVHC)
62037-80-3 x
X = NH
67118-55-2 x
X = K

Table 2 states the situation of the regulated PFAS on 2021-03-1. Readers should pay attention to update the information.

The results of PFOA related substances to be summed up.

For the halides a hydrolysation with water from the methanol extract is necessary.

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oSIST prEN 17681-1:2021
prEN 17681-1:2021 (E)
1 Scope

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 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 prEN 17681-2.

Classes of regulated compounds are listed in Table 2. Classes of other non-regulated

...