EN 17134-2:2023

SLOVENSKI STANDARD
01-september-2023
Tekstilije in tekstilni izdelki - Določevanje biocidnega dodatka - 2. del: Konzervansi
na osnovi klorofenola, metoda z uporabo plinske kromatografije
Textiles and textile products - Determination of biocide additives - Part 2: Chlorophenol-
based preservatives, method using gas chromatography
Textilien und textile Erzeugnisse - Bestimmung von Biozid-Zusatzstoffen - Teil 2:
Konservierungsmittel auf Chlorphenolbasis, Verfahren mittels Gaschromatographie
Textiles et produits textiles - Détermination des additifs biocides - Partie 2 :
Conservateurs à base de chlorophénol, méthode par chromatographie en phase
gazeuse
Ta slovenski standard je istoveten z: EN 17134-2:2023
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 17134-2
EUROPEAN STANDARD
NORME EUROPÉENNE
July 2023
EUROPÄISCHE NORM
ICS 59.080.01 Supersedes EN 17134:2019
English Version
Textiles and textile products - Determination of biocide
additives - Part 2: Chlorophenol-based preservatives,
method using gas chromatography
Textiles et produits textiles - Détermination des Textilien und textile Erzeugnisse - Bestimmung von
additifs biocides - Partie 2 : Conservateurs à base de Biozid-Zusatzstoffen - Teil 2: Konservierungsmittel auf
chlorophénol, méthode par chromatographie en phase Chlorphenolbasis, Verfahren mittels
gazeuse Gaschromatographie
This European Standard was approved by CEN on 12 June 2023.

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
© 2023 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 17134-2:2023 E
worldwide for CEN national Members.

Contents Page
European foreword . 4
Introduction . 5
1 Scope . 6
2 Normative references . 6
3 Terms and definitions . 6
4 Principle . 6
5 Reagents . 6
6 Apparatus .10
7 Preparation of test samples and test specimens .10
8 Procedure.10
8.1 Extraction with KOH .10
8.2 Acetylation of extracted CPs .11
8.2.1 General procedure of acetylation .11
8.2.2 Preparation for GC analysis .11
8.2.3 Acetylation in case of low recovery rates .11
8.3 Acetylation of the calibration standards .11
8.4 Gas chromatography with mass selective detection .11
9 Expression of results .11
9.1 General .11
9.2 Calculation of the individual chlorophenols .12
9.3 Sum of chlorophenols .12
9.4 Precision of the test method .12
10 Test report .12
Annex A (informative) Example of parameters for GC-MS determination of CPs .13
A.1 Measuring technique .13
A.2 Chromatographic conditions .13
A.3 MS conditions .13
Annex B (informative) Reliability of the method.15
B.1 General .15
B.2 Results of interlaboratory trials .16
B.2.1 Results of the first interlaboratory trial .16
B.2.2 Results of the second interlaboratory trial from one real test specimen and two
spikes of the real test specimen, with 4 laboratories .17
B.3 Influence of standard solutions .24
B.4 Influence of internal standards on the results of pentachlorophenol and other
chlorophenols .29
Annex C (informative) Test method for free mono- and dichlorophenols .37
C.1 General .37
C.2 Reagents . 37
C.3 Apparatus . 37
C.4 Preparation of test samples . 37
C.5 Procedure . 37
C.5.1 Extraction and acetylation of extracted CPs . 37
C.5.2 Acetylation of the calibration standards . 37
C.6 Expression of results . 38
C.7 Test report . 38
Bibliography . 39

European foreword
This document (EN 17134-2:2023) 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 January 2024, and conflicting national standards shall
be withdrawn at the latest by January 2024.
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 17134:2019.
This document is part of a series of documents:
EN 17134-1 , Textiles and textile products — Determination of biocide additives — Part 1: 2-Phenylphenol
and triclosan, method using liquid chromatography
EN 17134-2, Textiles and textile products — Determination of biocide additives — Part 2: Chlorophenol-
based preservatives, method using gas chromatography
EN 17134-3 , Textiles and textile products — Determination of biocide additives — Part 3: Permethrin,
method using liquid chromatography
A list of all parts in a series can be found on the CEN website: www.cencenelec.eu.
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.
Under preparation. Stage at the time of publication: prEN 17134-1:2023.
Under preparation. Stage at the time of publication: prEN 17134-3:2023.
Introduction
In Europe, according to Regulation (EU) 2019/1021 of the European Parliament and of the Council of 20
June 2019 on persistent organic pollutants [1] pentachlorophenol (PCP) and its salts and esters as
constituents of articles are prohibited. According to Commission Delegated Regulation (EU) 2021/277 of
16 December 2020 amending Annex I to Regulation (EU) 2019/1021 of the European Parliament and of
the Council on persistent organic pollutants as regards pentachlorophenol and its salts and esters [2],
articles containing PCP in concentrations equal or lower than 5 mg/kg are allowed.
Further chlorinated phenols are restricted by voluntary specifications (ecolabel criteria, industry
initiatives and standards).
WARNING — The use of this document involves hazardous materials. It does not purport to address all
of the safety or environmental problems associated with its use. It is the responsibility of users of this
document to take appropriate measures to ensure the safety and health of personnel and the
environment prior to application of the document and fulfil statutory and regulatory requirements for
this purpose.
1 Scope
This document specifies a test method using gas chromatography with a mass selective detector (GC-MS)
for detection and quantification of chlorophenols (CPs), which are either freely present or released from
salts and esters: pentachlorophenol (PCP), tetrachlorophenol- (TeCP), trichlorophenol- (TriCP),
dichlorophenol- (DiCP) and monochlorophenol- (MoCP) isomers. The method is applicable to textile
fibres, yarns, fabrics, coated fabrics, printed fabrics, plastic, and wooden parts of textile products (for
example buttons).
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 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696)
EN ISO 4787, Laboratory glass and plastic ware - Volumetric instruments - Methods for testing of capacity
and for use (ISO 4787)
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:
— ISO Online browsing platform: available at https://www.iso.org/obp
— IEC Electropedia: available at https://www.electropedia.org/
4 Principle
The sample is cut into small pieces and extracted with potassium hydroxide (KOH) solution at a defined
temperature. The extracted CPs are subsequently acetylated and the chlorinated acetates are analysed
13 2
and quantified using GC-MS. The quantitative determination is made by corrections with C- and H-
labelled internal standards.
5 Reagents
Unless otherwise specified, all reagents shall be of a recognized analytical grade.
5.1 Water, grade 3, according to EN ISO 3696.
®3 ®
5.2 Potassium hydroxide (KOH), CAS Registry Number (CAS RN ) 1310-58-3. ®
5.3 Potassium carbonate (K CO ), anhydrous, CAS RN 584-08-7.
2 3 ®
5.4 n-Hexane, CAS RN 110-54-3.

3 ® ®
CAS Registry Number (CAS RN ) is a trademark of the American Chemical Society (ACS). This information is
given for the convenience of users of this document and does not constitute an endorsement by CEN of the product
named. Equivalent products may be used if they can be shown to lead to the same results. ®
5.5 Acetic anhydride, CAS RN 108-24-7. ®
5.6 Tetrachloroguaiacol (TCG), CAS RN 2539-17-5, internal standard (IS). ®
5.7 Acetonitrile, CAS RN 75-05-8.
5.8 Chlorophenols
The following 19 CPs given in Table 1 are probably relevant.
Table 1 — List of probably relevant CPs ®
Substance Abbreviation CAS RN
2-chlorophenol 2-MoCP 95-57-8
3-chlorophenol 3-MoCP 108-43-0
4-chlorophenol 4-MoCP 106-48-9
2,3-dichlorophenol 2,3-DiCP 576-24-9
2,4-dichlorophenol 2,4-DiCP 120-83-2
2,5-dichlorophenol 2,5-DiCP 583-78-8
2,6-dichlorophenol 2,6-DiCP 87-65-0
3,4-dichlorophenol 3,4-DiCP 95-77-2
3,5-dichlorophenol 3,5-DiCP 591-35-5
2,3,4-trichlorophenol 2,3,4-TriCP 15950-66-0
2,3,5-trichlorophenol 2,3,5-TriCP 933-78-8
2,3,6-trichlorophenol 2,3,6-TriCP 933-75-5
2,4,5-trichlorophenol 2,4,5-TriCP 95-95-4
2,4,6-trichlorophenol 2,4,6-TriCP 88-06-2
3,4,5-trichlorophenol 3,4,5-TriCP 609-19-8
2,3,4,5-tetrachlorophenol 2,3,4,5-TeCP 4901-51-3
2,3,4,6-tetrachlorophenol 2,3,4,6-TeCP 58-90-2
2,3,5,6-tetrachlorphenol 2,3,5,6-TeCP 935-95-5
Pentachlorophenol PCP 87-86-5
5.9 Isotope labelled chlorophenols
The following 4 isotope labelled CPs given in Table 2 can be relevant as internal standards (IS).
Table 2 — List of probably relevant isotope labelled chlorophenols ®
Substance Abbreviation CAS RN
2-chlorophenol-D 2-MoCP-D 93951-73-6
4 4
2,4-dichlorophenol-D 2,4-DiCP-D 93951-74-7
3 3
13 13
2,3,4,6-tetrachlorophenol- C 2,3,4,6-TeCP- C 1246820-81-4
6 6
13 13
Pentachlorophenol- C PCP- C 85380-74-1
6 6
Instead of the isotope-labelled derivatives of tetra-, di- and monochlorophenol mentioned, other isotope-
labelled analogues of the same chlorination levels, for example 4-chlorophenol-D , may be used as
internal standards.
5.10 Potassium hydroxide (KOH) solution (c = 1 mol/l)
Prepare an aqueous KOH solution at a concentration of 1 mol/l.
EXAMPLE Weigh 56,1 g KOH (5.2) into a 1 l volumetric flask and dissolve with 100 ml water (5.1) (WARNING:
heat generation!). After cooling to room temperature fill up to 1 l with water (5.1).
5.11 Internal standard stock solution of isotope-labelled chlorophenols
Based on its requirements a laboratory shall decide which isotope-labelled CPs are required in an internal
standard stock solution.
Table 3 shows which isotope-labelled CPs shall be used as internal standards (IS) for the quantification
of CPs with particular chlorination levels. Alternative IS as outlined in 5.9 may be used.
Table 3 — Assignment of the isotope-labelled CPs to the CP groups
Isotope-labelled CP CP group
2-chlorophenol-D MoCP
2,4-dichlorophenol-D DiCP, TriCP
2,3,4,6-tetrachlorophenol- C6 TeCP
Pentachlorophenol- C PCP
Prepare a stock solution of the isotope-labelled CPs required at a concentration suitable for the used
analytical system, for example c = 0,1 mg/ml.
EXAMPLE To get a stock solution of isotope-labelled CPs at concentrations of 0,1 mg/ml, dissolve 10 mg of
each required isotope-labelled internal standard (5.9) in 100 ml KOH solution (5.10).
5.12 Extraction solution
The concentration of isotope-labelled CPs shall be adapted to the respective calibration range of the CPs
(see solutions 5.16).
EXAMPLE To prepare 1 l extraction solution with a concentration of each isotope-labelled CP (5.11) of
0,1 µg/ml, transfer 1,0 ml stock solution isotope-labelled CPs (5.11) in a 1 l volumetric flask and fill it up with KOH
solution (5.10). If a more sensitive measuring instrument is used and the calibration is lowered, reduce the
concentration of isotope-labelled internal CPs in the KOH accordingly.
5.13 Potassium carbonate (K CO ) solution (c = 0,1 mol/l).
2 3
Prepare an aqueous K CO solution at a concentration of 0,1 mol/l.
2 3
EXAMPLE Weigh 13,82 g K CO into a 1 l volumetric flask, dissolve with water (5.1) and fill up to the mark.
2 3
5.14 Tetrachloroguaiacol (TCG) solution
Prepare a TCG solution in acetonitrile as internal standard solution for injection control at a
concentration suitable for the used analytical system, for example c = 1 μg/ml.
EXAMPLE Dissolve 10 mg TCG (5.6) in 100 ml acetonitrile (5.7). Take 1,0 ml from this solution and dilute to
100 ml with acetonitrile (5.7).
5.15 CPs standard stock solution
Based on its requirements a laboratory shall decide which CPs from Table 1 in 5.8 need to be determined.
Based on this decision, standard stock solutions at a concentration suitable for the analytical system used
are required. CP standard stock solutions, either as single substance or mixed substance solutions (for
example, c = 50 µg/ml in acetone), are available commercially as certified standard solutions or may be
prepared from certified reference substances.
5.16 CPs calibration solutions
Prepare at least three calibration solutions of CPs from the CP standard stock solution(s) (5.15) at
suitable concentrations for the analysis. Transfer the required volume of CP standard stock solution(s)
(5.15) into a volumetric flask and fill it up to the mark with acetonitrile (5.7). Examples of concentrations
that have been found suitable are provided in Table 4.
Table 4 — Examples of calibration solutions
Volume of
Concentration of CPs
CPs working solution (5.15) Volume of volumetric flask
in calibration solution
(for example c = 50 µg/ml)
µg/ml µl ml
0,15 30
2,0 400 10
4,0 800
15 600
25 1 000
6 Apparatus
The usual laboratory apparatus and laboratory glassware, according to EN ISO 4787, shall be used, in
addition to the following:
6.1 Analytical balance, weighing with an accuracy of 0,1 mg.
6.2 Gas-tight glass vial, for example 20 ml headspace vial.
6.3 Heating block, sand bath or oven, suitable to maintain the KOH solution at a temperature of
(90 ± 1) °C.
6.4 GC vials, for example 2 ml.
6.5 Pasteur pipettes, graduated pipettes, suitable autopipettes.
6.6 Vortex shaker.
−1
6.7 Horizontal shaker, capable of at least 200 min .
6.8 Centrifuge.
6.9 Gas chromatograph with mass selective detector (GC-MS).
7 Preparation of test samples and test specimens
Dismantle the textile product and separate the different material types.
Each test specimen shall consist of a single material type, which is tested separately. If fabrics and prints
cannot be separated, they may be tested together. Up to three test specimens (of equal mass) of the same
material type may be tested together, taking into consideration the limits of detection (LoD) and
quantification (LoQ).
Each material type is cut into pieces of about 0,3 cm to 0,5 cm edge length.
8 Procedure
8.1 Extraction with KOH
Weigh approximately 1 g (minimum sample mass 0,2 g) of the cut test specimen (7) (to the nearest
0,01 g) in a glass vial (6.2). Add 10 ml extraction solution (5.12). After closing, the vial is transferred to a
heating apparatus (6.3) and left for 16 h ± 15 min at (90 ± 1) °C. The temperature in the vials is checked
in a vial (6.2) with blank KOH extraction solution (5.12).
If the test specimen to be examined is too voluminous to be completely covered with KOH solution for
the period of extraction, the test specimen shall be weighed down with glass balls or a comparable inert
object to ensure complete wetting. Alternatively, a larger amount of extraction solution shall be added.
Thereby, the different specimen mass to solution ratio shall be considered in the calculation (9.2).
NOTE Deviations from the specified extraction time and temperature can lead to significant variations in the
result.
By applying KOH extraction, MoCPs and DiCPs can be released from unknown compounds, for example
dyes. If it is only required to test for free MoCPs and DiCPs the procedure described in Annex C can be
applied.
8.2 Acetylation of extracted CPs
8.2.1 General procedure of acetylation
To get a limit of quantification (LoQ) of 0,1 mg/kg use the following procedure: After extraction, the
solution shall be cooled down to room temperature and shaken vigorously for approximately 1 min with
a vortex shaker (6.6) or for approximately 10 min with a horizontal shaker (6.7).
Transfer 4 ml of the extract into a new glass vial (6.2) and add 6 ml potassium carbonate solution (5.13),
2 ml n-hexane (5.4), 250 μl TCG solution (5.14) and 1 ml acetic anhydride (5.5).
8.2.2 Preparation for GC analysis
−1
Close the vial and shake it for (30 ± 1) min at a shaking rate of at least 200 min on a horizontal shaker
(6.7). An efficient mixing of the phases shall be ensured.
Let the two phases of the solution separate and centrifuge the vial, if required, before opening it. Open
the vial carefully (WARNING: There can be an overpressure in the vial!) and transfer an aliquot from the
upper phase into a GC vial (6.4) for analysis.
If a higher LoQ is required, it is possible to use less extract and/or more n-hexane (5.4). Perform a
validation of the method with these changed conditions.
By reducing the mass of the test specimen higher limit values can be covered.
8.2.3 Acetylation in case of low recovery rates
For test specimens with very low recovery rates of the isotope-labelled internal standards, take the whole
extract with the test specimen (8.1) and add 5 ml n-hexane (5.4), 625 μl TCG solution (5.14) and 2,5 ml
acetic anhydride (5.5) instead of the above-mentioned volumes. The n-hexane phase will contain more
matrix than from the solution without the test specimen. This can affect the instrumental analysis (8.4)
but empirically the recovery rates of the isotope-labelled internal standards improve. Proceed with 8.2.2.
8.3 Acetylation of the calibration standards
Transfer 100 μl of each CP calibration solution (5.16) into new glass vials (6.2). Add 4 ml extraction
solution (5.12), 6 ml potassium carbonate solution (5.13), 2 ml n-hexane (5.4), 250 μl TCG solution (5.14)
and 1 ml of acetic anhydride (5.5) to each vial. Proceed analogous to 8.2.2.
8.4 Gas chromatography with mass selective detection
Determine the compounds listed in Table 1 and acetylated in 8.2 and 8.3 by GC-MS (6.9) as required.
Examples of chromatographic and spectroscopic conditions are given in Annex A.
9 Expression of results
9.1 General
The quantitative determination is made using a multi-point calibration with at least three points. The
calibration curve is constructed by plotting the area against the known standard concentrations with
correction for the related isotope-labelled internal standards (Table 3). From the calibration curve,
interpolate the concentration of chlorophenol (ρ ), in μg/ml.
s
If the recovery of the isotope-labelled internal standards due to matrix effects is lower than the specified
recovery of the laboratory's quality guideline, other valid methods, such as addition procedures, may be
used to quantify the CP concentrations.
If the recovery rates of the isotope-labelled internal standards are very low, perform 8.2.3.
TCG is used to check whether the acetylation (8.3) and the injection were successful.
9.2 Calculation of the individual chlorophenols
The contents of CPs are calculated as mass fractions w, in mg/kg, of the test specimen according to
Formula (1):
ρ ××VV
si KOH n-hexane
w = (1)
i
Am×
KOH E
where
w the mass fraction of a CP(i) found, in mg/kg;
i
ρsi the interpolated CP(i) concentration according to 9.1, in μg/ml;
V the volume of the KOH extraction solution according to 8.1, in ml;
KOH
A aliquot of the KOH extraction solution according to 8.2.1 or 8.2.3, in ml;
KOH
V the volume of the added amount of n-hexane according to 8.2.1 or 8.2.3, in ml;
n-hexane
m the mass of the test specimen, in g.
E
9.3 Sum of chlorophenols
In certain cases, the sum of different CPs is requested as a final result. Only CPs that are clearly identified
shall be included in the sum.
The results of the identified CPs (as obtained in 9.2) are added to give the result of the sum. If the result
for a single CP is lower than the limit of quantification (LoQ) of the test method (9.4), this result shall not
be included in the sum.
9.4 Precision of the test method
This method is able to determine the concentrations of the substances listed in Table 1 with a limit of
quantification (LoQ) of 0,1 mg/kg or lower.
For the reliability (precision) of the procedure, see Annex B.
10 Test report
The test report shall include at least the following information:
a) identification of the submitted sample;
b) reference to this document, i.e. EN 17134-2:2023;
c) the mass fraction for each quantified CP, in mg/kg (as calculated in 9.2), rounded to a maximum of 2
significant figures with a maximum of 2 decimal points;
d) if requested, the mass fraction of the sum of CPs in mg/kg (as calculated in 9.3), rounded to a
maximum of 2 significant figures with a maximum of 2 decimal points;
e) any deviations from the procedure;
f) any unusual features observed;
g) the date of the analysis.
Annex A
(informative)
Example of parameters for GC-MS determination of CPs
A.1 Measuring technique
The CPs are determined by gas chromatography-mass spectrometry on a single quad/MS used in selected
ion monitoring (SIM) mode.
A.2 Chromatographic conditions
Column: Stationary phase: 5 % phenyl-, 95 % methyl-polysiloxane
Length: 30 m
Internal diameter: 0,25 mm
Film thickness: 0,25 μm
Carrier gas: Helium
Flo
...