EN ISO 14389:2014

SLOVENSKI STANDARD
01-september-2014
1DGRPHãþD
SIST EN 15777:2009
7HNVWLOLMH'RORþHYDQMHIWDODWRY7HWUDKLGURIXUDQVNDPHWRGD,62
Textiles - Determination of the phthalate content - Tetrahydrofuran method (ISO
14389:2014)
Textilien - Bestimmung des Phthalatanteils - Tetrahydrofuran-Verfahren (ISO
14389:2014)
Textiles - Détermination de la teneur en phtalates - Méthode au tétrahydrofurane (ISO
14389:2014)
Ta slovenski standard je istoveten z: EN ISO 14389:2014
ICS:
59.060.01 Tekstilna vlakna na splošno Textile fibres in general
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EUROPEAN STANDARD
EN ISO 14389
NORME EUROPÉENNE
EUROPÄISCHE NORM
June 2014
ICS 59.060.01 Supersedes EN 15777:2009
English Version
Textiles - Determination of the phthalate content -
Tetrahydrofuran method (ISO 14389:2014)
Textiles - Détermination de la teneur en phtalates - Textilien - Bestimmung des Phthalatanteils -
Méthode au tétrahydrofurane (ISO 14389:2014) Tetrahydrofuran-Verfahren (ISO 14389:2014)
This European Standard was approved by CEN on 20 June 2014.

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, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United
Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2014 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 14389:2014 E
worldwide for CEN national Members.

Contents Page
Foreword .3
Foreword
This document (EN ISO 14389:2014) has been prepared by Technical Committee ISO/TC 38 "Textiles" in
collaboration with 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 December 2014, and conflicting national standards shall be withdrawn
at the latest by December 2014.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
This document supersedes EN 15777:2009.
According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech
Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece,
Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,
Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom.
Endorsement notice
The text of ISO 14389:2014 has been approved by CEN as EN ISO 14389:2014 without any modification.

INTERNATIONAL ISO
STANDARD 14389
First edition
2014-05-01
Textiles — Determination of the
phthalate content — Tetrahydrofuran
method
Textiles — Détermination de la teneur en phtalates — Méthode au
tétrahydrofurane
Reference number
ISO 14389:2014(E)
©
ISO 2014
ISO 14389:2014(E)
© ISO 2014
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
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Tel. + 41 22 749 01 11
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Published in Switzerland
ii © ISO 2014 – All rights reserved

ISO 14389:2014(E)
Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Terms and definitions . 1
3 Principle . 1
4 Reagents . 1
5 Apparatus . 2
6 Procedure. 3
6.1 Preparation of standard solutions . 3
6.2 Ultrasonic extraction and determination of phthalates . 4
7 Calculation of the results . 5
7.1 Calculation based on the corrected mass (by default). 5
7.2 Calculation based on the total mass (when relevant) . 6
8 Test report . 7
Annex A (normative) Calculations . 8
Annex B (informative) Example of test parameters by GC-MS .10
Annex C (informative) Determination of PVC mass fraction by chemical method .12
Annex D (informative) Statistical data.15
Bibliography .22
ISO 14389:2014(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2. www.iso.org/directives
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received. www.iso.org/patents
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical Barriers
to Trade (TBT) see the following URL: Foreword - Supplementary information
The committee responsible for this document is ISO/TC 38, Textiles.
iv © ISO 2014 – All rights reserved

ISO 14389:2014(E)
Introduction
This International Standard covers a test method for the determination of some phthalates in textile
articles.
Phthalates are commonly used as plasticizers in polymers. Phthalates are an issue for textile
manufacturers and retailers due to their use within motifs, coated fabrics, plastisol prints, buttons, etc.
Phthalates are controversial because high doses of many phthalates have shown hormonal activity in
rodent studies. Studies on rodents involving large amounts of phthalates have shown damage to the
liver, the kidneys, the lungs, and the developing testes.
Due to their potential effect as endocrine disruptors, some of the listed phthalates are toxic in
reproduction. The listed phthalates are based on those which have been restricted in some regulations
(e.g. in the European Union).
INTERNATIONAL STANDARD ISO 14389:2014(E)
Textiles — Determination of the phthalate content —
Tetrahydrofuran method
WARNING — This International Standard calls for the use of substances and/or procedures that
might be injurious to health if adequate precautions are not taken. It refers only to technical
suitability and does not absolve the user from legal obligations relating to health and safety at
any stage. It has been assumed in the drafting of this International Standard that the execution
of its provisions is entrusted to appropriately qualified and experienced operators.
1 Scope
This International Standard specifies a method of determining phthalates in textiles with gas
chromatography–mass spectrometry (GC-MS) with mass selective detector.
This International Standard is applicable to textile products where there is a risk of the presence of
some phthalates.
2 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
2.1
plasticized or softened material
plastic material that is treated with chemicals to make it more flexible
Note 1 to entry: For this specific International Standard, the chemicals are phthalates.
EXAMPLE Examples of plastic material: coating, pigment print binder, etc.
2.2
overall treated textile
textile with a continuous finish, coating or print
2.3
locally treated textile
textile with a discontinuous finish, coating or print
2.4
representative specimen
specimen obtained by mixing pieces of all the different treated parts and colours
3 Principle
The phthalates are extracted from textile specimen by ultrasonic generator with tetrahydrofuran.
As the plastic polymer is partially or completed dissolved, the phthalate extraction is followed by the
precipitation of the dissolved polymer using the appropriate solvent (acetonitrile, n-hexane, etc.). After
centrifugation and dilution of the extract to volume, gas chromatography–mass spectrometry (GC-
MS) is used to identify individual phthalates in the specimen and quantify them by using an internal
standard (IS).
4 Reagents
Unless otherwise specified, use only reagents of recognized analytical grade.
ISO 14389:2014(E)
4.1 Tetrahydrofuran (THF), CAS number: 109-99-9.
4.2 Solvents used for the precipitation. Examples are:
4.2.1 Acetonitrile, CAS number: 75-05-8.
4.2.2 n-Hexane, CAS number: 110-54-3.
4.3 Di-cyclohexyl phthalate (DCHP), CAS number: 84-61-7, internal standard (IS).
4.4 Di-isononyl phthalate (DINP), CAS number 28553-12-0 or 68515-48-0.
4.5 Di-(2-ethylhexyl) phthalate (DEHP), CAS number 117-81-7.
4.6 Di-n-octyl phthalate (DNOP), CAS number 117-84-0.
4.7 Di-iso-decyl phthalate (DIDP), CAS number 26761-40-0 or 68515-49-1.
4.8 Butyl benzyl phthalate (BBP), CAS number 85-68-7.
4.9 Di-butyl phthalate (DBP), CAS number 84-74-2.
4.10 Di-iso-butyl phthalate (DIBP), CAS number 84-69-5.
4.11 Di-pentyl phthalate (DPP), CAS number: 131-18-0.
4.12 Di-iso-heptyl phthalate (DIHP), CAS number: 71888-89-6.
4.13 Di-methoxyethyl phthalate (DMEP), CAS number: 117-82-8.
5 Apparatus
5.1 Gas chromatograph-mass spectrometer (GC-MS), with mass selective detector (MSD).
5.2 Vial, of capacity 40 ml.
5.3 Thermostatic ultrasonic bath, with a frequency of (40 ± 5) kHz.
5.4 Glass flasks with glass stoppers, of capacity 100 ml.
5.5 Calibrated volumetric flasks, of capacities 50 ml and 100 ml.
5.6 Volumetric graduated pipette, of capacities 10 ml and 20 ml.
5.7 Balance, with a resolution of 0,1 mg.
5.8 Water bath.
5.9 Rotary evaporator.
2 © ISO 2014 – All rights reserved

ISO 14389:2014(E)
6 Procedure
WARNING — The vapour of the organic solvents is highly flammable, especially at high
temperature. Allow glassware to cool down before use.
Avoid direct contact between the samples and glassware and/or equipment used in order to minimize
cross-contamination. Glassware, after washing, should be given an extra rinse with 0,1 N nitric acid,
water and finally with acetone. Glassware should be completely dried before use. To avoid contamination,
do not use any plastic container (e.g. for water).
6.1 Preparation of standard solutions
6.1.1 Internal standard solution
Prepare a 1 000 mg/l stock standard solution of the internal standard in the solvent used for the
precipitation (4.2) after the ultrasonic extraction (see 6.2).
6.1.2 Preparation of stock standard solutions
Prepare a series of individual stock standard solutions of the individual phthalate ester in the solvent
used for the precipitation as shown in Table 1.
For example, weigh 50,0 mg of a phthalate in a 50 ml volumetric flask and fill the volumetric flask up
to the mark with the solvent used for the precipitation and mix thoroughly to dissolve completely the
substance.
Table 1 — Stock standard solutions
Phthalate
DCHP (IS) DINP DEHP DNOP DIDP BBP DBP DIBP DPP DIHP DMEP
ester
Concen-
tration, 1 000
mg/l
Most of the stock standards may be made in a mixed stock. This saves time and effort when preparing
calibration solutions. DINP, DIDP and DIHP have overlapping peaks. It is recommended to make up
these stock standard solutions separately, as their calibration solutions have to be made in higher (5x)
concentrations than for the other phthalates because of their multi-peak nature. Hence, the higher limit
of detection in Annex B.
6.1.3 Preparation of the calibration solutions
From the stock standard solutions, prepare at least five appropriate phthalate calibration solutions
(example of concentrations at 1 mg/l, 3 mg/l, 15 mg/l, 30 mg/l and 90 mg/l as described in the Table 2),
each containing an equal amount of the target phthalates (4.4 through 4.13) and an amount of internal
standard (4.3) in a mixture of tetrahydrofuran and the solvent used for the precipitation, mixed by
volume at a ratio of 1:2 (33 parts tetrahydrofuran to 66 parts of the other solvent), as shown in Table 2.
Each calibration solution should have a final internal standard concentration of 5 mg/l. Prepare one
calibration blank. Analyse the calibration solutions and calibration blank with the GC-MS. Qualitatively
analyse the result to ensure proper retention times and the absence of contamination and built up the
calibration curve.
ISO 14389:2014(E)
Table 2 — Examples of calibration solutions
Concentration Instructions
Blank In a 50 ml volumetric flask, add 0,25 ml of internal standard
(DCHP) stock solution; then, fill up to the mark with a mixture
of tetrahydrofuran and the solvent used for the precipitation,
mixed by volume at a ratio of 1:2 (33 parts tetrahydrofuran to
66 parts of the other solvent)
1 mg/l Add 0,1 ml of each stock standard solution in 100 ml volumetric
flask plus 0,5 ml of the internal standard (DCHP) stock solution;
then, fill up to the mark with a mixture of 33 parts of tetrahy-
drofuran to 66 parts of the solvent used for the precipitation.
3 mg/l Add 0,3 ml of each stock standard solution in 100 ml volumetric
flask plus 0,5 ml of the internal standard (DCHP) stock solution;
then, fill up to the mark with a mixture of 33 parts of tetrahy-
drofuran to 66 parts of the solvent used for the precipitation.
15 mg/l Add 0,75 ml of each stock standard solution in 50 ml volumet-
ric flask plus 0,25 ml of the internal standard (DCHP) stock
solution; then, fill up to the mark with a mixture of 33 parts of
tetrahydrofuran to 66 parts of the solvent used for the precipita-
tion.
30 mg/l Add 1,5 ml of each stock standard solution in 50 ml volumet-
ric flask plus 0,25 ml of the internal standard (DCHP) stock
solution; then, fill up to the mark with a mixture of 33 parts of
tetrahydrofuran to 66 parts of the solvent used for the precipita-
tion.
90 mg/l Add 4,5 ml of each stock standard solution in 50 ml volumet-
ric flask plus 0,25 ml of the internal standard (DCHP) stock
solution; then, fill up to the mark with a mixture of 33 parts of
tetrahydrofuran to 66 parts of the solvent used for the precipita-
tion.
If target ions other than 149 are used for quantification of DEHP, DNOP, DINP, DIDP and DIHP, all the
listed phthalates may be calibrated and quantified together.
Typical quantification ions for phthalates are shown in Annex B.
If DIDP and DINP overlap in the chromatogram; choose target ions indicated in Annex B.
In case the concentration of some phthalate in the extraction solution of a specimen lies outside the
limits of the calibration curve, dilute the solution with a mixture of 33 parts of tetrahydrofuran to 66
parts of the solvent used for the precipitation containing 5 mg/l of the internal standard, so that the
sample can be properly quantified.
NOTE The stock standard solutions are stored at 0 °C to 4 °C for up to 12 months, and the working solutions
are stored at 0 °C to 4 °C for up to six months, or sooner if ongoing quality control indicates problems.
6.2 Ultrasonic extraction and determination of phthalates
6.2.1 General
Ultrasonic extraction is performed using tetrahydrofuran on test specimens prepared in duplicate from
each textile sample, followed by precipitation of the (partially or completed) dissolved plastic component
using an appropriate solvent, centrifugation, and determination of phthalates. A blank is run in parallel
to avoid errors caused by contamination from the laboratory environment.
NOTE For example polyvinylchloride (PVC) is completely dissolved in tetrahydrofuran.
4 © ISO 2014 – All rights reserved

ISO 14389:2014(E)
6.2.2 Preparation of test specimen
A representative test specimen shall be prepared by mixing and cutting pieces from every coated
area/part of the textile sample. Cut the representative specimen into small pieces (less than 5 mm in
the greatest dimension), homogenize it, and weigh (0,30 ± 0,01) g of these pieces in each of two 40 ml
airtight vials (5.2) sealed with a PTFE septum. Ensure that the vials remain airtight in the ultrasonic
bath (5.3) throughout the entire extraction process.
Using a volumetric graduated pipette (5.6), add to each vial 10 ml of tetrahydrofuran (4.1) containing
5 mg/l of internal standard (4.3).
6.2.3 Extraction procedure
Place the vials in the ultrasonic bath (5.3) at (60 ± 5) °C for 1 h ± 5 min to allow the extraction of phthalates
(by complete or partial dissolution of the polymer).Then, remove the vials from the bath and let them
stand still until the extraction solution cools down to room temperature.
Using a volumetric graduated pipette, add dropwise to each vial 20ml of the solvent used for the
precipitation (4.2) containing 5mg/l of internal standard.
Shake the vials vigorously (preferably on a vortex type shaker) for at least 30 s and allow them to stand
still for (30 ± 2) min in order to allow the precipitation of polymer.
Centrifuge the vials at least 700 g (e.g. 2 500 r/min for 10 cm radius) for at least 10 min to drive and
settle any remaining suspended precipitates of polymer in organic phase to the bottom to obtain a
transparent organic solution. Then, withdraw and transfer a specimen aliquot of the organic solution
into two suitable GC sampling vials for GC-MS analysis.
CAUTION — Direct injection into GC-MS of suspended matter solution or cloudy solution might
contaminate the equipment.
If necessary, prepare further diluted solutions using an appropriate volume of a mixture of
tetrahydrofuran (4.1) and the solvent used for the precipitation (4.2) mixed by volume at a ratio of 1:2
(33 parts tetrahydrofuran to 66 parts of the other solvent) containing 5mg/l of the internal standard
(4.3) and then repeat the analysis.
6.2.4 Phthalates determination
Determinate the phthalates extracted in 6.2.3 by GC-MS (5.1). An example of a programme and the
parameters for GC-MS analysis of target phthalates are given in Annex B.
In some cases when the phthalates level is very low, it may be necessary to increase the mass of the test
specimens.
7 Calculation of the results
7.1 Calculation based on the corrected mass (by default)
From the calibration graph, determine the response of each phthalate, taking into account the internal
standard peak area, and interpolate the concentration of the phthalate, in milligrams per litre (mg/l),
ISO 14389:2014(E)
correcting for any dilutions. Subtract the blank concentration from the specimen concentration.
Calculate the result using Formula (1):
Vb××() Fa−
w = (1)
c
m ×10 000
c
where
w is the mass fraction of the individual phthalate, based on the corrected mass of the
c
test specimen;
V is 30 ml, that is the total volume of the phthalate solution before any dilution (10 ml of
tetrahydrofuran used for the extraction +20 ml of the solvent used in the precipitation
step);
m is the corrected mass of specimen (g);
c
a is the concentration of the individual phthalate of the blank solution (mg/l);
b is the concentration of the individual phthalate of the specimen solution (mg/l);
F is the dilution factor.
The determination of the corrected mass of test specimen is given in Annex A, as well as an example
of the calculation. Overall treated material is illustrated in Figure A.1 and locally treated material in
Figure A.2.
If the corrected mass of the test specimen, m , cannot be obtained, give a remark in the test report and
c
calculate the result according to 7.2.
7.2 Calculation based on the total mass (when relevant)
If the corrected mass of the test specimen, m , as described in Annex A, cannot be obtained and used for
c
the calculation of the results, then calculate the result using Formula (2).
Vb××Fa−
()
w = (2)
T
m ×10 000
T
where
w is the mass fraction of the individual phthalate, based on the total mass of the test
T
specimen;
V is 30 ml, that is the total volume of the phthalate solution before any dilution (10 ml of
tetrahydrofuran used for the extraction +20 ml of the solvent used in the precipitation
step);
m is the t
...