ISO 21084：2019 纺织品 烷基酚（AP）的测定方法.pdf

INTERNATIONAL STANDARD ISO 21084 First edition 2019-02 Textiles-Method for determination of alkylphenols(AP)!II Textiles-Methode de determination de la teneur en alkylphenols rAP)Reference number ISO 21084:2019(E)ISO 2019 I,.ISO 21084:2019(E)COPYRIGHT PROTECTED DOCUMENT ISO 2019 All rights reserved.Unless otherwise specified,or required in the context of its implementation,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 ISOs member body in the country of the requester.ISO copyright office CP 401 Ch.de Blandonnet 8 CH-1214 Vernier,Geneva Phone:[phone] Fa+41 22 749 09 47 Email:copyrightiso,org Website:www.iso.org Published in Switzerland ii ISO 2019-All rights reserved ISO 21084:2019(E)Contents Page Foreword.iv 1 2 Scope.Normative references.1.1 3 Terms and definitions.1 4 5 6 7 8 Principle.1 Reagents.1 Apparatus.2 6.1 Genera!.2 6.2 Apparatus and auxiliaries for preparing the sample.2 6.3 Chromatographic equipment.2 Procedure.2 7.1 Standard preparation.2 7.2 Sample preparation.2 7.3 Sample extraction.3 7.4 Sample analysis.3 Calculation and calibration.3 8.1 Calibration curve.3 8.2 External calibration.3 8.3 Calculation of each AP in sample.4 8.4 Reliability of the method.4 9 Test report.4 Annex A(informative)Examples of chromatographic condition-GC-MSjMS.5 Annex B(informative)Examples of chromatographic condition-LC-MSjMS and LC-FLD.8 Annex C(informative)Reliability of the method.10 ISO 2019-All rights reserved iii ISO 21084:2019(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(see WWw.jso,org/djrectjves).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(see wwwjsnnrg/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 voluntary nature of standards,the meaning of ISO specific terms and expressions related to conformity assessment,as well as information about ISOs adherence to the World Trade Organization(WTO)principles in the Technical Barriers to Trade(TBT)see the following URL:wwwjsQ,org/jso/foreword btml.This document was prepared by Technical Committee ISO/TC 38,Textiles.Any feedback or questions on this document should be directed to the users national standards body.A complete listing of these bodies can be found at wwwjsn nrg/members,html.iv ISO 2019-All rights reserved I INTERNATIONAL STANDARD ISO 21084:2019(E)Textiles-Method for determination of alkylphenols(AP)WARNING-This document calls for the use of substances/procedures that may be injurious to the health/environment if appropriate conditions are not observed.It refers only to technical suitability and does not absolve the user from legal obligations relating to health and safety/environment at any stage.1 Scope This document specifies the method for the determination of extractable alkyl phenols(AP)without derivatization step in textile and textile products.2 Normative references There are no normative references in this document.3 Terms and definitions No terms and definitions are listed in this document.ISO and IEC maintain terminological databases for use in standardization at the following addresses:ISO Online browsing platform:available at https:/!wwwisoorg/Ohp IEC Electropedia:available at http/!wwwelectropedia org I 4 Principle The test specimen is cut into small pieces,transferred to a sample vial and treated with methanol in ultrasonic water bath.The extract is filtered and collected.Subsequently,the collected extract is analysed by gas chromatograph with mass selective detector(GC-MS),liquid chromatograph with mass selective detector(LC-MS)or liquid chromatograph with fluorescence detector(LC-FLD).5 Reagents Unless otherwise specified,analytical grade chemicals shall be used.5.1 4-n-Octylphenol,CAS No.1806-26-4.5.2 4-tert-Octylphenol,CAS No.140-66-9.5.3 4-n-Nonylphenol,CAS No.104-405.5.4 4-Nonylphenol.CAS No.84852-153.5.5 Methanol,(HPLC grade).5.6 Acetone.5.7 Acetonitrile,(HPLC grade).ISO 2019-All rights reserved 1.ISO 21084:2019(E)5.8 Water,(HPLC grade).6 Apparatus 6.1 General Clean all glassware by rinsing with acetone(5.6)prior to use.6.2 Apparatus and auxiliaries for preparing the sample 6.2.1 Standard laboratory equipment and the following.6.2.2 Analytical balance with resolution of 0,01 g(for test specimen preparation).6.2.3 Analytical balance with resolution of 0,001 g(for standard preparation).6.2.4 Glass vial with screw cap(e.g.40 ml).6.2.5 Ultrasonic water bath to be set up at(70 5)C).6.2.6 Disposable syringe and membrane filter(with pore size of 0,45 m or less).6.2.7 Glass vial with septum cap(for chromatographic instrument).6.3 Chromatographic equipment 6.3.1 Gas chromatograph with mass selective detector(GC-MS),or 6.3.2 Liquid chromatograph with mass selective detector(LC-MS),or 6.3.3 Liquid chromatograph with fluorescence detector(LC-FLD).6.3.4 Capillary column for gas chromatograph,(5%-phenyl)-methylpolysiloxane phase,non-polar,bonded and cross-linked,low bleed.6.3.5 C18 reverse phase column for liquid chromatograph.7 Procedure 7.1 Standard preparation Octylphenols and nonylphenols are weighed accurately with analytical balance(2.U)and dissolved with methanol(5.5.)containing 1 000 mg!1 for stock solution.The stock solution can be preserved in the dark at less than 4C.7.2 Sample preparation The test specimen is cut into pieces with 5 mm x 5 mm and pieces are mixed homogeneously.The specimen is weighed 1 g to the nearest 0,01 g with analytical balance(li.Z.Z)and put into the 40 ml glass vial(6.Z.1)for extraction.2 ISO 2019-All rights reserved ISO 21084:2019(E)7.3 Sample extraction 10 ml of methanol(5.5)are added to glass vial(6.2A)for extraction.If sample is not sufficiently immersed in the extraction solvent,add more methanol and record the final volume for calculation of eachAP described in aJ.Then the sample vial is sonicated for extraction in ultrasonic water bath(6.2.S.)at 70C for 60 min.Subsequently,the extract is cooled down to room temperature,approximately 1 ml to 2 ml of extract is filtered into sample vial(ll.2.Z)using disposable syringe equipped with membrane filter(ll.Z&).The sample vial is closed with cap immediately for further analysis.In general,samples are examined without concentration,but the instrumental equipment of the laboratories may vary,the concentration procedure of extract is applicable for lower detection on limit.7.4 Sample analysis Qualitative and quantitative analysis of alkylphenols is performed by using GC-MS,LC-MS or LC-FLD.Guidelines for suitable chromatographic conditions are given in Annex A for GC-MS/MS and in Annex B for LC-MS/MS and LC-FLD.In case of positive results using GC-MS method,the results shall be confirmed using LC techniques.NOTE False-positive results using GC-MS method could be caused by decomposition of tris(nonylphenyl)phosphate(TNPP)due to high injection temperature.8 Calculation and calibration 8.1 Calibration curve Prepare a calibration curve of the response against the known standard concentration.From the calibration curve,the concentration of the AP(alkylphenols;octylphenols and nonylphenols)in mg/I(C5)is determined.NOTE Concentration ranges for the calibration standards are subject to change upon the need of each laboratory and equipment used.For quantification,the calibration curve shall have a correlation coefficient greater than 0,995(R2 greater than 0,990).8.2 External calibration The concentration of each AP in sample extract solution is calculated in mg/I according to Formyla(1):AS Cs=-xCc Ac where Cs is the concentration of each AP in sample extract solution,in mg/I;Cc is the concentration of each AP in calibration solution,in mg/I;AS is the area response of each AP in sample extract solution;AC is the area response of each AP in calibration solution.ISO 2019-All rights reserved(1)3 i I=ISO 21084:2019(E)8.3 Calculation of each AP in sample The AP level is calculated as mass portion,Xi,in mg/kg of the specimen according to Formula(2):Xi where Cs xVxDF M Xi is the concentration of each AP in sample,in mg/kg;Cs is the concentration of each AP and calculated according to Formula(1),in mg/I;V is the final volume of extract solution,in ml;M is the mass of test specimen,in g;DF is the dilution factor.8.4 Reliability of the method The reliability of the method is given in Annex C.9 Test report The test report shall include the following information:a)a reference to this document,i.e.ISO 21084:2019;b)identification of sample and the date of analysis;c)detection method and quantification method;d)the result of each AP(nonylphenols and octylphenols are reported individually);(2)e)details of any deviation from the procedure specified and of all circumstances that may have influenced the results.4 ISO 2019-All rights reserved i I,.:z i ij II !i j f I,!:z ISO 21084:2019(E)AnnexA(informative)Examples of chromatographic condition-GC-MSjMS A.1 Preliminary remark As the instrumental equipment of the laboratories may vary,no generally applicable instructions can be provided for chromatographic analyses.The following parameters have been successfully tested and used.A.2 Gas chromatographic conditions A.2.1 GC-MSjMS condition Capillary column:HP-5MS,length 35 m,inside diameter 0,25 mm,film thickness 0,25 m Injector mode:Splitless Injector temperature:250 C Injection volume:1 I Carrier gas:Helium(rate:1,0 ml/min)Collision gas:Nitrogen(rate:1,5 ml/min)Oven program:80 C(0 min),80 C to 230 C(7 Cjmin),230 C(2 min)Detection:Tandem mass spectrometer(MS/MS)Acquisition mode:MRM mode,see Table A 1 for MRM condition.Table A.1-MRM condition in GC-MS/MS Compounds m/z Ql)m/z Q3)135 107 4-tert-Octylphenol 135 77 107 77 4-nOctylphenol 107 51 107 77 4-n-Nonylphenol 107 51 107 77 121 77 135 77 4-Nonylphenol 149 107 163 107 191 107 See examples in Figure A I and Figure A 2.ISO 2019-All rights reserved Collision energy leV)10 30 20 40 20 40 20 20 30 10 20 20 5!,E;ISO 21084:2019(E),E y 8 000 000-3 2 0.-6 000 000-1 4 000 000-4 t;2 000 000-,i a A.I,g 12 14 16 18 X Key 1 4-tert-Octylphenol 2 4-Nonylphenol 3 4-n-Octylphenol 4 4-n-Nonylphenol X retention time,min y abundance Figure A.1-Total ion chromatogram(TIC)of alkylphenols in GC-MSjMS 6 ISO 2019-All rights reserved Key y 1000000 500000 400000 200000 200000 100000 300000 200000 100000 o 300000 200000 100000 o 60000 40000 20000 o 40000 20000 X retention time.min Y abundance 14,6 TIC total ion chromatogram 14,8 ISO 21084:2019(E)TIC MRM(l07,O-77.0)MRM(I2I,O-77.0)MRM(135,0-77,0)MRM(149,O 107.0)MRM(I63.0-107,0)MRM(191,0-107,0)15,0 15,2 15,4 15,6 15,8 16,0 X Figure A.2-MRM chromatogram of 4-nonylphenol(technical mixture)in GC-MS/MS ISO 2019-All rights reserved 7 ISO 21084:2019(E)AnnexB(informative)Examples of chromatographic condition-LC-MSjMS and LC-FLD B.l Liquid chromatographic conditions Mobile phase 1:Acetonitrile(ACN)Mobile phase 2:Water Column:ZORBAX Eclipse plus C18 1)(2,1 x 100 mm,1,8 m,pore size 95 A)Column temperature:40C Flow rate:0,3 mlfmin Injection volume:5 I Mobile phase condition:0 min to 12 min 65%ACN,12 min to 18 min 98%ACN B.2 Detector conditions B.2.1 Tandem mass spectrometer(MS/MS)Ionization mode:API-ES Polarity:Negative Desolvation temperature:350 C Desolvation gas flow(N2):lllfmin Nebulizer:50 psi Sheath gas flow rate:12lfmin Sheath gas temperature:350 C Capillary voltage:3 500 V Nozzle voltage:1 000 V Acquisition mode:MRM mode,see Table B 1 for MRM condition.Table B.l-MRM condition in LC-MS/MS Compounds mJzQ1)mJzQ3)4-tert-Octylphenol 205 133 4-Nonylphenol 219 133 4-n-Octylphenol 205 106 4-n-Nonylphenol 219 106 Collision energy(eV)22 30 20 20 1)This information is given for the convenience of users of this document and does not constitute an endorsement by ISO of this product.8 ISO 2019-All rights reserved B.2.2 Fluorescence detector(FLD)Wavelength:230 nm for excitation and 296 nm for emission See example in Figure B 1.y 1 100-3 50-2.J 0 2 4 6 8 Key 1 4tertOctylphenol 2 4Nonylphenol 3 4nOctylphenol 4 4-n-Nonylphenol X retention time,min y abundance 10 Figure B.l-Chromatogram of alkyl phenols in LC-FLD ISO 2019-All rights reserved ISO 21084:2019(E),4 12 X 9 ISO 21084:2019(E)AnnexC(informative)Reliability of the method The following statistical data presented in Tables C L c.z.,c.3.have been obtained for AP content in 3 kinds of samples through an interlaboratory test with 9 participating laboratories.Table C.1-Statistical data of the interlaboratory test(textile sample)Number of Number of A!ky!phenols Equipment x r S,R SR laboratories outliers mg/kg mg/kg mg/kg mg/kg mg/kg GC-MS/MS 6 91,2 5,9 2,1 52,6 19,0 4-n-Nonylphenol LC-MS/MS 6 81,8 5,7 2,0 36,9 13,3 where r=repeatability;R=reproducibility;x=mean value;Sr=standard deviation of the repeatability;SR=standard deviation of the reproducibility.Table C.2-Statistical data ofthe interlaboratory test(solution sample with low concentration)Number of Number of Alkylphenols Equipment x r S,R SR laboratories outliers mg/!mg/I mg/I mg/I mg/!GC-MS/MS 6 0,63 0,08 0,D3 0,39 0,14 4-n-Nonylphenol LC-MS/MS 6 0,53 0,D3 0,01 0,22 0,08 GC-MS/MS 6 0,79 0,06 0,02 0,47 0,17 4-n-Octylphenol LC-MS/MS 6 0,85 0,06 0,02 0,33 0,12 GC-MS/MS 6 1 0,97 0,25 0,09 0,58 0,21 4-Nonylpheno!LC-MS/MS 6 0,99 0,17 0,06 0,22 0,08 where r=repeatability;R=reproducibility;x=mean value;s,=standard deviation of the repeatability;SR=standard deviation of the reproducibility.10 ISO 2019-All rights reserved ISO 21084:2019(E)Table C.3-Statistical data of the interlaboratory test(solution sample with high concentration)Number of Number of Alkylphenols Equipment x r Sr R la