20082, 1498 2 180 240402022 EE, (Se) en) «lw > QQ Mem Amey eme~ (mex a Se ee ee ee ee en eed > oP Bw _ntps:wwn.doc88,comip-40599499678626.Ntml suet20.08.23, 14:98 BS 180 24040-2022 - EE < 18> QQ (hmm Amer 2 mE ~ Q a BS ISO 24040:2022 BSI Standards Publication Textiles — Determination of certain benzotriazole compounds bsi. > oP eB tps wow. doe86.comip-40599499578625.niml 2220.08.23, 14:96, me BS 180 24040-2022 - EE > QQ (we Ame - Zee ~ Q National foreword ‘This British Standard is the UK implementation of 150 24040:2022. ‘The UK participation in its preparation was entrusted to Technical Comittee TCI/100, Co-ordination of activities in textiles and clothing. Alist of organizations represented on this committee can be obtained on request to its committee manager. Contractual and legal considerations This publication has been prepared in good faith, however no representation, warranty, assurance or undertaking (express or implied) is or will be made, and no responsibility or liability is or will be accepted by BSI in relation to the adequacy, accuracy, completeness or reasonableness of this publication. Alland any such responsibility and liability is expressly disclaimed to the full extent permitted by the law. This publication Is provided as is, and Is to be used at the recipient's own risk, The recipient is advised to consider seeking professional guidance with respect to its use ofthis publication. This publication is not intended to constitutea contract, Users are responsible for its correct application, (© The British Standards Institution 2022 Published by BSI Standards Limited 2022 ISBN 978 0 539 173819 1€8 59,060.01 Compliance with a British Standard cannot confer immunity from legal obligations, ‘This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 April 2022. Amendments/corrigenda issued since publication. Date ‘Text affected > oP eB _ntps:wwn.doc88,comip-40599499678626.Ntml sat20.08.23, 14:96, BS 180 24040-2022 - EE <> QQ Dem Ame ~ 2 mx INTERNATIONAL Iso STANDARD 24040 First edition 2022-04-01 Textiles — Determination of certain benzotriazole compounds Textiles — Détermination de certains composés benzotriazole referer Sumber wo suoggoea See oso 2022 ESS Iso REAAAEE, AATRASCE -ntps:iww.doc88,comip-40599499678626.Ntml 4420.08.23, 14:96, BS 180 24040-2022 - EE < 18> QQ (hmm Amer 2 mE ~ Q BS ISO 24040:2022 10 24040:2022(E) Si tree ena Sand Saleat 22700009 8 copmigneice.ony waiters Aa ii (0180 2022- Arighs reserved _ntps:twwn.doc88,comip-40599499678626.Ntml si2t20.08.23, 14:96, BS 180 24040-2022 - EE < 19> QQ Mae Ame 2m ~ Q 180 24040:2022 Contents Page Foreword iv Introduction. v 1 Scope as 4 2 Normative references a 3 Terms and definitions 1 4 Principle 1 5 Reagents 1 6 Apparatus a 66 Waterbath and rotary evaporator 2 68 Chromatographic equipment zi 7 Procedure. 2 71 Preparation of standard solutions 2 TAL Preparation of stock standard solutions 2 7.41.2 _ Preparation ofthe calibration solutions 3 72 Preparation of test specimen 3 | 73. Extraction procedure 3 ‘Chromatographic determi 3 ' 9 Calculation 3 10 Testreport 4 | ‘Annex A (informative) Test parameters by LC-MS/MS. 5 ‘Annex B informative} Test parameters by LC-DAD. 8 ‘Annex ¢ (informative) Test parameters by GC-MS 10 & Se a 11802022 Alright rseensed Aa _ntps:wwn.doc88,comip-40599499678626.Ntml 6120.08.23, 14:96, BS 180 24040-2022 - EE < 18> QQ (hmm Amer 2 mE ~ Q 10 24040:2022 Foreword 180 (the International Organization for Standardization) isa worldwide federation of national standards bodies (10 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, 150 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 wwvwaiso.org/directives). “Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. 150 shall not be held responsible for identifying any or all such patent rights. Details of Any patent rights identified during the development of the dacument willbe inthe Introduction and/or ‘on the ISO list of patent declarations received (see ww wise ore/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 of the voluntary nature of standards, the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISO's adherence to the ‘World ‘Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT), see wwrviso, ‘This document was prepared by Technical Committee IS0/TC 38, Textiles Any feedback or questions on this document should be directed to the user's national standards body. A ‘complete isting of these bodies can be found at wwwyiso.org/members. html. Se a w (© 180.2022 - Alright reserve REAAAEE, RRTRASCE -ntps:iww.doc88,comip-40599499678626.Ntml nen20.08.23, 14:96, BS 180 24040-2022 - EE < 18> QQ (wm Amer 2 me ~ Q BS Iso 24040:2022 180 24040:2022 Introduction Benzotriazole compounds, which have a phenolic group attached to benzotriazole structure, can absorb the full spectrum of UV light and are mainly used as UVestabilizer for polymers such as textlles, plastics, polyurethanes and constituent in formulations used for coating of surfaces such as sun-protective ‘clothing and parasols. Certain benzotriazole compounds including UV-320, UV-327, UV-328 and UV-350 are toxic. UV-320 and UV-328 have been identified as PBT-substances, while UV-327 and UV-350 have been identified as vPvB-substances. Human exposure to certain benzotriazole compounds can occur through diverse sources such as skin ‘contact. A series of studies have shown the occurrence of certain benzotriazole compaunds In aquatic, terrestrial, atmospheric environment and as a result of anthropogenic activities. Considering thelr toxicity on several animal species, minimization of exposure ta certain benzotriazole compounds is recognized as important to the preservation of human health, This document provides a method for the determination of certain benzotriazole compounds including UV-320, UY-327, UV-328 and UV-350 intextiles. ‘The method described in this document is based on the use of liquid chromatogeaphy-tandem mass spectrometry (LC-MS/MS), liquid chromatography-diode array detector (LC-DAD) or gas chromatography with mass spectrometry (GC-MS) for textile materials (fibres and fabrics). Further investigations regarding the extraction efficiency of solvents are needed in connection to accessories (for example, plastic buttons) on textile products. > oP eB (150 2022 - Alright reserved y _ntps:twwn.doc88,comip-40599499678626.Ntml zt20.08.23, 14:96, BS 180 24040-2022 - EE < 18> QQ (wm Amer 2 me ~ Q > oP eB ‘This page deliberately left blank _ntps:wwn.doc88,comip-40599499678626.Ntml eat20.08.23, 14:96, BS 180 24040-2022 - EE < 18> QQ (wm Amer 2 me ~ Q INTERNATIONAL STANDARD 180 24040:2022 Textiles — Determination of certain benzotriazole compounds WARNING — This document calls for the use of substances and/or procedures that may 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. ‘The execution of its provisions is entrusted to appropriately qualified and experienced people. 1 Scope ‘This document specifies a method for determining the amount of certain benzoteiazole compounds (UV- 320, UV-327, UV-328, UV-350) in textiles by using liquid chromatography-tandem mass spectrometry (LC-MS/MS) oF liquid chromatography-diode array detector (L.C-DAD) or gas chromatography with mass spectrometry (GC-MS), ‘The method is applicable to all kinds of textile materials (fibres and fabrics). ; 2 Normative references ‘The following documents are referred to in the text in such a way that some or all of thelr content constitutes requirements of this document. For dated references, only the edition cited applies, For undated references, the latest edition ofthe referenced document (including any amendments) applies. IS0 3696, Water for analytical laboratory use — Specification and test methods 3. Terms and definitions i Noterms ul definitions are listed inthis document. {80 and IEC maintain terminological databases for use in standardization at the fllowingadresses: — 180 Online browsing platform: available at huinsw/awwwisoors/obp Blectropedia: available at hitps//ww.electropedi.orgd 4 Principle | Extract the benzotriazole compounds from textile specimen by ultrasonic generator with acetonitrile : Determine and identify the benzotriazole compounds in the specimen by liquid chromatography: tandem mass spectrometry (LC-MS/MS) or liquid chromatography-diode array detector (LC-DAD) or {gas chromatography with mass spectrometry (GC-MS). 5 Reagents Unless otherwise specified, use only reagents of recognized analytical grade, SA 2-(H-sechuty-S-tert-butyl2-hydrosyphenyl benzotriazole (UV-350), CAS No, 3643.78 5.2 2-(3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole (UV-320), No. 3846-717. Se SB 2:{3.Sedictectsayl2-hydromy pny) otitrinzsle (UVA2N),CAS No-2SS7R51 1802022 -Alrights reserved A 1 REAAAEE, RATRASCE Intpswwn.doe88, comip-40598499678826.Ntml sor20.06.23, 14:38, BS 180 24040-2022 - EE < 18> QQ (wm Amer 2 me ~ Q BS Iso 24040:2022 180 24040:2022 ‘The stock standards can be made in a mixed stock. This saves time and effort when preparing calibration solutions. 7.2. Preparation of the calibration solutions From the stock standard solutions, prepare at least five appropriate calibration solutions to establish the calibration curve, EXAMPLE Calibration solutions of 0.5 ug/ml 0.8 ug/ml, 1 ng/sml, 1.5 ug/ml, 2 ug/ml are applicable for LOS/15, Calibration solutions of 5 yg/ml, g/ml, 10 pa/ml, 15 jig/ml, 20 ug/ml are applicable for LC> DAD oF GEMS. 7.2. Preparation of test specimen Prepare a representative test specimen of the sample. Cut it into small pieces with 2 maximum dimension less than 5 mm and mix them homogeneously. Weigh (1,00 + 0,01) g of the pieces with a balance (6.1) and place them into a glass vial with a tight closure (6.3). 7.3. Extraction procedure Add 15 ml of acetonitrile (5.6) and extract the pieces at about 60 °C in an ultrasonic bath (6.4) for (15 + 1) min. Filter and transfer the extract into a 50 ml round-bttom flask (6.5). Add 15 ml of } acetonitrile (5,6) to the residue in the glass vial and extract the residue at about 60 °C in an ultrasonic bath for (15 1) min. Filter and merge the extract into the 50 ml round-bottom flask ‘The extract obtained is concentrated near to dryness by the evaporator (6) in the water bath at 40°C, and 2 ml of methanol (5.5) is added to dissolve the residue. Filtor the solution through an organic phase \ filtration membrane (6.7). The filtrate is ready for determination of benzotriazole compounds {mn parallel, run a blank to control contaminations, 8 Chromatographic determination Determine the benzotriazole compounds in the solution (7.3) by LC-MS/MS, LC-DAD or GC-MS (6.8) , Examples oftest parameters for LC-MS/MS, LC-DAD and GC-MS are shown in Annexes 8, Band C. ‘When the benzotriazole compounds level is beyond thellinear detector response range of the equipment, itis necessary to dilute the specimen liquid properly. 9 Calculation | Calibration curves including the concentration range of each benzotriazole compounds are prepared with at least five calibration points. The calibration curves are plotted by the responses against the concentrations of calibration solutions. Quantify the concentration of each benzotriazole compound by using the calibration curve. The content of each benzotriazole compound is expressed by the mass ratio of benzotriazole compound to test specimen, in % or mg/kg, Calculate the result by using, Bormula (1) or (2). > oP eB (150 2022 - Alright reserved 3 _ntps:twwn.doc88,comip-40599499678626.Ntml se20.08.23, 14:96, BS 180 24040-2022 - EE <> @Q Mam Amey 2m Q 1s0 24040:2022 ax 7) jaxt0 000 a where 1X isthe content ofthe benzotriazole compound, jin the textile specimen, in 9 isthe concentration ofthe benzotriazole compound, Gp_isthe concentration ofthe benzotviazole compound, isthe final volume ofthe specimen solution, i mi im isthemassof the test specimen, ing nthe specimen solution in g/ml; nthe blank solution, in jg/; ae @ where 2X; isthe content of the benzotriazole compound, in the textile specimen, in mg/l Gi Isthe concentration ofthe benzotriazole compound i in the specimen solution, in yg/ isthe concentration ofthe benzotriazole compound, jin the blank solution in g/ml: V isthe final volume ofthe specimen solution, in ml } im Isthemass ofthe test specimen, ing + 10 Test report ‘The test report shall include at least the following information: 8) areference to this document, i. 160 24040:2022, 1b). the date ofthe test: {all details necessary for complete identification of the sample tested; 44), detection method used by LC-MS/MS, LC-DAD oF GC-MS; ‘the content ofeach benzotriazole compound: |) any deviation from the procedure specified Se a 4 (© 180.2022 - Alright reserve tps doe88, comip-40598499678626.Ntml sm20.08.23, 14:96, BS 180 24040-2022 - EE < 18> QQ (wm Amer 2 me ~ Q 1s0 24040:2022 Annex A (informative) Test parameters by LC-MS/MS ‘As the instrumental equipment of the laboratories can vary, no generally applicable parameters can be provided for chromatographic analyses. The following parameters have been found suitable. Stationary phase: Zorbax® Eclipse Plus C184, 3,5 ym, 2,1 mm x $0 mm; Eluent 1 Methanol; Eluent 2: 0,01 moi/) ammonium formate: Flow rate: 0,3 ml/mi Gradient \ ‘Time (min) Eluent 1 (%, vole Eluent2(¥, vol; ‘ ‘umefraction) ume fraction) ° 88 12 ' 7 50 10 8 00 ° } 10 100 ° 105 88 2 12 a8 12 t Column temperature: 20°C; | Injection volume: 10h Detection made: “Multiple reaction monitoring (MRM); Spray gas: Nitrogen: t lonization: Electrospray ion source (ESI), positive: Capillary voltage: 4000¥; Gas flow: 12i/min; Dry gas temperature: 350°C; Nebulizer pressure: 241 KPa ‘Typical ions: see Table Ad. & 2 _ Zorba tips Plus C8 san example of slab product vale commercial. This inormatg ven for the convenience of users of this document and doesnot constitute an endorsement by 15D ofthis prog. (150 2022 - Alright reserved As REAAAEE, AATRASCE Intpswwn.doe88, comip-40598499678826.Ntml ss20.06.23, 14:38, BS 180 24040-2022 - EE < 18> QQ (hmm Amer 2 mE ~ Q a BS ISO 24040:2022 ‘Table A.1 — Typical ions for LC-MS/MS MRM nz Declustering | Collision ‘eieioePinsele potential energy, omp« Precursorion | Production ‘ rn zee 120) 9 uvsso> an 212 120) a7 uvs20e 324 ee ue 3 zz 100) 2 2aze 120) 2 uvaze 382 = 2 2 az 136 2 uvser 350 74 = = — Quantication on s_uy.s20 cannot be confused with UV-320 and UV-350 (hase on diferent typical ons} although Ebay have the same molecular weight “The detection limits of LC-MS/MS method for benzotriazole compounds are 1 mg/kg __ Under the given analysis conditions, the chromatograms of benzotriazole compounds are shown in i FlgumsAto A x 1 100 80 60 ° 2 4 6 8 wm 2X MRM mass transition 324-268 MRM mass transition 326-5212 relative abundance, expressed asa percentage time, expressed in min vv-350 uv320 Figure A. — LC-MS/MS chromatogram for UV-350 and UV-320 > oP eB 6 (©180-2022~ Al righ reserved tps: doe88, comip-40598499678626.Ntml sa20.06.23, 14:38, BS 180 24040-2022 - EE < 18> QQ (hmm Amer 2 mE ~ Q a 1s0 24040:2022 100 80 60 0 20 2X MRM mass transition 352->202 ~ MRM mass transition 352-2212 Y relative abundance, expressed asa percentage , X thes expressed in min } Figure A.2 — LC-MS/MS chromatogram for UV-328 109 a0 oo 40 aX IRM mass transition $58->302 MRM mass transition 350-5246 Y relative abundance, expressed asa percentage X time, expressed in min Figure A.3 — LC-MS/MS chromatogram for UV-327 > oP eB (150 2022 - Alright reserved tps doe88, comip-40598499678626.Ntml +52120.06.23, 14:38, BS 180 24040-2022 - EE < 18> QQ (wm Amer 2 me ~ Q 10 24040:2022 Annex B (informative) Test parameters by LC-DAD ‘As the instrumental equipment of the laboratories can vary, no generally applicable parameters can be provided for chromatographic analyses. The following parameters have been found suitable. Stationary phase: Zorbax® Eclipse XDB C18", 5 wm, 446mm * 250 mm; Ehuent Methanol fluent 2 0.01 mol/Lammoniam formate: Gradient Time in) Ehuent (vo! Eluent2 (vol umetraction) ue ration) ; ° 0 20 30 100 ° | 45 100 ° so ao 20 | 0 a0 20 Flow rate: 10 ml/min, + cohimn temperature: 40% | Injection volume 20k Detection DAD, spectrograph, 210 nm to 400 nm; | Quantification: at 305 nm and 345 nm. ‘The detection limits oF1.C-DAD method for henzotriazole compounds are 10 mg/ks, Under the given analysis conditions, the chromatogram of benzotriazole compounds is shown | in Figure Ba, 2) Zorbax® Eclipse XDB 10 is an example ofa stable product aalable commercial. This information ivy, for the convenience of users ofthis document and does not constitute an endorsement by 150 ofthis product, 8 (© 180.2022 - Alright reserve REAAAEE, AATRASCE Intpswwn.doe88, comip-40598499678826.Ntml 182120.08.23, 14:96, Key y x 1 2 3 4 BS 180 24040-2022 - EE mg > @Q (we Away 2 mt ~ BS Iso 24040:2022 180 24040:2022 abundance, expressed in mAU time, expressed in min vaso v.320 uvaze vva7 Figure B.1 — LC-DAD chromatogram for benzotriazole compounds (150 2022 - Alright reserved _ntps:twwn.doc88,comip-40599499678626.Ntml > oP eB se20.06.23, 14:38, BS 180 24040-2022 - EE < 18> QQ (wm Amer 2 me ~ Q 10 24040:2022 Annex C (informative) Test parameters by GC-MS ‘As the instrumental equipment of the laboratories can vary, no generally applicable parameters can be provided for chromatographic analyses. The following parameters have been found suitable. Capillary column: TraceGOLD® 76-5MS", length: 30 m, internal diameter 0,25 mm, film thickness: 0,25 ums Injector temperature: 310°C; Injection volume: 10 ul Carrier gas: helium, flow rate: 1,0 ml/min; Temp. programme: 150 °C (1 min), 150 °C to 270 °C (30 °C/min), : 270°C to 280°C (2°C/min); |} Transferline temperature: 280°C: Ionization mode: Ft; | tonization energy: 70ev; Injector system: split/splitless injector, split at 1.0 min; | Scan mode: selected ion monitor detection; | typlcat ons see Table C. Table C1 — Typical ions for GC-MS , Benzotriazole compound | Quantifier,mz | Qualifier,im/z van 308 [300,323,309 uvs0 308 [308,298,323 v.88 322 322,323, 951 : wvs27 342 342,344, 357 ‘The detection limits of GC-MS method for benzotriazole compounds are 10 mg/kg, Under the given analysis conditions, the chromatogram of benzotriazole compounds is shown in Eigure G1. 3) _TraceGOLD@ 16-5MS isan example of suitable product avalable commercial. This information i gen ig ‘the convenience of users of this document and does not constitute an endorsement by ISO of ths product. 10 (© 180.2022 - Alright reserve tps doe88, comip-40598499678626.Ntml se20.08.23, 14:96, BS 180 24040-2022 - EE < 18> QQ (wm Amer 2 me ~ Q 1s0 24040:2022 ‘ative abundance, expressed as a percentage time, expressed in min v.320 vv.350 vv28 v.27 senexag Figure C.1 — GC-MS chromatogram for benzotriazole compounds, > oP eB (150 2022 - Alright reserved u REAAAEE, AATRASCE Intpswwn.doe88, comip-40598499678826.Ntml v920.08.23, 14:96, BS 180 24040-2022 - EE < 19> QQ (Dime Ame - 2a ~ Q a British Standards Institution (BSI) laa CSIs a Re ac oie) ets ‘About us. (Pechentazpetherorbeed pene arden sans oltre ‘Me ee ended na Sane rasen cay asta {epee among reste op caer pce Spintec sone ues hee Information on standards | Sepa thie ac neon nee Ce ‘journal earns on che resect ‘laste tad caperce be roe a CuonSee a Copyright in BSI publications Zien or psn yee cpa foray et ahr erm pn do osc dad sp ahs pe org bon” } aversnnscer non sSeorwncarane. Storing and using standards (ret owsnd rrel conpry eo +The mye won mae thn are ceric a i ‘este Se aes vr ny aon oe ces ease + Asn ier cony mayb ete psa along 2c ry ny {cme cranial jer you se reneyy hss bee ecu be ‘srs bsi. _ntps:twwn.doc88,comip-40599499678626.Ntml reparing Briti British Standards and other standardization lice Reproducing extracts (orator rare Subscriptions ge an ee dew gr ‘ah Stadane Ot (254) un ar ee 609 hn anette any oyart asap ‘eucan tepin uth wi ve eer ane a (Sours nthe puree osu cnn sege ens ‘Sot by Sn 8 Sabet Meroe Sc dara mee sini BY bry Merb ‘Beata ay for anon ve ey ‘Sensors {Dla rare sda cone 38 beng mtr an anes pe eraltvgleanteros bern [inensayertend ieseroes eameeycorc™ Sei ettsecarananhere ann. caer Revisions ‘it Sie thr pbs eed yee rie ‘ster me mga oot aa ‘Susie gan nore enaoge Coe Useful Contacts segs al: ssocshetsicuseon owing carte at: nonierzcrvebs9019.0% Conrigh & eansng ate cngiototirepeon BSI Group Headquarters 293 oad VAAL > o B 20124120.08.23, 14:96, BS 180 24040-2022 - EE < 18> QQ (wm Amer 2 me ~ SC, BSR, SHER, RENE, ReUENE! SURO, SUTTER sooo ns Evan RRB? FNRI PRT RLABH AMT Re mene no RFR ah RRM) _ntps:wwn.doc88,comip-40599499678626.Ntml 25 150 4657-21 > oP Bw Omer ania