© ISO 2016 Textiles — Determination of certain flame retardants — Part 1 Brominated flame retardants Textiles — Détermination de certains retardateurs de flamme — Partie 1 Retardateurs de flamme bromé[.]
INTERNATIONAL STANDARD ISO 17881-1 First edition 2016-02-01 Textiles — Determination of certain flame retardants — Part 1: Brominated flame retardants Textiles — Détermination de certains retardateurs de flamme — Partie 1: Retardateurs de flamme bromés Reference number ISO 17881-1:2016(E) © ISO 2016 ISO 17881-1:2016(E) COPYRIGHT PROTECTED DOCUMENT © ISO 2016, Published in Switzerland All rights reserved Unless otherwise specified, no part o f 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 o f the requester ISO copyright o ffice Ch de Blandonnet • CP 401 CH-1214 Vernier, Geneva, Switzerland Tel +41 22 749 01 11 Fax +41 22 749 09 47 copyright@iso.org www.iso.org ii © ISO 2016 – All rights reserved ISO 17881-1:2016(E) Contents Page Foreword iv Scope Principle Reagents Apparatus Procedure 5.1 5.2 5.3 Preparation of standard solutions 5.1.1 Stock standard solution 5.1.2 Internal standard solution 5.1.3 Working solution Preparation of test specimen Ultrasonic wave extraction Flame retardants determination Calculation Test report Annex A (informative) Test parameters by GC-MS Annex B (informative) Round Robin test © ISO 2016 – All rights reserved iii ISO 7881 -1 : 01 6(E) Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies) The work o f 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 o f electrotechnical standardization The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part In particular the different approval criteria needed for the di fferent types o f ISO documents should be noted This document was dra fted in accordance with the editorial rules of the ISO/IEC Directives, Part (see www.iso.org/directives) Attention is drawn to the possibility that some o f the elements o f this document may be the subject o f patent rights ISO shall not be held responsible for identi fying any or all such patent rights Details o f any patent rights identified during the development o f the document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents) Any trade name used in this document is in formation given for the convenience o f users and does not constitute an endorsement For an explanation on the meaning o f ISO specific terms and expressions related to formity 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 in formation The committee responsible for this document is ISO/TC 38, Textiles ISO 17881 consists of the following parts, under the general title Textiles — Determination of certain flame retardants: — Part 1: Brominated flame retardants — Part 2: Phosphorus flame retardants iv © ISO 2016 – All rights reserved INTERNATIONAL STANDARD ISO 17881-1:2016(E) Textiles — Determination o f certain flame retardants — Part 1: Brominated flame retardants WARNING — This International Standard calls for the use o f substances and/or procedures that may be injurious to health i f adequate precautions are not taken It re fers only to technical suitability and does not absolve the user from legal obligations relating to health and sa fety at any stage It has been assumed in the dra fting o f this International Standard that the execution o f its provisions is entrusted to appropriately qualified and experienced people Scope This part o f ISO 17881 specifies a test method for determining some brominated flame retardants in textiles by gas chromatography – mass spectrometry (GC-MS) The method is applicable to all kinds of textile products Principle The flame retardants are extracted from textile specimen by ultrasonic generator with toluene The flame retardants in the specimen are identified by GC-MS and quantified by using internal standard method Reagents Unless otherwise specified, use only reagents o f recognized analytical grade , CAS no 2052-07-5 Monobromobiphenyl (MonoBB) Dibromobiphenyl (DiBB) 3 Tribromobiphenyl (TriBB) Tetrabromobiphenyl (TetraBB) Pentabromo-1,1’-biphenyl (PentaBB) Hexabromobiphenyl (HexaBB) Heptabromo-1,1’-biphenyl (HeptaBB) Octabromobiphenyl (OctaBB) Nonabromobiphenyl (NonaBB) , CAS no 57422-77-2 , CAS no 59080-34-1 , CAS no 60044-24-8 , CAS no 59080-39-6 , CAS no 60044-26-0 , CAS no 88700-06-5 , CAS no 67889-00-3 10 Decabromobiphenyl (DecaBB) , CAS no 69278-62-2 , CAS no 13654-09-6 11 Tetrabromodiphenylether (TetraBDE) © ISO 2016 – All rights reserved , CAS no 5436-43-1 ISO 17881-1:2 016(E) , CAS no.32534-81-9 Pentabromodiphenylether (PentaBDE) 3 Hexabromodiphenylether (HexaBDE) Heptabromodiphenylether (HeptaBDE) Octabromodiphenylether (OctaBDE) Decabromodiphenylether (DecaBDE) Hexabromocyclododecane (HBCDD) Decachlorobiphenyl Toluene , CAS no 207122-15-4 , CAS no 207122-16-5 , CAS no 337513-72-1 , CAS no 1163-19-5 , CAS no 25637-99-4 , CAS no.2051-24-3, internal standard (IS) NOTE Since brominated flame retardants have many isomers, this method might not cover all o f them Determination o f the isomers o f flame retardants in Clause can refer to this method according to the principle Apparatus 4.1 Gas chromatography – mass spectrometry (GC-MS) 4.2 Ultrasonic generator 4.3 Evaporator device 4.4 Brown glass vial 4.5 Flask 4.6 Filtration membrane 4.7 Balance , with a frequency from 35 kHz to 45 kHz , with water bath at 50 °C , 40 ml with tight closure , 100 ml , 0,45 µm , an accuracy o f 0,1 mg Procedure 5 1 Preparation o f standard solutions Stock standard solution Prepare 000 µg/ml o f stock standard solutions with individual flame retardant (3.1 internal standard (3.18) in toluene (3.19) to 3.17) and Some commercial re ference material solutions may be available in a di fferent solvent Internal standard solution Prepare 10 µg/ml standard solution o f decachlorobiphenyl in toluene © ISO 2016 – All rights reserved ISO 17881-1:2 016(E) Working solution P rep a re an ad m i xture worki ng s olution o f 17 fl ame re ta rda nts i n i nterna l s ta ndard s olution ( 5.1.2) and d i lute it to a s erie s o f s u itable concentration s dep end i ng on te s t ne e d s S ele c t at le as t five d i lution s o f the c a l ibration s e ts to cre ate c a l ibration c u r ve and p er form G C-M S ana lys i s Preparation o f test specimen Prepare a representative test specimen of the sample Cut it into small pieces and weigh (1,00 ± 0,01) g of the pieces with a balance ( ) 4.7 Ultrasonic wave extraction Put the pieces in a vial with tight closure ( ) and add 20 ml of toluene Place the vial in an ultrasonic generator ( ) and extract the pieces for 30 at room temperature Filter and transfer the ) Add 10 ml of toluene to the residue in the vial and place the vial in the ultrasonic generator to extract the residue for 15 at room temperature Filter and merge the ) ) Add ml of internal standard solution f (5.1.2 4.4 e x trac t i nto 0 m l fl a s k (4 e x trac t i nto the fl a s k (4 E vap orate the e xtrac t to ne a r d r yne s s b y evap orator device (4 ) to d i s s olve the re s idue a nd then fi lter b y fi ltration membrane (4 6) T he fi ltrate i s re ady or de term i nation o f flame re tardants Flame retardants determination 5.3 given in Annex A as an example Run a blank to control contamination D e term i ne the flame re tardants i n the s olution ( ) b y G C-M S (4.1) T he te s t p ara me ters b y G C -M S are When the flame re ta rdants level i s ver y low, it i s ne ce s s ar y to i ncre as e the ma s s o f the pie ce s i n order to reach at least three times the detection limit When the flame re ta rdant level i s b eyond the l i ne ar de te c tor re s p on s e range o f the e qu ipment, it i s ne ce s s ar y to d i lute the s p e ci men l iquid prop erly Calculation Qua nti fy the concentration o f e ach fla me re tardant by u s i ng the c a l ibration c u r ve T he content o f e ach flame re tardant i s e xpre s s e d b y the mas s ratio o f flame re tardant to te s t s p e c i men, i n μg/g C a lc u late the re s u lt b y u s i ng Formu l a (1) Xi = ( Ci − C0 ) × V m (1) where Xi i s the content o f the fl ame re tardant, i, i n the te xti le s p e c i men, i n μg/g; Ci i s the concentration o f the fl ame re ta rd ant, i, i n the s p e c i men s olution, i n μg/m l; C i s the concentration o f the fl ame re ta rd ant, i, i n the b lan k s olution, i n μg/m l; V i s the fi na l volu me o f the s p e ci men s olution, i n m l; m is the mass of the test specimen, in g © ISO 2016 – All rights reserved ISO 17881-1:2016(E) Test report The test report shall include the following information: a) a re ference to th i s p a r t o f I S O 178 81 , i e I S O 178 81-1 : 016; b) a l l de tai l s ne ce s s ar y c) the content o f e ach flame re tardant; d) any devi ation from for identi fic ation o f the s a mple te s te d; the pro ce du re s p e c i fie d © ISO 2016 – All rights reserved ISO 17881-1:2016(E) Annex A (informative) Test parameters by GC-MS A.1 Instrument parameters As the instrumental equipment o f the laboratories may vary, no generally applicable parameters can be provided for chromatographic analyses The following parameters have been found success fully a) VF-5ht, length 15 m, inside diameter 0,25 mm, film thickness 0,1 μm or equivalent; Capillary column: b) Temperature programme: c) Injector temperature: d) Transfer line temperature: e) Carrier gas: 100 °C for min, 100 °C to 310 °C (20 °C/min), 310 °C for min; 280 °C; 300 °C; Helium with a purity o f no less than 99,999 % delivered at 1,5 ml/min; f) Ionization mode: g) Ionization energy: h) Detection mode: i) Injector system: Splitless, split at min; j) μl EI; 70 eV; Selected ion monitor detection; Injector volume: A.2 Typical ions and detection limit Typical ions and detection limit for flame retardants are shown in Table A.1 Table A.1 — Typical ions and detection limit No Flame retardant Monobromobiphenyl (MonoBB) Dibromobiphenyl (DiBB) Tribromobiphenyl (TriBB) Tetrabromobiphenyl (TetraBB) Pentabromo-1,1’-biphenyl (PentaBB) Hexabromobiphenyl (HexaBB) Heptabromo-1,1’-biphenyl (HeptaBB) Octabromobiphenyl (OctaBB) Nonabromobiphenyl (NonaBB) © ISO 2016 – All rights reserved Typical ions/amu Target ion 152 152 230 310 388 468 546 544 705 Target ion 234, 232, 152 312, 310, 152 392, 390, 230 470, 310, 308 550, 390, 388 628, 468, 466 705, 546, 544 785, 546, 544 864, 705, 703 Detection limit (μg/g) 5 5 5 10 10 10 ISO 7881 -1 : 01 6(E) Table A.1 No 10 11 12 13 14 15 16 17 18 Flame retardant D e c abro mo b ip henyl ( D e c a B B ) Te trabromo d ip henyle ther ( Te tra B D E ) (continued) Typic a l ion s/a mu Target ion 783 326 Target ion 4, 78 , 78 48 8, 486, 32 Pentab ro mo d iphenyle ther ( Penta B D E ) 40 4, , 4 H e xab romo d ip henyle ther ( H e xa B D E ) 484 43 , 4, H ep tabromo d ip henyle ther(H ep ta B D E ) 562 2 , 62 , 45 O c tab romo d ip henyle ther (O c ta B D E ) 42 01 , 42 , D e c ab ro mo d ip henyle ther ( D e c aB D E ) 79 9 9, 79 9, 79 H e xab romo c yclo de c a ne ( H B C D D) D e c ach loro bip henyl (I S ) 157 49 19, 9, 49 , 42 , 14 Detection limit (μg/g) 10 5 5 10 10 — © ISO 2016 – All rights reserved ISO 17881-1:2016(E) Annex B (informative) Round Robin test T he Rou nd Robi n te s t wa s c arrie d out b y five tex ti le lab oratorie s i n C h i na A total of nine samples were prepared, three from cotton woven fabrics (no.1 to 3), three from p olye s ter woven fabrics (no to ) , and th re e from co tton/5 p olye s ter woven fabrics (no to 9) e ach conta i n i ng s i x fla me re ta rda nts , i e D i B B , PentaB B , D e c aB B , PentaB DE , D e c aB DE , a nd H B C DD The three samples from each fabric were at three concentration levels of 50mg/kg, 200 mg/kg, and 0 mg/ kg T h re e te s t s p e c i men s from e ach s ample were te s te d i n e ach l ab orator y The results of the Round Robin test are shown in Table B.1 Table B — Results o f the Round Robin tes t Sample no E xp ected Substance DiBB PentaBB DecaBB PentaBDE DecaBDE HBCDD DiBB PentaBB DecaBB PentaBDE DecaBDE HBCDD DiBB PentaBB DecaBB PentaBDE DecaBDE HBCDD DiBB PentaBB DecaBB PentaBDE DecaBDE HBCDD value (mg/ kg) 50 50 50 50 50 50 200 200 200 200 200 200 500 500 500 500 500 500 50 50 50 50 50 50 © ISO 2016 – All rights reserved Mean Recovery (mg/ kg) (%) 49, 62 9, 45 , 0 90,00 4,76 9, 42 , 85,03 46, ,4 46, ,1 19 9, 9, 19 , 9, 42 19 , 9 ,70 9,9 4,9 183,85 ,9 Repeatability Sr (mg/ kg) 2,08 ,9 1,63 ,46 1,82 2,78 6,71 6,77 6,28 8,26 9, 51 6,16 19 , 96,03 49 ,4 98,30 ,9 ,4 ,49 ,19 478 ,75 ,75 479, 95 , 85 ,4 96,08 475 , 95 ,06 ,14 92 , 4,9 9,7 47, 20,72 9,47 CVr (%) 4, 4, ,64 5,72 6,16 11,52 , 69 ,9 7,9 17, ,9 ,79 ,42 3,36 ,41 3,28 4, 5,17 3,21 2,85 4, 4, 3 ,9 4,14 ,14 4, 5 41 ,70 ,4 ,43 ,43 46, ,70 87,68 CVR (%) 14, 3,88 43 , SR (mg/kg) ,4 01 18,65 35,11 2,38 1,30 2,00 2,23 Reproducibility 7, 5,17 ,9 4, 5,08 7,57 14, ,49 10,35 , 69 20,68 7,70 ,4 17,82 3,85 7, 6,28 ,41 8,26 11,25 4, 01 9,45 12,12 27,11 2,51 5,66 19,74 4,1 23 , 59 4,91 28,18 3,50 6,30 7,42 7,82 8,85 6, 59 ,9 7, 59 14, 15,77 18,76 19,1 15,0 ISO 17881-1:2016(E) Table B Sample no E xp ected Substance DiBB PentaBB DecaBB PentaBDE DecaBDE HBCDD DiBB PentaBB DecaBB PentaBDE DecaBDE HBCDD DiBB PentaBB DecaBB PentaBDE DecaBDE HBCDD DiBB PentaBB DecaBB PentaBDE DecaBDE HBCDD DiBB PentaBB DecaBB PentaBDE DecaBDE HBCDD value (mg/ kg) 200 200 200 200 200 200 500 500 500 500 500 500 50 50 50 50 50 50 200 200 200 200 200 200 500 500 500 500 500 500 (continued) Repeatability Repro ducibi lity Mean Recovery (mg/ kg) (%) Sr (mg/ kg) CVr (%) SR (mg/ kg) 19 , 47 96,24 7,9 , 14 10 , 19 , 95 , 10,80 6,57 7,65 5,65 5,03 3,63 11,75 16,27 15,06 15,05 12,76 , 69 ,69 185,75 92 , 87 9, 4, 7,9 9 4, 0 180,58 90,29 ,9 , 19 483 , 82 , 76 47 , ,9 47 , 41 4, 468 , 93 ,68 485 , 21 7, 47, 14 4, 4 , 67 9, 45 , 90,06 40, 33 80,66 45 , 43 90,86 42 , 85 ,0 9,4 , 70 202,38 1 ,19 9, 4, 8 9, 4, 19 ,9 ,9 17 9,1 8 9, 59 47 ,9 ,19 49 4,4 98,89 503,78 100,76 47 7,9 95 , 59 47 , ,9 9, 3 7, 9,4 6,55 17,75 13,65 3,54 4, 7,21 2,82 2,70 1,52 16, 59 3,54 ,9 13,84 25,24 , 69 18,11 17,67 21,12 1,52 3,23 ,7 4, 01 ,9 2,73 2,06 2,70 2,21 7,37 6,05 5,11 3,06 5,89 8,12 ,9 4, 5 ,9 ,19 ,89 ,9 4, 2,11 3,68 4, ,9 5,61 7,9 8,00 7,07 6,38 2,86 5,26 6,06 3,87 ,64 9,1 15,65 ,79 22,15 12 ,34 10 , 69 10,50 12,36 5,80 15,31 7,78 15,56 5,55 6,11 3,06 8,10 6,57 2,27 3,22 2,57 19,7 4,1 35,29 4, 13 ,0 20,70 5,53 6,15 8,76 4, 7,07 7,65 31,27 11,23 16,22 12,26 4, CVR (%) 41 , 19 23,03 ,9 ,9 4, , 69 8,65 4, 6 ,9 1,87 7,35 2,67 © ISO 2016 – All rights reserved ISO 7881 -1 : 01 6(E) ICS 59.080.01 Price based on pages © ISO 2016 – All rights reserved