1、BSI Standards PublicationFootwear Critical substances potentially present in footwear and footwear components Test method to quantitativelydetermine polycyclic aromatichydrocarbons (PAH) in footwear materialsPD CEN ISO/TS 16190:2013National forewordThis Published Document is the UK implementation of
2、 CEN ISO/TS16190:2013.The UK participation in its preparation was entrusted to TechnicalCommittee TCI/69, Footwear, leather and coated fabrics.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessa
3、ry provisions ofa contract. Users are responsible for its correct application. The British Standards Institution 2013.Published by BSI Standards Limited 2013ISBN 978 0 580 81936 0ICS 61.060Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document was pub
4、lished under the authority of theStandards Policy and Strategy Committee on 30 September 2013.Amendments/corrigenda issued since publicationDate Text affectedPUBLISHED DOCUMENTPD CEN ISO/TS 16190:2013TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN ISO/TS 16190 July 2013 I
5、CS 61.060 English Version Footwear - Critical substances potentially present in footwear and footwear components - Test method to quantitatively determine polycyclic aromatic hydrocarbons (PAH) in footwear materials (ISO/TS 16190:2013) Chaussures - Substances critiques potentiellement prsentes dans
6、la chaussure et les composants de chaussure - Mthodes dessai pour dterminer quantitativement les hydrocarbures aromatiques polycycliques (HAP) dans les matriaux de chaussure (ISO/TS 16190:2013) Schuhe - Mglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische Substanzen - Prfverfahren zu
7、r quantitativen Bestimmung von PAK in Schuhwerkstoffen (ISO/TS 16190:2013) This Technical Specification (CEN/TS) was approved by CEN on 15 July 2013 for provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requ
8、ested to submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form
9、. It is permissible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, De
10、nmark, 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 COMMITT
11、EE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN ISO/TS 16190:2013: EPD CEN ISO/TS 16190
12、:2013CEN ISO/TS 16190:2013 (E) 2 Contents Page Foreword 3 PD CEN ISO/TS 16190:2013CEN ISO/TS 16190:2013 (E) 3 Foreword This document (CEN ISO/TS 16190:2013) has been prepared by Technical Committee CEN/TC 309 “Footwear“, the secretariat of which is held by AENOR, in collaboration with Technical Comm
13、ittee ISO/TC 216 “Footwear“. 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. According to the CEN-CENELEC Internal Regulations, the na
14、tional standards organizations of the following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latv
15、ia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Endorsement notice The text of ISO/TS 16190:2013 has been approved by CEN as CEN ISO/TS 16190:2013 without any modification. PD CEN ISO/TS
16、16190:2013ISO/TS 16190:2013(E) ISO 2013 All rights reserved iiiContents Page1 Scope . 12 Normative references 13 Principle 14 Chemicals . 15 Apparatus and materials 26 Procedure. 36.1 Preparation of standard solutions . 36.2 Sample preparation 46.3 Extraction 56.4 Determination . 57 Quantification 5
17、8 Performance of the method 59 Test report . 6PD CEN ISO/TS 16190:2013TECHNICAL SPECIFICATION ISO/TS 16190:2013(E)Footwear Critical substances potentially present in footwear and footwear components Test method to quantitatively determine polycyclic aromatic hydrocarbons (PAH) in footwear materialsC
18、AUTION The use of polycyclic aromatic hydrocarbons (PAH) can be hazardous.1 ScopeThis Technical Specification specifies a method to determine the amounts of polycyclic aromatic hydrocarbons (PAH) in footwear and footwear components.2 Normative referencesThe following documents, in whole or in part,
19、are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.ISO/TR 16178:2012, Footwear Critical substances potent
20、ially present in footwear and footwear componentsISO 17993:2002, Water quality Determination of 15 polycyclic aromatic hydrocarbons (PAH) in water by HPLC with fluorescence detection after liquid-liquid extractionISO 28540:2011, Water quality Determination of 16 polycyclic aromatic hydrocarbons (PAH
21、) in water Method using gas chromatography with mass spectrometric detection (GC-MS)3 PrincipleThe test sample is extracted using n-hexane at 60 C in an ultrasonic bath for 1 h. An aliquot is then analysed using chromatographic techniques.See ISO/TR 16178:2012, Table 1, which defines which materials
22、 are concerned by this determination.4 ChemicalsAll chemicals shall be analytical grade.4.1 n-Hexane, CAS1)number: 110-54-3.4.2 Certificated PAH stock solution, with 18 different components specified in 6.4 to each 100 g/ml.NOTE Commercial solutions are available on the market.4.3 Internal standards
23、: Naphthalene-d8, CAS number: 1146-65-2 Pyrene-d10, CAS number: 1718-52-1 Perylene-d12, CAS number: 1520-96-3 Anthracene-d10 CAS number: 1719-06-81) CAS: Chemical Abstract Service. ISO 2013 All rights reserved 1PD CEN ISO/TS 16190:2013ISO/TS 16190:2013(E) Phenanthrene-d10 CAS number 1517-22-2 Triphe
24、nylbenzenze CAS number: 612-71-5 Benzoapyrene-d12 CAS number: 63466-71-7NOTE The following list shows examples of correspondence between PAH and deuterated internal standards.Name Internal standardNaphthalene Naphthalene-d8Acenaphthylene Pyrene-d10 or Anthracene-d10 or Phenanthrene-d10Acenaphthene P
25、yrene-d10 or Anthracene-d10 or Phenanthrene-d10Fluorene Pyrene-d10 or Anthracene-d10 or Phenanthrene-d10Phenanthrene Pyrene-d10 or Anthracene-d10 or Phenanthrene-d10Anthracene Pyrene-d10 or Anthracene-d10 or Phenanthrene-d10Fluoranthene Pyrene-d10 or Anthracene-d10 or Phenanthrene-d10Pyrene Pyrene-d
26、10 or Anthracene-d10 or Phenanthrene-d10Benzoaanthracene Pyrene-d10 or Anthracene-d10 or Phenanthrene-d10Benzoepyrene Pyrene-d10 or Anthracene-d10 or Phenanthrene-d10Benzojfluoranthene Pyrene-d10 or Anthracene-d10 or Phenanthrene-d10Chrysene Pyrene-d10 or Anthracene-d10 or Phenanthrene-d10Benzobfluo
27、ranthene Benzoapyrene-d12 or Perylene-d12 or TriphenylbenzeneBenzokfluoranthene Benzoapyrene-d12 or Perylene-d12 or TriphenylbenzeneBenzoapyrene Benzoapyrene-d12 or Perylene-d12 or TriphenylbenzeneIndeno1,2,3-cdpyrene Benzoapyrene-d12 or Perylene-d12 or TriphenylbenzeneDibenzoa,hanthracene Benzoapyr
28、ene-d12 or Perylene-d12 or TriphenylbenzeneBenzog,h,iperylene Benzoapyrene-d12 or Perylene-d12 or Triphenylbenzene4.4 Preservation: Certificated PAH stock solution (4.2) and internal standards (4.3) shall be stored at 4 C 3 C and preserved in the dark.5 Apparatus and materials5.1 Analytical balance.
29、5.2 Lockable jar with lid.5.3 Ultrasonic bath (temperature controlled).5.4 Micropipettes, 50 l and 100 l.5.5 Pipette, 0,5 to 5 ml capacity.5.6 Volumetric flasks of 10 ml and 100 ml.2 ISO 2013 All rights reservedPD CEN ISO/TS 16190:2013ISO/TS 16190:2013(E)5.7 Suitable chromatographic techniques for P
30、AH analysis.EXAMPLES High performance liquid chromatography (HPLC) method: fluorescence detector (FLD) and diode array detector (DAD); mass selective detector (MS or MS-MS) method: gas chromatograph with mass selective detector (GC-MS or GC-MS-MS).5.8 PTFE-membrane filter, pore width 0,45 m.6 Proced
31、ure6.1 Preparation of standard solutions6.1.1 Internal standard stock solution (each 100 g/ml)Use the analytical balance (5.1) and weigh 0,01 g of each internal standard (4.3) into several 100 ml volumetric flasks (5.6) and fill up to the mark with n-hexane (4.1).The maximum shelf life of this inter
32、nal standard stock solution is 3 months. It shall be stored at 4 C 3 C and preserved in the dark.NOTE Commercial solutions are available on the market.6.1.2 Internal standard solution (5 g/ml)Transfer 0,5 ml of each internal standard solution (6.1.1) to a 10 ml volumetric flask (5.6) and fill up to
33、the mark with n-hexane (4.1). ISO 2013 All rights reserved 3PD CEN ISO/TS 16190:2013ISO/TS 16190:2013(E)6.1.3 PAHThe following 18 PAH are relevant:Naphthalene CAS number: 91-20-3Acenaphthylene CAS number: 208-96-8Acenaphthene CAS number: 83-32-9Fluorene CAS number: 86-73-7Phenanthrene CAS number: 85
34、-01-8Anthracene CAS number: 120-12-7Fluoranthene CAS number: 206-44-0Pyrene CAS number: 129-00-0Benzoaanthracene CAS number: 56-55-3Benzoepyrene CAS number: 192-97-2Benzojfluoranthene CAS number: 205-82-3Chrysene CAS number: 218-01-9Benzobfluoranthene CAS number: 205-99-2Benzokfluoranthene CAS numbe
35、r: 207-08-9Benzoapyrene CAS number: 50-32-8Indeno1,2,3-cdpyrene CAS number: 193-39-5Dibenzoa,hanthracene CAS number: 53-70-3Benzog,h,iperylene CAS number: 191-24-26.1.4 PAH standard solution (0,5 g/ml)Place 9 ml of n-hexane (4.1) in a 10 ml volumetric flask (5.6), add 50 l of PAH stock solution (4.2
36、) and then top up to the calibration mark with n-hexane (4.1).6.1.5 PAH calibration solution (0,05 g/ml)Put 1 ml of PAH standard solution (6.1.4) and 0,1 ml of internal standard solution (6.1.2) into a 10 ml volumetric flask (5.6) and fill up to the mark with n-hexane (4.1).6.2 Sample preparationDis
37、mantle the footwear and separate the different material types into three categories: leather, textile and polymer.Each test sample shall consist of a single material type (leather or textile or polymer) which is tested separately.Each material type is cut into pieces up to 3 mm edge length.4 ISO 201
38、3 All rights reservedPD CEN ISO/TS 16190:2013ISO/TS 16190:2013(E)6.3 ExtractionWeigh 1 g 0,001 g test sample (ms) with the analytical balance (5.1) into the lockable jar (5.2) and mix with 9,9 ml n-hexane (4.1) and 0,1 ml internal standard solution (6.1.2). Extract at 60 C in an ultrasonic bath (5.3
39、) for 1 h.After cooling to room temperature, filter the solution (if necessary through a PTFE membrane filter (5.8).6.4 Determination6.4.1 HPLC methodDetermine the PAH according to ISO 17993:2002, 8.5. An example of chromatographic conditions is given in ISO 17993:2002, Annex A.Internal standard use
40、 is not mandatory for the HPLC method.6.4.2 GC-MS methodDetermine the PAH according to ISO 28540:2011, Clause 10.An example of chromatographic conditions is given in ISO 28540:2011, Annex A.7 QuantificationThe content of individual substances is calculated according to the following equation as a ma
41、ss fraction w in mg/kg:wAc VAmAA=PAH-SPAH-StdPAH-StdSt.StdSinint.whereAPAH-Sis the peak area of PAH components in the sample;APAH-Stdis the peak area of PAH components in the calibration solution;cPAH-Stdis the concentration of PAH components in the calibration solution (g/ml);V is the final volume
42、of the sample (ml) (V = 10 ml according to 6.3);mSis the mass of the sample (g);Aint. Stdis the peak area of internal standard in calibration solution;Aint. Sis the peak area of internal standard in the sample.8 Performance of the methodThe laboratory shall determine for each PAH the limit of quanti
43、fication, taking into account the chosen technique (6.4).This quantification limit shall be lower or equal to 0,2 mg/kg for each PAH. ISO 2013 All rights reserved 5PD CEN ISO/TS 16190:2013ISO/TS 16190:2013(E)9 Test reportThe test report shall include at least the following:a) reference to this test
44、method;b) date of the test;c) all details necessary for complete identification of the sample tested;d) different material types (6.2) that have been tested;e) condition of storage before the test, if available;f) the technique chosen in 6.4;g) the amount determined for each of the 18 PAH in mg/kg;h
45、) any deviation from the present standard.6 ISO 2013 All rights reservedPD CEN ISO/TS 16190:2013This page deliberately left blankBSI is the national body responsible for preparing British Standards and other standards-related publications, information and services.BSI is incorporated by Royal Charte
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