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 16190:2013Copyright European Committee for Standardization Provided by IHS und
2、er license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-National forewordThis Published Document is the UK implementation of CEN ISO/TS16190:2013.The UK participation in its preparation was entrusted to TechnicalCommittee TCI/69, Footwear, leather and co
3、ated 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 necessary provisions ofa contract. Users are responsible for its correct application. The British Standards Institution 2013.Published by
4、 BSI Standards Limited 2013ISBN 978 0 580 81936 0ICS 61.060Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document was published under the authority of theStandards Policy and Strategy Committee on 30 September 2013.Amendments/corrigenda issued since p
5、ublicationDate Text affectedPUBLISHED DOCUMENTPD CEN ISO/TS 16190:2013Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SP
6、EZIFIKATION CEN ISO/TS 16190 July 2013 ICS 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
7、critiques potentiellement prsentes dans 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 vorhanden
8、e kritische Substanzen - Prfverfahren zur 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 t
9、wo years the members of CEN will be requested 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
10、at national level in an appropriate form. 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, Bulga
11、ria, 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, Tur
12、key and United Kingdom. EUROPEAN COMMITTEE 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
13、 ISO/TS 16190:2013: EPD CEN ISO/TS 16190:2013Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-CEN ISO/TS 16190:2013 (E) 2 Contents Page Foreword 3 PD CEN ISO/TS 16190:2013Copyrigh
14、t European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-CEN ISO/TS 16190:2013 (E) 3 Foreword This document (CEN ISO/TS 16190:2013) has been prepared by Technical Committee CEN/TC 309 “Footwear“,
15、 the secretariat of which is held by AENOR, in collaboration with Technical Committee 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 a
16、ll such patent rights. According to the CEN-CENELEC Internal Regulations, the national 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 Republ
17、ic 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/TS 16190:2013 has been a
18、pproved by CEN as CEN ISO/TS 16190:2013 without any modification. PD CEN ISO/TS 16190:2013Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/TS 16190:2013(E) ISO 2013 All rights
19、 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 58 Performance of the method 59 Test report . 6PD C
20、EN ISO/TS 16190:2013Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-TECHNICAL SPECIFICATION ISO/TS 16190:2013(E)Footwear Critical substances potentially present in footwear and f
21、ootwear components Test method to quantitatively determine polycyclic aromatic hydrocarbons (PAH) in footwear materialsCAUTION The use of polycyclic aromatic hydrocarbons (PAH) can be hazardous.1 ScopeThis Technical Specification specifies a method to determine the amounts of polycyclic aromatic hyd
22、rocarbons (PAH) in footwear and footwear components.2 Normative referencesThe following documents, in whole or in part, 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 edit
23、ion of the referenced document (including any amendments) applies.ISO/TR 16178:2012, Footwear Critical substances potentially present in footwear and footwear componentsISO 17993:2002, Water quality Determination of 15 polycyclic aromatic hydrocarbons (PAH) in water by HPLC with fluorescence detecti
24、on after liquid-liquid extractionISO 28540:2011, Water quality Determination of 16 polycyclic aromatic hydrocarbons (PAH) 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
25、 aliquot is then analysed using chromatographic techniques.See ISO/TR 16178:2012, Table 1, which defines which materials 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 c
26、omponents specified in 6.4 to each 100 g/ml.NOTE Commercial solutions are available on the market.4.3 Internal standards: 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.
27、 ISO 2013 All rights reserved 1PD CEN ISO/TS 16190:2013Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/TS 16190:2013(E) Phenanthrene-d10 CAS number 1517-22-2 Triphenylbenzenz
28、e 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 Pyrene-d10
29、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-d10 or Anth
30、racene-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-d10Benzobfluoranthene B
31、enzoapyrene-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 Benzoapyrene-d12 or
32、 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.5.2 Lockab
33、le 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 16190:2013Copyright European Committee for Standardization Provided by IHS under lice
34、nse with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/TS 16190:2013(E)5.7 Suitable chromatographic techniques for PAH analysis.EXAMPLES High performance liquid chromatography (HPLC) method: fluorescence detector (FLD) and diode array detector (DAD); mass
35、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 Procedure6.1 Preparation of standard solutions6.1.1 Internal standard stock solution (each 100 g/ml)Use the analytical balance (5.1) and weigh 0,0
36、1 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 internal 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
37、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 the mark with n-hexane (4.1). ISO 2013 All rights reserved 3PD CEN ISO/TS 16190:2013Copyright European Committee for Standardization Provide
38、d by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/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: 86-7
39、3-7Phenanthrene CAS number: 85-01-8Anthracene 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
40、-2Benzokfluoranthene CAS number: 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 5
41、0 l of PAH stock solution (4.2) 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 (
42、4.1).6.2 Sample preparationDismantle 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
43、 to 3 mm edge length.4 ISO 2013 All rights reservedPD CEN ISO/TS 16190:2013Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/TS 16190:2013(E)6.3 ExtractionWeigh 1 g 0,001 g tes
44、t 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) for 1 h.After cooling to room temperature, filter the solution (if necessary through a PTFE membra
45、ne 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 is not mandatory for the HPLC method.6.4.2 GC-MS methodDetermine the PAH according to ISO 28540:201
46、1, 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 mass fraction w in mg/kg:wAc VAmAA=PAH-SPAH-StdPAH-StdSt.StdSinint.whereAPAH-Sis the peak area of PAH
47、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 of the sample (ml) (V = 10 ml according to 6.3);mSis the mass of the sample (g);Aint. Stdis the peak
48、 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 quantification, 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 16190:2013Copyright European Committee for Standardization Provided by IHS under li
