1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationFootwear Critical substances potentially present in footwear and footwear components Test method to quantitativelydetermine dimethylfumarate(DMFU) in footwear materialsPD CEN ISO
2、/TS 16186:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-National forewordThis Published Document is the UK implementation of CEN ISO/TS16186:2012.The UK participation in it
3、s preparation was entrusted to Technical CommitteeTCI/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 necessary provisions of acontract. Users are responsibl
4、e for its correct application. The British Standards Institution 2012 Published by BSI Standards Limited 2012 ISBN 978 0 580 76675 6 ICS 61.060Compliance with a British Standard cannot confer immunity from legal obligations.This Published Document was published under the authority of the Standards P
5、olicy and Strategy Committee on 31 August 2012.Amendments issued since publicationAmd. No. Date Text affectedPUBLISHED DOCUMENTPD CEN ISO/TS 16186:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without
6、license from IHS-,-,-TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN ISO/TS 16186 August 2012 ICS 61.060 English Version Footwear - Critical substances potentially present in footwear and footwear components - Test method to quantitatively determine dimethyl fumarate (DMF
7、U) in footwear materials (ISO/TS 16186:2012) Chaussure - Substances critiques potentiellement prsentes dans la chaussure et les composants de chaussure - Mthodes dessai pour dterminer quantitativement le dimthylfumarate (DMFu) dans les matriaux de chaussure (ISO/TS 16186:2012) Schuhe - Mglicherweise
8、 in Schuhen und Schuhbestandteilen vorhandene kritische Substanzen - Prfverfahren zur quantitativen Bestimung von Dimethylfumarat (DMFU) in Schuhwerkstoffen (ISO/TS 16186:2012) This Technical Specification (CEN/TS) was approved by CEN on 6 August 2012 for provisional application. The period of valid
9、ity of this CEN/TS is limited initially to three years. After two 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 s
10、ame way as for an EN and to make the CEN/TS available promptly 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 membe
11、rs are the national standards bodies of Austria, Belgium, Bulgaria, 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, Portuga
12、l, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any
13、means reserved worldwide for CEN national Members. Ref. No. CEN ISO/TS 16186:2012: EPD CEN ISO/TS 16186:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-CEN ISO/TS 16186:2012
14、(E) 2 Contents Page Foreword 3PD CEN ISO/TS 16186:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-CEN ISO/TS 16186:2012 (E) 3 Foreword This document (CEN ISO/TS 16186:2012) h
15、as been prepared by Technical Committee CEN/TC 309 “Footwear“, 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
16、CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Croatia, Cyprus, Cze
17、ch 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, Turkey and the United Kingdo
18、m. PD CEN ISO/TS 16186:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-Footwear Critical substances potentially present in footwear and footwear components Test method to qua
19、ntitatively determine dimethyl fumarate (DMFU) in footwear materials1 ScopeThis Technical Specification gives a test method for determining the amounts of dimethyl fumarate (DMFU) in footwear materials, desiccant sachets and other commodities. The test method is not applicable to metal parts. The ma
20、terials to which it is applicable are given in ISO/TR 16178:2012, Table 1. NOTE In Europe, DMFU is prohibited in biocidal products as per Directive 98/8/EC. The substance must be used with caution to avoid any health problems in the chemistry laboratory. More recently, EU Commission Decision 2009/25
21、1/EC requires EU member states to ensure that products containing the biocide DMFU are not placed or made available on the market in the European Union. Decision 2009/251/EC establishes a maximum concentration of DMFU in products and parts of products of 0,1 mg/kg.2 Normative referencesThe following
22、 referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.ISO 4787, Laboratory glassware Volumetric instruments Methods f
23、or testing of capacity and for useISO/TR 16178:2012, Footwear Critical substances potentially present in footwear and footwear components3 Principle of methodThe sample is cut into small pieces and extracted with acetone in a sealed vial at a defined temperature in an ultrasonic bath. At this step,
24、two different procedures are proposed, to be used depending on the material being tested:a) the first procedure, without purification and concentration of the extracted solution, can be used for samples giving a simple chromatograph, for example, textiles;b) the second procedure, with purification a
25、nd concentration of the extract, can be used for samples with a complex matrix effect, such as leather.4 Reagents4.1 GeneralThe substances given in Table 1 shall be used at a defined purity grade (at least 99,5 %).TECHNICAL SPECIFICATION ISO/TS 16186:2012(E) ISO 2012 All rights reserved 1PD CEN ISO/
26、TS 16186:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/TS 16186:2012(E)Table 1 ReagentsNo Substances CASanumber1 Dimethyl fumarate 624-49-72 Dimethyl maleate 624-48-63
27、d2-DMFU Dimethyl fumarate 23057-98-94 Acetone 67-64-1aChemical abstract service.4.2 Stock solutions and working solutions4.2.1 Stock solution of internal standard (1 g/l)Weigh 10 mg of d2-DMFU into a 10 ml volumetric flask and fill to the mark with acetone. Transfer the content into an amber 10 ml v
28、ial with PTFE stopcock and keep at 4 C.4.2.2 Acetone working solution with internal standard (1 mg/l)Prepare this solution by means of 1:1 000 dilution of the stock solution of internal standard with acetone.4.2.3 Stock solution (1 g/l)Weigh 50 mg of dimethyl fumarate and 50 mg of dimethyl maleate,
29、with an accuracy of 0,1 mg, in a 50 ml volumetric flask, and fill to the mark with the acetone.4.2.4 Acetone working solution of dimethyl fumarate and dimethyl maleate (1 mg/l)Prepare this solution by means of 1:1 000 dilution of the stock solution with acetone.5 EquipmentThe usual equipment and lab
30、oratory glassware, according to ISO 4787, shall be used, in addition to the following.5.1 Analytical balance, with a precision of at least 0,1 mg.5.2 Glass vial that can be tightly sealed, 40 ml.5.3 Ultrasonic bath with adjustable temperature.5.4 PTFE membrane filter with a pore width of 0,45 m.5.5
31、Sample vials of 1 ml and PTFE-capped.5.6 GC-MS (gas chromatographmass spectroscopy).Other techniques may be used, provided it can be demonstrated that at least the same analytical performance can be obtained.6 SamplingIn the footwear, the upper and the complex lining plus insock shall be tested.The
32、test piece shall consist of a single material (leather, textile or polymer).2 ISO 2012 All rights reservedPD CEN ISO/TS 16186:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-
33、ISO/TS 16186:2012(E)Cut the homogenous textile, leather or polymer samples into pieces of up to 0,5 cm edge length. Desiccant samples may be used without any processing.7 Procedures7.1 Standard procedure7.1.1 ExtractionWeigh 1,000 g of the sample in a 40 ml glass vial (5.2), add 1 ml of the solution
34、 of internal standard (4.2.2) and 9 ml of acetone, and seal the vial. Extract the sample at 60 C for 1 h in an ultrasonic bath. After cooling to room temperature, filter this solution (if necessary) through a PTFE membrane filter (5.4). Transfer an aliquot of the extract to a GC-MS vial and seal wit
35、h a PTFE cap.7.1.2 Calibration solutions of dimethyl fumarate and dimethyl maleatePrepare a working solution (1 g/ml) by 1:1 000 dilution of the stock solution of dimethyl fumarate and dimethyl maleate (4.2.3). From this solution, mixed standards with concentrations of 0,005 g/ml, 0,01 g/ml, 0,05 g/
36、ml and 0,1 g/ml of dimethyl fumarate and dimethyl maleate, and 0,1 g/ml of the internal standard are made.For this purpose, 5 l, 10 l, 50 l and 100 l of the working solution of dimethyl fumarate and dimethyl maleate (4.2.4), and 100 l of the acetone working solution with internal standard (4.2.2) sh
37、all be filled up to 1 000 l with acetone in sample vials.Using this procedure, the concentration corresponding to the maximum regulation level of 0,1 mg/kg is 10 ppb.7.2 Procedure for complex matrix7.2.1 ExtractionWeigh 1,000 g of the sample into a 40 ml glass vial (5.2). Add 100 l of the solution o
38、f internal standard (4.2.2) and 9,9 ml of acetone, and seal the vial. Extract the sample at 60 C for 1 h in an ultrasonic bath.7.2.2 Clean-up stepsTransfer 5 ml of the extract to a conical tube and reduce to around 0,2 ml under a gentle stream of nitrogen.Reconstitute the extract to 1 ml with n-hexa
39、ne.Purify the extract on a Florisil cartridge (2 g/6 ml) by the following procedure.a) Conditioning 6 ml of n-hexane. Add the sample solution to the cartridge.b) Washing 2 ml of n-hexane.2 ml of n-hexane/acetone, of volume fraction 80/20 (V/V)These two fractions are discarded. ISO 2012 All rights re
40、served 3PD CEN ISO/TS 16186:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/TS 16186:2012(E)c) Elution4 ml of n-hexane/acetone 80/20 (V/V)The extract is reduced to 0,5 ml
41、 under a gentle stream of nitrogen, filtered (if necessary) through a PTFE membrane filter and transferred to a GC-MS vial.7.2.3 Calibration solutions of dimethyl fumarate and dimethyl maleateTable 2 indicates the method to be used to prepare the calibration solutions of dimethyl fumarate and dimeth
42、yl maleate.Table 2 Calibration solutions of dimethyl fumarate and dimethyl maleateStandard L1 L2 L3 L4 L5Volume of acetone working solution of dimethyl fumarate and dimethyl maleate (4.2.4)50 l 100 l 150 l 200 l 250 lVolume of acetone working solution of internal standard (4.2.2)100 l 100 l 100 l 10
43、0 l 100 lVolume of acetone (volume of acetone required to make a total of 1 ml)850 l 800 l 750 l 700 l 650 lConcentration of dimethyl fumarate and dimethyl maleate50 g/l 100 g/l 150 g/l 200 g/l 250 g/lConcentration of the internal standard in the corresponding standard100 g/l 100 g/l 100 g/l 100 g/l
44、 100 g/lWith this procedure, the concentration corresponding to the maximum regulation level of 0,1 mg/kg is 100 ppb.8 Determination with GC-MS8.1 Measuring methodValidated testing methods other than the one given in this Technical Specification are permitted provided a comparable precision and dete
45、ction limit (see 8.3 and 8.4) can be reached.Another requirement is sufficient separation of the dimethyl fumarate and dimethyl maleate in order to avoid false positive results by dimethyl maleate.See Annex A for examples.8.2 PrecisionBased on a correlation study with 11 participating laboratories (
46、see Annex B), the whole analysis, including the sample preparation and the determination by GC-MS, has a repeatability (VK) of 10 % at a concentration range between 0,7 and 0,8 mg/kg (desiccant, leather and textiles).8.3 Detection limitThe detection limit should be lower than the legal limit of 0,1
47、mg/kg. It can be lowered by concentration of the sample solution or reduction of the extraction volume.9 Test reportThe test report shall include at least the following:a) reference to this test method and ISO/TS 16186;4 ISO 2012 All rights reservedPD CEN ISO/TS 16186:2012Copyright European Committe
48、e for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/TS 16186:2012(E)b) all details necessary for complete identification of the sample tested;c) procedure used (standard or complex matrix).d) determination of the extracted dimethyl fumarate.e) any deviation by agreement or otherwise from the procedure specified. ISO 2012 All rights reserved 5PD CEN ISO/TS 16186:2012Copyright European Committee for Standardization Provided
