1、BSI Standards PublicationPD CEN ISO/TS 16189:2013Footwear Critical substancespotentially present in footwearand footwear components Test method to quantitativelydetermine dimethylformamidein footwear materials (ISO/TS16189:2013)PD CEN ISO/TS 16189:2013 PUBLISHED DOCUMENTNational forewordThis Publish
2、ed Document is the UK implementation of CEN ISO/TS 16189:2013.The UK participation in its preparation was entrusted to Technical Committee TCI/69, Footwear, leather and coated fabrics.A list of organizations represented on this committee can be obtained on request to its secretary.This publication d
3、oes not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2013. Published by BSI Standards Limited 2013ISBN 978 0 580 81935 3 ICS 61.060 Compliance with a British Standard cannot confer immunity from le
4、gal obligations.This Published Document was published under the authority of the Standards Policy and Strategy Committee on 31 August 2013.Amendments issued since publicationDate Text affectedTECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN ISO/TS 16189 July 2013 ICS 61.06
5、0 English Version Footwear - Critical substances potentially present in footwear and footwear components - Test method to quantitatively determine dimethylformamide in footwear materials (ISO/TS 16189:2013) Chaussures - Substances critiques potentiellement prsentes dans la chaussure et les composant
6、s de chaussure - Mthodes dessai pour dterminer quantitativement le dimthylformamide dans les matriaux de chaussure (ISO/TS 16189:2013) Schuhe - Mglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische Substanzen - Prfverfahren zur quantitativen Bestimmung von Dimethylformamid in Schuhwer
7、kstoffen (ISO/TS 16189:2013) 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 requested to submit their comments, particularly o
8、n 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. It is permissible to keep conflicting nation
9、al 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, Denmark, Estonia, Finland, Former Yugoslav Repub
10、lic 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 COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMAL
11、ISATION 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 16189:2013: EPD CEN ISO/TS 16189:2013CEN ISO/TS 16189:2013 (E) 3 Foreword This
12、 document (CEN ISO/TS 16189:2013) has 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 su
13、bject 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 national standards organizations of the following countries are bound to announce this Technical Specification: Austria, Belg
14、ium, 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, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switze
15、rland, Turkey and the United Kingdom. Endorsement notice The text of ISO/TS 16189:2013 has been approved by CEN as CEN ISO/TS 16189:2013 without any modification. PD CEN ISO/TS 16189:2013ISO/TS 16189:2013(E) ISO 2013 All rights reserved iiiContents PageForeword iv1 Scope . 12 Normative references 13
16、 Method principle 14 Reagents and solvents . 14.1 Reagents 14.2 Stock solutions 15 Equipment . 26 Preparation of sample 26.1 Sampling . 26.2 Extraction 27 Determination with GC-MS 37.1 Calibration standard 37.2 Examples of instrumental method . 38 Quantification 38.1 Calibration curve . 39 Performan
17、ce of the method 410 Test report . 4Annex A (informative) Suggested parameters for GC-MS determination of DMFo . 5Bibliography 6PD CEN ISO/TS 16189:2013ISO/TS 16189:2013(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO mem
18、ber 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, governmen
19、tal 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 of electrotechnical standardization.International Standards are drafted in accordance with the rules given in the ISO/IEC Direct
20、ives, Part 2.The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies
21、 casting a vote.In other circumstances, particularly when there is an urgent market requirement for such documents, a technical committee may decide to publish other types of normative document: an ISO Publicly Available Specification (ISO/PAS) represents an agreement between technical experts in an
22、 ISO working group and is accepted for publication if it is approved by more than 50 % of the members of the parent committee casting a vote; an ISO Technical Specification (ISO/TS) represents an agreement between the members of a technical committee and is accepted for publication if it is approved
23、 by 2/3 of the members of the committee casting a vote.An ISO/PAS or ISO/TS is reviewed after three years in order to decide whether it will be confirmed for a further three years, revised to become an International Standard, or withdrawn. If the ISO/PAS or ISO/TS is confirmed, it is reviewed again
24、after a further three years, at which time it must either be transformed into an International Standard or be withdrawn.Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all s
25、uch patent rights.ISO/TS 16189 was prepared by the European Committee for Standardization (CEN) Technical Committee CEN/TC 309, Footwear, in collaboration with ISO Technical Committee ISO/TC 216, Footwear, in accordance with the agreement on technical cooperation between ISO and CEN (Vienna Agreemen
26、t).iv ISO 2013 All rights reservedPD CEN ISO/TS 16189:2013TECHNICAL SPECIFICATION ISO/TS 16189:2013(E)Footwear Critical substances potentially present in footwear and footwear components Test method to quantitatively determine dimethylformamide in footwear materials1 ScopeThis Technical Specificatio
27、n specifies a method to determine the amounts of dimethylformamide (DMFo) in footwear and footwear components containing polyurethane (PU) coated material.NOTE In the footwear industry, when PU is injected (reaction moulded), this process does not require the use of DMFo. DFMo can be used for PU coa
28、ted material.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 edition of the referenced document (includi
29、ng any amendments) applies.ISO/TR 16178:2012, Footwear Critical substances potentially present in footwear and footwear components3 Method principleThe sample is cut into small pieces and extracted with methanol in a sealed vial at 70 C in an ultrasonic bath. An aliquot of the extract is analysed wi
30、th GC-MS in SIM mode.ISO/TR 16178:2012, Table 1 defines which materials are concerned by this determination.4 Reagents and solvents4.1 ReagentsThe substances are given in Table 1.Table 1 ReagentsNumber Substances CAS Number aPurity1 Dimethylformamide (DMFo) 68-12-2 Certificated standard2 Dimethylfor
31、mamide-d7 (DMFo-d7) 4472-41-7 Certificated standard3 Methanol 67-56-1 Analytical gradeaCAS: Chemical Abstract Service.4.2 Stock solutions4.2.1 Internal standard Stock solution (1 000 mg/l)10 mg of DMFo-d7 is weighted with an accuracy of 0,1 mg in a 10 ml volumetric flask and filled up to the mark wi
32、th methanol. The content is further transferred in an amber 10 ml vial with PTFE stopcock and keep at 4 C. ISO 2013 All rights reserved 1PD CEN ISO/TS 16189:2013ISO/TS 16189:2013(E)4.2.2 Internal standard Working solution (200 mg/l)The solution is prepared by 1:5 dilution of the stock solution (4.2.
33、1) with methanol.4.2.3 Target compound Stock solution (1 000 mg/l)10 mg of DMFo is weighed with an accuracy of 0,1 mg in in a 10 ml volumetric flask and filled up to the mark with methanol. The content is further transferred in an amber 10 ml vial with PTFE stopcock and keep at 4 C.4.2.4 Target comp
34、ound Working solution (200 mg/l)The solution is prepared by 1:5 dilution of the stock solution (4.2.3) with methanol.5 EquipmentUsual laboratory equipment, in addition to the following.5.1 Analytical balance (precision at least 0,1 mg).5.2 Glass vial which can be tightly sealed, 20 ml.5.3 Ultrasonic
35、 bath with adjustable temperature.5.4 PTFE-membrane filter pore width 0,45 m.5.5 2 ml sample vials with PTFE-capped.5.6 Volumetric flask, 10ml.5.7 Amber vessels.5.8 Micropipettes, 20 l to 10 ml.5.9 Gas chromatograph with mass selective detector (GC-MS).6 Preparation of sample6.1 SamplingSamples of P
36、U coated materials are cut into pieces up to 3 mm edge length.A maximum of three PU coated materials (equal in mass) can be mixed together.6.2 ExtractionA test sample of 1 g 0,001 g is weighed (ms) with the analytical balance (5.1) in a 20 ml glass vial (5.2). Then 9 ml of methanol and 1 ml of the i
37、nternal standard working solution (4.2.2) are added and the vial is sealed.The sample is extracted at 70 C for 1 h in an ultrasonic bath.After cooling to room temperature the solution is filtered (if necessary) through a PTFE membrane filter (5.4). An aliquot of the extract is transferred to a GC-MS
38、 vial and sealed with a PTFE-cap (5.5).2 ISO 2013 All rights reservedPD CEN ISO/TS 16189:2013ISO/TS 16189:2013(E)7 Determination with GC-MS7.1 Calibration standardSix calibration points are used to establish the calibration curve. They are all prepared in 10 ml volumetric flasks, as given in Table 2
39、.Table 2 Preparation of calibrationStandard L1 L2 L3 L4 L5 L6Volume of target compound working solution (4.2.4)25 l 50 l 100 l 250 l 500 l 1 000 lConcentration of target compound in the cali-bration solutions (mg/l)0,5 1 2 5 10 20Volume of the methanol working solution of internal standard (4.2.2)1
40、000 l 1 000 l 1 000 l 1 000 l 1 000 l 1 000 lConcentration of the internal standard (mg/l) 20 20 20 20 20 20NOTE Filled to the mark with methanol.7.2 Examples of instrumental methodAn example is given in Annex A.8 Quantification8.1 Calibration curveSet up the linear regression function by using the
41、ratio (Ae/Ais) and (Ce/Cis) with the help of the formula:AAaCCbeiseis=+ whereAeis the area of the peak of dimethylformamide;Aisis the area of the peak of dimethylformamide-D7;Ceis the concentration of dimethylformamide in the calibration standard in milligrams per litre (mg/l);Cisis the concentratio
42、n of dimethylformamide-D7 in the calibration standard in milligrams per litre (mg/l);a is the slope of the linear function;b is the ordinate intercept of the calibration curve (the units depend on the evaluation). ISO 2013 All rights reserved 3PD CEN ISO/TS 16189:2013ISO/TS 16189:2013(E)The content
43、of DMFo is calculated according to the following equation as a mass fraction w in mg/kg:WVmAAbaC=( ) echisiswhereW is the content of the dimethylformamide in the specimen (mg/kg);V is the volume of the solvent used for the extraction (ml) (in most cases this value will be equal to 10 ml);m is the ma
44、ss of the tested specimen (g);Aechis the area of the peak of dimethylformamide in the sample;Aisis the area of the peak of dimethylformamide-D7 in the sample;Cisis the concentration of dimethylformamide-D7 in the sample in milligrams per litre (mg/l);a is the slope of the linear function;b is the or
45、dinate intercept of the calibration curve (the units depend on the evaluation).9 Performance of the methodThis quantification limit of this test method is 5 mg/kg of DMFo in PU coated materials.10 Test reportThe test report shall include at least the following:a) reference to this test method;b) dat
46、e of the test;c) all details necessary for complete identification of the sample tested;d) condition of storage before the test, if available;e) the amount determined of the extracted dimethylformamide in mg/kg;f) any deviation from the present standard.4 ISO 2013 All rights reservedPD CEN ISO/TS 16
47、189:2013ISO/TS 16189:2013(E)Annex A (informative) Suggested parameters for GC-MS determination of DMFoA.1 Measuring methodA.1.1 Measuring parameterThe DMFo is analysed by gas chromatography/mass spectrometry on a single quad/MS use in a simultaneous SIM/SCAN mode.A.1.2 Chromatographic conditionsColu
48、mn:Polar stationary phase based on Polyethylene GlycolLength: 30 mInternal diameter: 250 mFilm thickness: 0,5 mCarrier gas: HeliumOven:60 C for 2 min250 C at 20 C/min250 C for 2 minInjector: 240 C in splitless mode with an injection volume of 1 l.A.1.3 Detection conditionsTransfer line: 240 CThe sin
49、gle quad MS work in simultaneous SIM/SCAN mode.The mass SCAN range is between 40 amu and 200 amu.The SIM mode focus on the following ions:Compounds IonsDMFo73 (quantifier)44 (qualifier)DMFo-d7 80 (quantifier) ISO 2013 All rights reserved 5PD CEN ISO/TS 16189:2013ISO/TS 16189:2013(E)Bibliography1 ISO 3696, Water for analytical laboratory use Specification and test methods2 ISO 4787, Laboratory glassware Volumetric instruments Methods for testing of capacity an
