DIN EN ISO 18219-2016 Leather - Determination of chlorinated hydrocarbons in leather - Chromatographic method for short-chain chlorinated paraffins (SCCP) (ISO 18219 2015) German v.pdf

1、February 2016 English price group 8No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 59.140.30!%LL2“2414115www.din.de

2、DIN EN ISO 18219Leather Determination of chlorinated hydrocarbons in leather Chromatographic method for short-chain chlorinated paraffins (SCCP)(ISO18219:2015);English version EN ISO 18219:2015,English translation of DIN EN ISO 18219:2016-02Leder Bestimmung von chlorierten Kohlenwasserstoffen in Led

3、er Chromatographisches Verfahren fr kurzkettige Chlorparaffine (SCCP) (ISO 18219:2015);Englische Fassung EN ISO 18219:2015,Englische bersetzung von DIN EN ISO 18219:2016-02Cuir Dosage des hydrocarbures chlors dans le cuir Mthode chromatographique pour les paraffines chlores chane courte (PCCC) (ISO

4、18219:2015);Version anglaise EN ISO 18219:2015,Traduction anglaise de DIN EN ISO 18219:2016-02www.beuth.deDocument comprises 12 pagesDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.02.16 DIN EN ISO 18219:2016-02 2 A comma is used as

5、 the decimal marker. National foreword This document (EN ISO 18219:2015) has been prepared by Technical Committee ISO/TC “International Union of Leather Technologists and Chemists Societies (IULTCS)” in collaboration with the Technical Committee CEN/TC 289 “Leather” (Secretariat: UNI, Italy). The re

6、sponsible German body involved in its preparation was DIN-Normenausschuss Materialprfung (DIN Standards Committee Materials Testing), Working Committee NA 062-05-52 AA Chemische Prfverfahren fr Leder. The DIN Standards corresponding to the International Standards referred to in this document are as

7、follows: ISO 2418 DIN EN ISO 2418 ISO 4044 DIN EN ISO 4044 National Annex NA (informative) Bibliography DIN EN ISO 2418, Leather Chemical, physical and mechanical and fastness tests Sampling location DIN EN ISO 4044, Leather Chemical tests Preparation of chemical test samples EUROPEAN STANDARD NORME

8、 EUROPENNE EUROPISCHE NORM EN ISO 18219 October 2015 ICS 59.140.30 English Version Leather - Determination of chlorinated hydrocarbons in leather - Chromatographic method for short-chain chlorinated paraffins (SCCP) (ISO 18219:2015) Cuir - Dosage des hydrocarbures chlors dans le cuir - Mthode chroma

9、tographique pour les paraffines chlores chane courte (PCCC) (ISO 18219:2015) Leder - Bestimmung von chlorierten Kohlenwasserstoffen in Leder - Chromatographische Verfahren fr kurzkettige Chlorparaffine (SCCP) (ISO 18219:2015) This European Standard was approved by CEN on 29 August 2015. CEN members

10、are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application t

11、o the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management

12、Centre has the same status as the official versions. CEN members 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, Lith

13、uania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-

14、1000 Brussels 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 18219:2015 EContents Page Foreword .4Introduction . 51 Scope . 66666662 Normative references 63 Principle 4 Apparatus and materials5 Chemicals .6 Sampling 7 Sam

15、ple preparation and analysis 7.1 Preparation of SCCP calibration solution (50 g/ml) with 59 % chlorination degree . 77.2 Extraction of leather . 77.3 Clean up . 87.4 GC-MS Determination . 88 Evaluation 89 Test report .9Annex A (informative) Chromatographic analysis operating parameters .10DIN EN ISO

16、 18219:2016-02 EN ISO 18219:2015 (E) 2uropean Foreword . 3E666777European foreword This document (EN ISO 18219:2015) has been prepared by Technical Committee IULTCS “International Union of Leather Technologists and Chemists Societies“ in collaboration with the Technical Committee CEN/TC 289 “Leather

17、” the secretariat of which is held by UNI. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by April 2016, and conflicting national standards shall be withdrawn at the latest by April 2016. Attention

18、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 national standards organizations of the f

19、ollowing countries are bound to implement this European Standard: 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, Netherland

20、s, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Endorsement notice The text of ISO 18219:2015 has been approved by CEN as EN ISO 18219:2015 without any modification. DIN EN ISO 18219:2016-02 EN ISO 18219:2015 (E) 3 ForewordISO (the

21、 International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member 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 committe

22、e 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 of electrotechni

23、cal standardization.The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in

24、 accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).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 such patent rights. D

25、etails of any patent rights identified during the development of 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 information given for the convenience of users and does not constitute an

26、 endorsement.For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary informationISO 18219 was p

27、repared by the Chemical Test Commission of the International Union of Leather Technologists and Chemists Societies (IUC Commission, IULTCS) in collaboration with the European Committee for Standardisation (CEN) Technical Committee CEN/TC 289, Leather, the secretariat of which is held by UNI, in acco

28、rdance with the agreement on technical co-operation between ISO and CEN (Vienna Agreement).IULTCS, originally formed in 1897, is a world-wide organization of professional leather societies to further the advancement of leather science and technology. IULTCS has three Commissions, which are responsib

29、le for establishing international methods for the sampling and testing of leather. ISO recognizes IULTCS as an international standardizing body for the preparation of test methods for leather.DIN EN ISO 18219:2016-02 EN ISO 18219:2015 (E) 4 IntroductionShort-chain chlorinated paraffins (SCCP) are cl

30、assified as dangerous to the environment, since they are very toxic to aquatic organisms and may cause long-term adverse effects in the aquatic environment.In 2002, the European Directive 2002/45/EC restricted the sale and use of short-chain chlorinated paraffins (C10-C13) in product preparations fo

31、r the fatliquoring of leather. Preparations containing concentrations equal or higher than 1 % of SCCP were forbidden. This Directive is included as part of the EU Regulation 1907/2006 (REACH). Within this EU Regulation, in October 2008, the short-chain chlorinated paraffins were added to the Candid

32、ate List of Substances of Very High Concern (SVHC).DIN EN ISO 18219:2016-02 EN ISO 18219:2015 (E) 5 1 ScopeThis International Standard specifies a chromatographic method to determine the amount of short-chain chlorinated paraffins (SCCP) C10-C13in processed and unprocessed leathers.Annex A is for in

33、formation only.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 (inclu

34、ding any amendments) applies.ISO 2418, Leather Chemical, physical and mechanical and fastness tests Sampling locationISO 4044, Leather Chemical tests Preparation of chemical test samples3 PrincipleThe test sample is extracted using n-hexane at 60 C in an ultrasonic bath for 60 min. After SPE clean u

35、p, an aliquot is then analysed using a gas chromatograph fitted to a mass selective detector with chemical ionization (GC-ECNI-MS).Liquid chromatography system with single quad (LC-MS) or triple quad mass spectrometry (LC-MS/MS) can also be used if the user has demonstrated that the accuracy of meas

36、urement is equivalent to that of the GC-ECNI-MS method.4 Apparatus and materialsNormal laboratory apparatus and, in particular, the following.4.1 Analytical balance.4.2 Sealable vessel, with lid, 20 ml, suitable for extraction with n-hexane.4.3 Ultrasonic bath, (temperature controlled).4.4 Pipette,

37、1 ml to 10 ml capacity.4.5 Volumetric flask, 2 ml.4.6 Solid phase extraction (SPE) system, with vacuum device and normal phase SPE cartridges, for example 500 mg/6 ml, e.g. Chromabond columns, Sorbent: SiOH, 6 ml, 500 mg.4.7 PTFE membrane filter.DIN EN ISO 18219:2016-02 EN ISO 18219:2015 (E) 6 4.8 G

38、as chromatograph and mass selective detector with chemical ionization (GC-ECNI-MS).5 ChemicalsIf not otherwise defined, analytical reagent grade chemicals shall be used.5.1 n-hexane, CAS1)No.: 110-54-3.5.2 Dichloromethane, CAS No: 75-09-2.5.3 Internal standard solution, 1,1,1,3,10,11-hexachloroundec

39、ane, CAS No: 601523-28-8, 1 000 g/ml.NOTE Other suitable internal standard can be used.5.4 Standard solutions, SCCP, C10-C13,with different chlorine content, each 100 g/ml:5.4.1 SCCP C10-C1355,5 % Cl, technical grade.5.4.2 SCCP C10-C1363 % Cl, technical grade.NOTE These SCCP calibration solutions ar

40、e available commercially.5.5 Nitrogen gas.6 SamplingThe sampling shall be made according to ISO 2418. If a sampling according to ISO 2418 is not possible (e.g. in case of leather from finished products like shoes, clothing, etc.), the details of the sampling must be stated in the test report. Glue r

41、esiduals must be mechanically removed from leather samples.The leather samples shall be ground or cut into smaller pieces, not larger than 2 mm to 3 mm, according to ISO 4044.7 Sample preparation and analysis7.1 Preparation of SCCP calibration solution (50 g/ml) with 59 % chlorination degree533 l of

42、 SCCP C10-C1355,5 % Cl standard solution (5.4.1) and 467 l SCCP C10-C1363 % Cl standard solution (5.4.2) are transferred into a 2 ml volumetric flask (4.5). 20 l of internal standard solution (5.3) is added and the flask filled up to the volume with n-hexane (5.1).The calibration standard with 59 %

43、chlorine content shall be used for the quantification of all samples, independent of their chlorination degree (if known).7.2 Extraction of leather0,5 g 0,001 g test leather sample is weighed with the analytical balance (4.1) into the sealable vessel (4.2). 9,9 ml n-hexane (5.1) and 100 l internal s

44、tandard (5.3) are added and the vessel sealed and extracted at 60 C in an ultrasonic bath (4.3) for 60 min 2 min.1) Chemical Abstracts Service.DIN EN ISO 18219:2016-02 EN ISO 18219:2015 (E) 7 7.3 Clean upThe SPE cartridges (4.6) are pre-treated with 2 ml n-hexane (5.1) per 100 mg sorbent. The cartri

45、dges shall not be dried during or after the pre-treating. The extraction solution (7.2) is decanted through the cartridges and the eluate is collected in a new vessel. The cartridge is flushed into the vessel with 5 ml of a 50:50 (v/v) mixture from n-hexane (5.1) and dichloromethane (5.2). This solu

46、tion is reduced to 1,0 ml under a gentle stream of nitrogen, filtered through a PTFE membrane filter (4.7) and transferred to a GC-MS vial.7.4 GC-MS DeterminationThe solution is analysed using GC-ECNI-MS (4.8). An example of a suitable GC-ECNI-MS method is given in Annex A.8 EvaluationPeak areas fro

47、m the four quantification masses of the standard are summed up and equated with standard concentration. Peak areas of the samples are summed up too and the concentration is calculated with response of the standard.To check the linearity of the analytical system, a calibration standard as reference s

48、tandard is analysed after each tenth sample and at the end of the sequence. The deviation in reference to the calibration standard should be within 20 %, otherwise the analytical system has to be checked before retrying the analysis.Sample extract should always be diluted in the concentration range of the standard.The integration of the samples has only