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1、DRAFT FOR DEVELOPMENT DD CEN/TS 14494:2003 Leather Chemical tests Determination of the content of pentachlorophenol in leather ICS 59.140.30 ? Licensed Copy: London South Bank University, London South Bank University, Tue Dec 12 05:27:45 GMT+00:00 2006, Uncontrolled Copy, (c) BSI DD CEN/TS 14494:200
2、3 This Draft for Development was published under the authority of the Standards Policy and Strategy Committee on 10 April 2003 BSI 10 April 2003 ISBN 0 580 41534 1 National foreword This Draft for Development is the English language version of CEN/TS 14494:2003. This publication is not to be regarde
3、d as a British Standard. It is being issued in the Draft for Development series of publications and is of a provisional nature because there is a need for users to establish some experience with the method. It should be applied on this provisional basis, so that information and experience of its pra
4、ctical application may be obtained. Comments arising from the use of this Draft for Development are requested so that UK experience can be reported to the European organization responsible for its conversion to a European standard. A review of this publication will be initiated 2 years after its pub
5、lication by the European organization so that a decision can be taken on its status at the end of its 3-year life. Notification of the start of the review period will be made in an announcement in the appropriate issue of Update Standards. According to the replies received by the end of the review p
6、eriod, the responsible BSI Committee will decide whether to support the conversion into a European standard, to extend the life of the Technical Specification or to withdraw it. Comments should be sent in writing to the Secretary of BSI Technical Committee TCI/69, Leather and footwear, at British St
7、andards House, 389 Chiswick High Road, London W4 4AL, giving the document reference and clause number and proposing, where possible, an appropriate revision of the text. A list of organizations represented on this committee can be obtained on request to its secretary. Cross-references The British St
8、andards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. S
9、ummary of pages This document comprises a front cover, an inside front cover, the CEN/TS title page, pages 2 to 8, an inside back cover and a back cover. The BSI copyright date displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. DateCo
10、mments Licensed Copy: London South Bank University, London South Bank University, Tue Dec 12 05:27:45 GMT+00:00 2006, Uncontrolled Copy, (c) BSI TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN/TS 14494 March 2003 ICS 59.140.30 English version Leather Chemical tests Determ
11、ination of the content of pentachlorophenol in leather This Technical Specification (CEN/TS) was approved by CEN on 27 October 2002 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 t
12、heir 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. It is permissible to keep conflicting national standards in force
13、 (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, Czech Republic, Denmark, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Luxembourg, Malta,
14、Netherlands, Norway, Portugal, Slovakia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels 2003 CENAll rights of exploitation in any form and by an
15、y means reserved worldwide for CEN national Members. Ref. No. CEN/TS 14494:2003 E Licensed Copy: London South Bank University, London South Bank University, Tue Dec 12 05:27:45 GMT+00:00 2006, Uncontrolled Copy, (c) BSI CEN/TS 14494:2003 (E) 2 Contents 1Scope 4 2Normative references . 4 3Principle.
16、4 4Definitions 4 5Apparatus and auxiliary devices. 4 6Chemicals 5 7Sampling and preparation of samples 5 8Procedures. 5 9Expression of results 7 10Test report 7 Annex A (informative) Reliability of the method 8 Licensed Copy: London South Bank University, London South Bank University, Tue Dec 12 05:
17、27:45 GMT+00:00 2006, Uncontrolled Copy, (c) BSI CEN/TS 14494:2003 (E) 3 Foreword This document (CEN/TS 14494:2003) has been prepared by CEN/TC 289, “Leather“ the Secretariat of which is held by UNI. It is based on the English translation of DIN 53313 Draft 1999 and describes a procedure where PCP i
18、s acetylated before the chromatographic detection and the amount of the detected PCP acetate is quantified via an internal standard correction. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to anounce this European Standa
19、rd: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Slovak Republic, Spain, Sweden, Switzerland and the United Kingdom. Annex A is informative. Licensed Copy: London South Bank University
20、, London South Bank University, Tue Dec 12 05:27:45 GMT+00:00 2006, Uncontrolled Copy, (c) BSI CEN/TS 14494:2003 (E) 4 1 Scope This Technical Specification specifies a method for determining the content of pentachlorophenol (PCP), its salts and esters in leather. 2 Normative references This Technica
21、l Specification incorporates by dated or undated reference, provisions from other publications. These normative references are cited at the appropriate places in the text and the publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of these publicatio
22、ns apply to this Technical Specification only when incorporated in it by amendment or revision. For undated references the latest edition of the publication referred to applies (including amendments). EN ISO 3696:1995, Water for analytical laboratory use Specification and test methods (ISO 3696:1987
23、) EN ISO 4044, Leather - Preparation of chemical test samples (ISO 4044:1998) EN ISO 2418, Leather - Chemical, physical and mechanical and fastness tests - Sampling location (ISO 2418:2002) EN ISO 2419, Leather Physical and mechanical tests - Sample preparation and conditioning (ISO 2419:2002) 3 Pri
24、nciple First of all the leather is submitted to steam distillation. After extraction into n-hexane the PCP is acetylated by acetic anhydride and the PCP acetates analysed by gas chromatography with an ECD detector. Quantification is performed by an external standard and correction made with an inter
25、nal standard. 4 Definitions The concentration of pentachlorophenol can consist of free pentachlorophenol, its salts and esters. PCP is detected gas-chromatographically as its derivative, PCP acetate. The PCP content is given in mg/kg sample. 5 Apparatus and auxiliary devices 5.1Gas chromatograph wit
26、h ECD or MSD 5.2Analytical balance weighting to an accuracy of 0,1 mg 5.3Suitable apparatus designed for steam distillation 5.4Shaking machine 5.5Volumetric flasks 500 ml, 50 ml 5.6Erlenmeyer flask 100 ml 5.7Separating funnel 250 ml 5.8Pasteur-pipette, graduated pipette, suitable autopipette License
27、d Copy: London South Bank University, London South Bank University, Tue Dec 12 05:27:45 GMT+00:00 2006, Uncontrolled Copy, (c) BSI CEN/TS 14494:2003 (E) 5 6 Chemicals Unless otherwise specified, analytical grade chemicals should be used. Water must be distilled or deionised, Grade 3 in accordance wi
28、th EN ISO 3696:1995. 6.1 Stock solutions 6.1.1 Pentachlorophenol, 100 g/ml in acetone 6.1.2 PCP acetate 10 g/ml in n-hexane 6.1.3 PCP acetate Standard 0,04 mg/l PCP acetate (corresponds to 0,0346 mg PCP/l) in n-hexane 6.1.4 Tetrachloroguajacol TCG (Tetrachloromethoxyphenol) 100 g/ml in acetone, mark
29、er and internal standard, melting point 118 C - 119 C 6.2 Sulphuric acid, 1M 6.3 n-hexane for residue analysis 6.4 Potassium carbonate, K2CO3 6.5 Acetic anhydride, C4H6O3 6.6 Molecular sieve 10-20 mesh beads, pore diameter 0,3 nm. Or anhydrous sodium sulphate 6.7 Distilled water in accordance with G
30、rade 3 of EN ISO 3696:1995. 6.8 Triethylamine 6.9 Acetone 7 Sampling and preparation of samples If possible sample in accordance with EN ISO 2418 and grind leather in accordance with EN ISO 4044. If sampling in accordance with EN ISO 2418 is not possible (e.g. leathers from finished products like sh
31、oes, garments) details about sampling have to be given in the test report. Condition the ground test sample in accordance with EN ISO 2419 prior to weighing. 8 Procedures 8.1 Steam-distillation Approximately 1,0 g of the leather sample is weighed accurately into the distillation vessel (5.3) and 20
32、ml 1M sulphuric acid (6.2) and 0,1 ml TCG stock-solution (6.1.4) are added. The content of the vessel is submitted to a steam distillation by using a suitable steam distillation apparatus. A 500 ml volumetric flask (5.5) with 5 g K2CO3 (6.4) is used as a receiver. About 450 ml are distilled. Make up
33、 to volume with water. In the case of extreme foaming the heat source should be reduced. Licensed Copy: London South Bank University, London South Bank University, Tue Dec 12 05:27:45 GMT+00:00 2006, Uncontrolled Copy, (c) BSI CEN/TS 14494:2003 (E) 6 8.2 Liquid-Liquid Extraction and acetylation 100
34、ml of the distillate obtained in 8.1 is transferred into a 250 ml separating funnel (5.7). 20 ml n-hexane (6.3) and 1,5 ml acetic anhydride (6.5) and 0,5 ml triethylamine (6.8) are added to the solution and shaken for 30 minutes vigorously on a mechanical shaker (see NOTE). After phase separation th
35、e organic layer is transferred to a 100 ml conical flask (5.6) and the aqueous layer is shaken again with 20 ml n-hexane. The combined n-hexane extracts are dehydrated, with either molecular sieves or anhydrous sodium sulphate (6.6) in a 100 ml conical flask (5.6) for about 10 min. Afterwards the n-
36、hexane extract is decanted quantitatively under washing with n-hexane into a 50 ml volumetric flask (5.5). It is made up to volume with n-hexane. This solution is analysed by GC (5.1). NOTEThe derivatisation step is a two-phase-reaction and depends very strongly on the intensity of shaking. Use a su
37、itable mechanical shaker with a high shaking frequency. Do not try to shake by hand because this will produce incorrect results. 8.3 Preparation of calibration mixture for acetylated PCP and TCG 8.3.1 Derivatisation of PCP and TCG Standard for recovery rate To calculate the recovery, a PCP / TCG sta
38、ndard mixture is prepared like the sample. Therefore 100 l of stock-solution (6.1.1) and 100 l TCG (6.1.4) is measured into the distillation vessel together with 20 ml sulphuric acid (6.2). This solution is treated in the same way as the sample. NOTEThe recovery rate shall be higher than 90 %. 8.3.2
39、 PCP acetate Standard (External standard) In addition a PCP acetate Standard (6.1.3) is analysed directly by gas-chromatography. The final concentration for the GC is 0,04 mg/l PCP acetate. This standard is included in the calculation. 8.3.3 Derivatisation of TCG-Standard 20 l of the TCG-solution (6
40、.1.4) are acetylated in 30 ml of 0,1 M/l K2CO3 in the same way as the sample and the organic layer is transferred into a 50 ml volumetric flask (5.5). A TCG-Standard is analysed in the same way as the sample. 8.4 Capillary Gas Chromatography (GC) The described chromatographic conditions are only exa
41、mples. Capillary column:fused quartz, (medium polarity ) e.g. 95 % dimethyl-5 % diphenylpolysiloxane, length 50 m, inner diameter: 0,32 mm, film thickness: 0,25 m Detector/detector temperature:ECD / 280 C Injection system:split / splitless 60 seconds Injection volume: 2 l Licensed Copy: London South
42、 Bank University, London South Bank University, Tue Dec 12 05:27:45 GMT+00:00 2006, Uncontrolled Copy, (c) BSI CEN/TS 14494:2003 (E) 7 Injector temperature:250 C Carrier gas:Helium Make up gas:Argon (95 %) / Methane (5 %) Temperature Programme:80 C (1 min) 6 C/min 280 C (10 min) ? Expression of resu
43、lts The areas of the single peaks will be compared with the areas of the standard which are analysed at the same time and calculated. The PCP concentration is calculated as a mass portion M in mg/kg leather sample according to the following equation: EA FVCA M PCPSt TCGPCPStPCP PCP = SampleA ncalibr
44、atioA F TCG TCG TCG = A= Peak area C= Concentration PCP-Standard g/ml (6.1.3) (0,04 mg PCP acetate is equivalent to 0,0346 mg free PCP) E= Weight of sample in g V= final sample volume in ml = Dilution rate F= Factor internal Standard (TCG) Indices: PCPSt= Pentachlorophenol Standard TCG:Internal Stan
45、dard 10 Test report The test report shall include the following: a) reference to this Technical Specification; b) type, origin and designation of the analysed leather sample and the sampling method used; c) the analytical result for PCP content in mg/kg rounded to one decimal place; d) any deviation
46、s from the analytical procedure; e) date of the test. Licensed Copy: London South Bank University, London South Bank University, Tue Dec 12 05:27:45 GMT+00:00 2006, Uncontrolled Copy, (c) BSI CEN/TS 14494:2003 (E) 8 Annex A (informative) Reliability of the method Quantification limit of PCP: 0,1 mg/
47、kg Recovery of PCP: 96 - 107 %(0,09 ppm - 3 ppm) Recovery of PCP-Acetate-Standard: 80 % The quantification of Tri- and Tetrachlorophenol is possible. The method has been tested in an interlaboratory trial with 3 different leathers. (A, B and C). LeatherMean in mg/kgSr in mg/kgr in mg/kgsR in mg/kgR
48、in mg/kg A6.70.21.20.72.3 B16.80.21.44.45.8 C5.00.10.90.31.5 Sr= Standard deviation of repeatability r=repeatability SR=Standard deviation of reproducibility R=reproducibility Licensed Copy: London South Bank University, London South Bank University, Tue Dec 12 05:27:45 GMT+00:00 2006, Uncontrolled
49、Copy, (c) BSI Licensed Copy: London South Bank University, London South Bank University, Tue Dec 12 05:27:45 GMT+00:00 2006, Uncontrolled Copy, (c) BSI DD CEN/TS 14494:2003 BSI 389 Chiswick High Road London W4 4AL BSI British Standards Institution BSI is the independent national body responsible for preparing British Standards. It presents the UK view on standards in Europe and at the international level. It is incorporated by Royal Charter. Revisions British Standards ar