DIN EN 16143-2013 Petroleum products - Determination of content of Benzo(a)pyrene (BaP) and selected polycyclic aromatic hydrocarbons (PAH) in extender oils - Procedure using doubl.pdf

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1、May 2013 Translation by DIN-Sprachendienst.English price group 12No 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 75

2、.100!%$/Q“2011246www.din.deDDIN EN 16143Petroleum products Determination of content of Benzo(a)pyrene (BaP) and selectedpolycyclic aromatic hydrocarbons (PAH) in extender oils Procedure using double LC cleaning and GC/MS analysis;English version EN 16143:2013,English translation of DIN EN 16143:2013

3、-05Minerallerzeugnisse Bestimmung des Gehaltes an Benzo(a)pyren (BaP) und ausgewhlten polycyclischenKohlenwasserstoffen (PAKs) in Extenderlen Verfahren mittels doppelter LC-Vorreinigung und GC/MS-Analyse;Englische Fassung EN 16143:2013,Englische bersetzung von DIN EN 16143:2013-05Produits petroliers

4、 Dtermination de la teneur en Benzo(a)pyrene (BaP) et en certains hydrocarburesaromatiques polycycliques (HAP) dans les huiles de dilution Mthode par double purification chromatographique en phase liquide et par GC/MS;Version anglaise EN 16143:2013,Traduction anglaise de DIN EN 16143:2013-05www.beut

5、h.deDocument comprises 24 pagesIn case of doubt, the German-language original shall be considered authoritative.04.13DIN EN 16143:2013-05 2 A comma is used as the decimal marker. National foreword This document (EN 16143:2013) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fu

6、els, lubricants and related products of petroleum, synthetic and biological origin” (Secretariat: NEN, Netherlands). The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee NA 062-06-14 AA Chromatograph

7、ische Analyse of the Fachausschuss Minerall- und Brennstoffnormung (FAM). EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16143 February 2013 ICS 75.100 English Version Petroleum products - Determination of content of Benzo(a)pyrene (BaP) and selected polycyclic aromatic hydrocarbons (PAH) in e

8、xtender oils - Procedure using double LC cleaning and GC/MS analysis Produits petroliers - Dtermination de la teneur en Benzo(a)pyrne (BaP) et en certains hydrocarbures aromatiques polycycliques (HAP) dans les huiles de dilution - Mthode par double purification chromatographique en phase liquide et

9、par GC/MS Minerallerzeugnisse - Bestimmung des Gehaltes an Benzo(a)pyren (BaP) und ausgewhlten polycyclischen Kohlenwasserstoffen (PAKs) in Extenderlen - Verfahren mittels doppelter LC-Vorreinigung und GC/MS-Analyse This European Standard was approved by CEN on 14 December 2012. CEN members are boun

10、d 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 to the CE

11、N-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 Centre h

12、as 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, Lithuania, L

13、uxembourg, Malta, Netherlands, Norway, Poland, Portugal, 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 2013

14、CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16143:2013: EEN 16143:2013 (E) 2 Contents Page Foreword . 3 Introduction 4 1 Scope 5 2 Normative references . 5 3 Terms and definitions 5 4 Principle 6 5 Reagents and materials . 6 6

15、Apparatus . 7 7 Sampling and sample handling . 8 7.1 General sampling procedure . 8 7.2 Preparation of a sample solution 8 8 Clean-up procedure . 9 8.1 General . 9 8.2 First clean-up step using silica column 9 8.3 Second clean-up step using Sephadex-LH 20 column . 9 9 Test procedure . 10 9.1 General

16、 practices for quality assurance . 10 9.2 Calibration 10 9.3 Analysis 12 9.4 Identification . 12 9.5 Calculation of results . 12 10 Expression of results . 13 11 Precision . 13 11.1 General . 13 11.2 Repeatability, r . 14 11.3 Reproducibility, R. 14 12 Test report 14 Annex A (normative) Relevant phy

17、sical chemical data for PAHs . 15 Annex B (informative) Additional user information . 17 Bibliography 22 DIN EN 16143:2013-05 EN 16143:2013 (E) 3 Foreword This document (EN 16143:2013) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of pe

18、troleum, synthetic and biological origin”, the secretariat of which is held by NEN. 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 August 2013, and conflicting national standards shall be withdra

19、wn at the latest by August 2013. 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 all such patent rights. This document has been prepared under a mandate given

20、 to CEN by the European Commission and the European Free Trade Association. According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, D

21、enmark, 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 Kingdom. DIN EN 1614

22、3:2013-05 EN 16143:2013 (E) 4 Introduction This document has been prepared under a mandate given to CEN by the European Commission (EC) 1 and the European Free Trade Association (EFTA). EU Directive 2005/69/EC 2 sets restrictions on the marketing and use of polycyclic aromatic hydrocarbons (PAHs) in

23、 extender oils and tyres. Tyres are produced using extender oils that may contain PAHs not added intentionally. Due to the fact that PAHs can be incorporated during the production process into the rubber matrix, they can be present in various amounts in the final products. The presence of PAHs can b

24、e detected qualitatively and quantitatively using benzoapyrene (BaP) as marker. BaP and PAHs are dangerous substances classified according to the Directive 67/548/EEC 3 as carcinogenic, mutagenic and toxic for reproduction. Precision data for each analyte have been developed in CEN/TC 19 inter-labor

25、atory studies according to EN ISO 4259 4. These studies recognised the difficulties of this type of very complex trace analysis, which are not only due to the fact that suitable samples are very rare and almost impossible to find. Insufficient purity for some charges of the used internal standards a

26、s reported by some participating laboratories, as well as an overlap of triphenylene and Chrysene peaks on some systems, were matters that led to a test method standard being produced with less precision than was desirable. Although the “2R“ rule for limit setting for BaP is not fully met for the li

27、mits targeted by the EU Directive, the results (in terms of reproducibility) from the CEN/TC 19 Round Robin Test are much better than those resulting from comparable exercises with alternate methods. The complexity of the sample preparation steps and subsequent GC-MS analysis showed that laboratorie

28、s need sufficient expertise to properly perform the analyses described in this document. Therefore, only a limited number of laboratories were able to participate in and contribute to the Round Robin test conducted by CEN/TC 19. In consideration of the progression of the standardization project, no

29、additional time or resources were left e.g. to conduct additional Round Robin Tests, and the test method therefore is produced in its actual form. Further experience in the future may lead to improved precision and a more comprehensive scope. DIN EN 16143:2013-05 EN 16143:2013 (E) 5 1 Scope This Eur

30、opean Standard specifies a procedure for the determination of the content of benzoapyrene (BaP) in extender oils which are commonly used in the rubber industry for the production of tyres or parts of tyres. The method also yields the sum of the eight individual polycyclic aromatic hydrocarbons (PAHs

31、) listed in Table 1. The procedure has been tested and verified for the PAHs listed in Table 1 (those required by the European Commission 1) and additional PAHs as listed in Table A.2. Analysis of other PAHs is possible in principle, but sufficient quality assurance performed by the user is necessar

32、y to secure the analysis. The application range for this method is from approximately 4 mg/kg to approximately 15 mg/kg for the eight individual PAHs and from approximately 0,5 mg/kg to approximately 2 mg/kg for BaP. NOTE 1 The intended working range for this method is in the 0,1 mg/kg to 15 mg/kg r

33、ange. For the lower levels precision has not yet been established. NOTE 2 For the purposes of this European Standard, the term “% (m/m)” is used to represent the mass fraction (). Table 1 List of individual PAHs in extender oils Name of PAH Abbreviation CAS Registry number benzo(a)pyrene BaP 50-32-8

34、 benzo(e)pyrene BeP 192-97-2 benzo(a)anthracene BaA 56-55-3 chrysene CHR 218-01-9 benzo(b)fluoranthene BbFA 205-99-2 benzo(j)fluoranthene BjFA 205-82-3 benzo(k)fluoranthene BkFA 207-08-9 dibenzo(a,h)anthracene DBahA 53-70-3 See Table A.1 for additional data on some PAH. 2 Normative references The fo

35、llowing 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 (including any amendments) applies. EN ISO 3170,

36、Petroleum liquids Manual sampling (ISO 3170) EN ISO 3171, Petroleum liquids Automatic pipeline sampling (ISO 3171) 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. DIN EN 16143:2013-05 EN 16143:2013 (E) 6 3.1 polycyclic aromatic hydrocarbons PAHs

37、hydrocarbon molecules that consist of three or more condensed aromatic rings 3.2 extender oil specific oil fraction which is used in the rubber industry for the production of rubber parts, especially tyres 4 Principle The product under investigation is submitted to a double cleaning step using colum

38、n chromatography (LC). The polycyclic aromatic hydrocarbons and components of interest (see Clause 1) are separated by gas chromatography (GC). Identification and quantification is performed by mass spectroscopic (MS) detection in Selected Ion Monitoring (SIM) mode. 5 Reagents and materials 5.1 Solv

39、ents. In this context, the requirement “free from PAH“ means that in the analysis of a blank sample, no peaks from the PAH compounds of interest larger than the signal-to noise-ratio of the chromatogram should be found. 5.1.1 Acetone, free from PAH, for chromatography, CAS Registry number 67-64-1. 5

40、.1.2 Cyclohexane, free from PAH, for chromatography, CAS Registry number 110-82-7. 5.1.3 n-Pentane, free from PAH, for chromatography, CAS Registry number 109-66-0. 5.1.4 Propanol-2, free from PAH, for chromatography, CAS Registry number 67-63-0. 5.2 LC separation phase materials. 5.2.1 Silica gel,

41、of high purity grade, for example TYPE ICN 02747. 5.2.2 SephadexLH201)of high purity grade. 5.3 Standards. The standards shall be chosen so that they behave in the same way as the corresponding analytes and that they can be readily quantified. Suitable compounds that can be used as standards are lis

42、ted in Table A.1. 5.3.1. Internal standards, deuterated or C13 marked PAH, with 98% purity (see also Table A.1). 5.3.2 Injection standards, 4,4,5,5,6,6-Decafluorobiphenyl or deuterated/C13 marked PAH, typically blended at 50x10-3g/l concentration. 5.3.3 Master standard, a commercially available stan

43、dard solution containing certified concentrations of the PAHs of interest. 1) Sephadex is the trade name of a product supplied by GE Healthcare Bio-Sciences AB, SE-751 84 Uppsala. This information is given for the convenience of users of this European Standard and does not constitute an endorsement

44、by CEN of the product named. Equivalent products may be used if they can be shown to lead to the same results. DIN EN 16143:2013-05 EN 16143:2013 (E) 7 5.4 Carrier gas, Helium 99,996 purity. 5.5 UV-light source, with radiation predominantly at 366 nm. 5.6 Pasteur pipette. 5.7 LC Chromatography glass

45、 column, consisting of: 5.7.1 Column a: ID 10mm, length 160 mm. 5.7.2 Column b: ID 23mm, length 100 mm. 5.8 Syringes, for injection, blending of solutions and internal standards syringes with the following capacities: 1 l, 5 l, 10 l, 25 l, 50 l, 100 l and 250 l. 5.9 Volumetric flasks, capacity 1 ml,

46、 5 ml and 100 ml. 5.10 Conical bottom flasks, capacity 10 ml. 5.11 Pipettes, class A, capacity 2 ml. 6 Apparatus 6.1 Gas chromatograph with mass spectrometer. The analysis system consists of a commercial GC system connected with an MS detector and data station. The system shall be used with direct o

47、r split analysis on capillary column and shall allow operation using the chromatography parameters given in Table 2. NOTE The mass-spectrometer is run in the “Selected Ion” (SIM) mode under 70 eV ionisation. When a high resolution type mass spectrometer is used, the second step of the cleaning proce

48、dure (see 8.3) can be by-passed if the desired detection limits can be met. 6.2 Gas chromatographic columns. Fused silica type capillary columns with dimensions are listed in Table 2. A commonly used liquid phase is 5 % phenyl-methylpolysiloxane of 0,25 m film thickness. Other columns of comparable

49、or improved performance can also be used, such as a strongly recommended DB-5ms column (5 % phenyl-methylpolysiloxane). DIN EN 16143:2013-05 EN 16143:2013 (E) 8 Table 2 Typical gas chromatographic parameters Parameter Value GC-column 30 m x 0,25 mm x 0,25 m Stationary phase 5 % phenyl-methylpolysiloxane Oven initial temperature 60 C Initial time 2 min Temperature program 5 C/min to 300 C, hold for 12 min Injection according to Grob, splitless Injection temperature 275 C to 300 C Temperature transfer line 275 C to 300