BS EN 16143:2013 BS 2000-605:2013 BSI Standards Publication Petroleum products — Determination of content of Benzo(a)pyrene (BaP) and selected polycyclic aromatic hydrocarbons (PAH) in extender oils — Procedure using double LC cleaning and GC/MS analysis BS EN 16143:2013 BRITISH STANDARD National foreword This British Standard is the UK implementation of EN 16143:2013 The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum Testing and Terminology A list of organizations represented on this committee can be obtained on request to its secretary Energy Institute, under the brand of IP, publishes and sells all Parts of BS 2000, and all BS EN petroleum test methods that would be Part of BS 2000, both in its annual publication “Standard methods for analysis and testing of petroleum and related products and British Standard 2000 Parts” and individually Further information is available from: Energy Institute, 61 New Cavendish Street, London W1G 7AR Tel: 020 7467 7100 Fax: 020 7255 1472 This publication does 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 2013 ISBN 978 580 71783 ICS 75.100 Compliance with a British Standard cannot confer immunity from legal obligations This British Standard was published under the authority of the Standards Policy and Strategy Committee on 28 February 2013 Amendments issued since publication Date Text affected BS EN 16143:2013 EN 16143 EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM February 2013 ICS 75.100 English Version Petroleum products - Determination of content of Benzo(a)pyrene (BaP) and selected polycyclic aromatic hydrocarbons (PAH) in extender oils - Procedure using double LC cleaning and GC/MS analysis Produits petroliers - Détermination de la teneur en Benzo(a)pyrène (BaP) et en certains hydrocarbures aromatiques polycycliques (HAP) dans les huiles de dilution - Méthode par double purification chromatographique en phase liquide et par GC/MS Mineralölerzeugnisse - Bestimmung des Gehaltes an Benzo(a)pyren (BaP) und ausgewählten polycyclischen Kohlenwasserstoffen (PAKs) in Extenderölen - Verfahren mittels doppelter LC-Vorreinigung und GC/MS-Analyse This European Standard was approved by CEN on 14 December 2012 CEN members 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 to 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 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, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom EUROPEAN COMMITTEE FOR STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR 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 EN 16143:2013: E BS EN 16143:2013 EN 16143:2013 (E) Contents Page Foreword .3 Introduction Scope Normative references .5 Terms and definitions Principle Reagents and materials 6 Apparatus 7 7.1 7.2 Sampling and sample handling General sampling procedure Preparation of a sample solution 8 8.1 8.2 8.3 Clean-up procedure General .9 First clean-up step using silica column Second clean-up step using Sephadex-LH 20 column 9 9.1 9.2 9.3 9.4 9.5 Test procedure 10 General practices for quality assurance 10 Calibration 10 Analysis 12 Identification 12 Calculation of results 12 10 Expression of results 13 11 11.1 11.2 11.3 Precision 13 General 13 Repeatability, r 14 Reproducibility, R 14 12 Test report 14 Annex A (normative) Relevant physical chemical data for PAHs 15 Annex B (informative) Additional user information 17 Bibliography 22 BS EN 16143:2013 EN 16143:2013 (E) Foreword This document (EN 16143:2013) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, 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 withdrawn 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 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, 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 Kingdom BS EN 16143:2013 EN 16143:2013 (E) 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 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 be detected qualitatively and quantitatively using benzo[a]pyrene (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-laboratory 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 as 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 limits 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 laboratories 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 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 BS EN 16143:2013 EN 16143:2013 (E) Scope This European Standard specifies a procedure for the determination of the content of benzo[a]pyrene (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) listed in Table The procedure has been tested and verified for the PAHs listed in Table (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 necessary to secure the analysis The application range for this method is from approximately mg/kg to approximately 15 mg/kg for the eight individual PAHs and from approximately 0,5 mg/kg to approximately mg/kg for BaP NOTE The intended working range for this method is in the 0,1 mg/kg to 15 mg/kg range For the lower levels precision has not yet been established NOTE For the purposes of this European Standard, the term “% (m/m)” is used to represent the mass fraction (ω) Table — List of individual PAHs in extender oils Name of PAH Abbreviation CAS Registry number benzo(a)pyrene BaP 50-32-8 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 DBahA 53-70-3 dibenzo(a,h)anthracene See Table A.1 for additional data on some PAH Normative references The 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 (including any amendments) applies EN ISO 3170, Petroleum liquids — Manual sampling (ISO 3170) EN ISO 3171, Petroleum liquids — Automatic pipeline sampling (ISO 3171) Terms and definitions For the purposes of this document, the following terms and definitions apply BS EN 16143:2013 EN 16143:2013 (E) 3.1 polycyclic aromatic hydrocarbons PAHs 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 Principle The product under investigation is submitted to a double cleaning step using column 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 Reagents and materials 5.1 Solvents 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 5.1.2 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, of high purity grade, for example TYPE ICN 02747 5.2.2 Sephadex® LH20 1) 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 listed 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 standard 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 by CEN of the product named Equivalent products may be used if they can be shown to lead to the same results BS EN 16143:2013 EN 16143:2013 (E) 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 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: µl, µl, 10 µl, 25 µl, 50 µl, 100 µl and 250 µl 5.9 Volumetric flasks, capacity ml, ml and 100 ml 5.10 Conical bottom flasks, capacity 10 ml 5.11 Pipettes, class A, capacity ml 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 or split analysis on capillary column and shall allow operation using the chromatography parameters given in Table 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 procedure (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 A commonly used liquid phase is % phenyl-methylpolysiloxane of 0,25 µm film thickness Other columns of comparable or improved performance can also be used, such as a strongly recommended DB-5ms column (5 % phenyl-methylpolysiloxane) BS EN 16143:2013 EN 16143:2013 (E) Table — Typical gas chromatographic parameters Parameter Value GC-column 30 m x 0,25 mm x 0,25 µm Stationary phase % phenyl-methylpolysiloxane Oven initial temperature 60 °C Initial time Temperature program °C/min to 300 °C, hold for 12 Injection according to Grob, splitless Injection temperature 275 °C to 300 °C Temperature transfer line 275 °C to 300 °C MS Detector temperature according to the instrument manufacturer Injection volume µl to µl Carrier gas Helium, with a linear velocity of 40 cm/sec Depending on chromatographic conditions (e.g column length), it can happen that the different benzofluoranthene isomers co-elute In these cases, determining the sum of the three isomers rather than reporting each isomer separately should be considered Another alternative would be to use longer GCcolumns (60 m instead of 30 m) See B.2 for further advice on the peak overlap of the isomers Ferrules used shall not contain more than 40 % graphite (a suitable ferrule is made of 60 % polyimide and 40 % graphite) to decrease the risk that PAHs are absorbed 6.3 7.1 Sample concentrator, typically a rotary evaporator or similar digital evaporator device Sampling and sample handling General sampling procedure Samples shall be taken according to EN ISO 3170 or EN ISO 3171, as well as in accordance with the requirements of national standards or regulations for the sampling of the product under test If samples are not tested immediately, they shall be stored tightly sealed and in a cool and dark place It shall be secured that glassware is thoroughly cleaned and that all new materials that may come into contact with the sample are checked by blank analysis that they give no interference NOTE Interferences which can affect the results can occur due to contaminations from glassware, solvents and other materials that can come into contact with the sample Such interferences will form an artefact or will increase the detector baseline Interferences can also come from components in samples that co-elute with the specific PAHs of interest 7.2 Preparation of a sample solution Approximately 70 mg of the sample is introduced to the nearest 0,1 mg into a ml volumetric flask (5.9) and dissolved in ml n-pentane (5.1.3) Before the sample clean-up, the sample solution is spiked with internal standard The concentration of internal standard shall be adjusted such that it is in the same range as the expected PAHs in the sample BS EN 16143:2013 EN 16143:2013 (E) The quota, Qr, between the Qualifier-Ion and the Target-Ion in percentage is calculated according to Formula (2): Qr = 100 × ( AQ / AT ) (2) where AQ is the area of the Qualifier-Ion; AT is the area of the Target-Ion NOTE The relationships between the Qualifier-Ion and the Target-Ion can be found in an MS-reference library They can however vary depending on the type of MS used (Quadrupole versus Ion trap) The relative response factor (RRFi) for any PAH i is calculated according to Formula (3): RRFi = ( Ai / Aj ) × (W j / Wi ) (3) where Ai is the area of the Target –Ion of the PAH i in the calibration standard; Aj is the area of the Target –Ion of the internal standard j in the calibration standard; Wi is the mass of the PAH i in the calibration standard in ng; Wj is the mass of the internal standard j in the calibration standard in ng If the RRFi over the whole working area persistently has < 20 relative standard deviation (rsd), this may be used as “invariant”, and the mean value may be used for the quantitative calculations The RRFi shall be checked daily through analysis of one or several calibration standards If the daily check shows that the actual RRFi differ by more than ± 20 percent relative from the expected RRFi a completly new calibration shall be performed 9.3 Analysis After the GC system and the MS-detector are correctly adjusted, the calibration standards are analysed; from them the performance of the instrument is calculated µl to µl of sample is injected and the MS response is checked at least every tenth sample by injecting a calibration standard and a blank sample The blank sample shall also ensure that the analytical system does no longer contain rest concentrations of PAHs 9.4 Identification A correct identification of a PAHs is based on: the RRTi being within a retention time of 0,15 % of that calculated from the calibration, and the qualifier/target ratio not differing by more than 30 % from the value obtained during calibration 9.5 Calculation of results The qualitative calculation of PAHs is based on the areas of the PAH Target-Ion and the area of the Internal standard The concentrationω i is calculated according to Formula (4): 12 BS EN 16143:2013 EN 16143:2013 (E) ωi = W js Ais × × 10 A js RRFis × W ts (4) where ωi is the concentration of the PAH i in the sample in mg/kg; Ais is the area of the Target –Ion of the PAH i in sample extract; Ajs is the area of the Target –Ion of the internal standard j in the sample extract; Wts is the total sample mass (see 7.2) in mg; Wjs is the mass of the internal standard j related to in the sample solution (7.2), in mg; RRFis is the relative response factor for the PAH i relative to a chosen internal standard j If the area of the Target-Ion for any of the PAHs is outside the calibration range, the sample solution shall be diluted with cyclohexane without adding additional Injection standard The recovery (sample cleaning losses) for the internal standard is calculated relative to the Injection standards using Formula (5): R j = (100 / W j ) × ( Ajs / Ass ) × (Ws / RRFs ) (5) where Rj is the recovery of the internal standard(s) in %; Ajs is the area of the Target –Ion of the internal standard j in the Sample extract; Ass is the area of the Target-Ion for the Injection standard s in the sample extract; Wj is the mass of the internal standard j added to the sample in mg; Ws is the mass of the Injection standards added to the sample in mg; RRFs is the relative response factor for the internal standard j, calculated from the Injection standards The recovery of the internal standard shall be between 50 % and 150 % Test portions which not meet this condition shall be discarded 10 Expression of results Report the sum of PAHs (ω) in mg/kg, rounded to the nearest 0,1 mg/kg Report the contents for individual PAH compounds (ωi) in mg/kg, rounded to the nearest 0,1 mg/kg 11 Precision 11.1 General Precision data for each analyte have been developed in CEN/TC 19 interlaboratory studies according to EN ISO 4259 [4] 13 BS EN 16143:2013 EN 16143:2013 (E) 11.2 Repeatability, r The difference between two test results, obtained by the same operator using the same apparatus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the values calculated from the following formula only in one case in twenty For benzo[a]pyrene (BaP): r = 0,311 X + 0,013 (6) For the sum of the eight individual PAHs: r = 0,070 X + 0,584 (7) where X represents the mean of the two results being compared expressed in mg/kg 11.3 Reproducibility, R The difference between two single and independent test results, obtained by different operators working in different laboratories on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the values calculated from the following formula only in one case in twenty For benzo[a]pyrene (BaP): R = 0,427 X + 0,129 (8) For the sum of the eight individual PAHs: R = 0,169 X + 1,228 (9) where X represents the mean of the two results being compared expressed in mg/kg 12 Test report The test report shall contain the following information: a) a reference to this European Standard, i.e EN 16143; b) the type and complete identification of the product tested; c) the used method of sampling (see Clause 7); d) the result of the test (see Clause 10), or if the repeatability has been checked, the final quoted result obtained; e) all operating details not specified in this European Standard, or regarded as optional, together with details of any incidents which may have influenced the test result(s); f) 14 the date of the test BS EN 16143:2013 EN 16143:2013 (E) Annex A (normative) Relevant physical chemical data for PAHs Table A.1 present the internal standards needed for the procedure as described in this European Standard Table A.2 present the information on the PAHs used for the assessment of the procedure and precision as described in this European Standard Table A.1 — List of internal standards Name Ring system Internal standard Injection standard benzo[a]anthracene 3+ benzo[a]anthracene-d12 Decafluorobiphenyl chrysene 3+ benzo[a]anthracene-d12 Decafluorobiphenyl fluoranthene 3+ benzo[a]anthracene-d12 Decafluorobiphenyl pyrene 3+ benzo[a]anthracene-d12 Decafluorobiphenyl benzo[k]fluoranthene 4+ benzo[b]fluoranthene-d12 Decafluorobiphenyl benzo[b]fluoranthene 4+ benzo[b]fluoranthene-d12 Decafluorobiphenyl benzo[j]fluoranthene 4+ benzo[b]fluoranthene-d12 Decafluorobiphenyl benzo[a]pyrene benzo[a]pyrene-d12 Decafluorobiphenyl benzo[e]pyrene benzo[a]pyrene-d12 Decafluorobiphenyl dibenzo[a,h]anthracene benzo[a]pyrene-d12 Decafluorobiphenyl indeno[1,2,3-cd]pyrene 5+ benzo[a]pyrene-d12 Decafluorobiphenyl benzo[ghi]perylene 5+ benzo[a]pyrene-d12 Decafluorobiphenyl 15 BS EN 16143:2013 EN 16143:2013 (E) Table A.2 — Additional physical data for selected PAH Formula Molecular mass (g/mol) Melting point range (°C) Boiling point range (°C) Vapour pressure at 25 °C, (kPa) Fluoranthene C16H10 202,26 107-111 375-393 6,5 * 10-7 Pyrene C16H10 202,26 150-156 360-404 3,1 * 10-6 benzo[a]anthracene C18H12 228,30 157-167 435 1,5 * 10-8 Chrysene C18H12 228,30 252-256 441-448 5,7 * 10-10 benzo[b]fluoranthene C20H12 252,32 167-168 481 6,7 * 10-8 benzo[k]fluoranthene C20H12 252,32 198-217 481 2,1 * 10-8 benzo[j]fluoranthene C20H12 252,32 198-217 481 7,0 * 10-8 benzo[a]pyrene C20H12 252,32 177-179 493-496 7,3 * 10-10 benzo[e]pyrene C20H12 252,32 178-179 193 7,4 * 10-10 indeno[1,2,3-cd]pyrene C22H12 276,34 275-278 525 1,3 * 10-11 dibenzo[a,h]anthracene C22H12 276,34 162-163 - approx 10-11 benzo[ghi]perylene C22H14 278,35 266-270 524 1,3 * 10-11 Name 16 BS EN 16143:2013 EN 16143:2013 (E) Annex B (informative) Additional user information B.1 Chromatograms In order to assist the user of this document, examples of standard and more complicated chromatograms are shown in Figures B.1, B.2 and B.3 (time on the X-axis and abundance on the Y-axis) Table B.1 presents the peak identification as shown in the chromatograms Figure B.1 —Chromatogram of a PAHs standards mixture 17 BS EN 16143:2013 EN 16143:2013 (E) Figure B.2 —Chromatogram of an RAE sample after both clean-up steps (Silica and Sephadex LH-20) Figure B.3 —Chromatogram of an MES sample after both clean-up steps (Silica and Sephadex LH-20) 18 BS EN 16143:2013 EN 16143:2013 (E) Table B.1 — Compound identification in example chromatograms Peak No Peak No Compound Compound Benzo[a]anthracene-d12 Benzo[b]fluoranthene Benzo[a]anthracene Benzo[k]fluoranthene Cyclopenta[cd]pyrene Benzo[j]fluoranthene Triphenylene 10 Benzo[e]pyrene Chrysene 11 Benzo[a]pyrene-d12 Benzo[b]fluoranthene-d12 12 Benzo[a]pyrene 13 Dibenzo[ah]anthracene B.2 Potential peak-overlap B.2.1 Overlap of benzofluoranthene isomers Benzo(b)fluoranthene, benzo(k)fluoranthene and benzo(j)fluoranthene can co-elute as shown in Figure B.4 when chromatographic conditions are not optimal See 6.2 for possible improvements for better resolution of these peaks Figure B.4 — Peak overlap B.2.2 Overlap between chrysene and triphenylene Chrysene and triphenylene can co-elute depending on the chromatographic column used If complete peak separation is needed, the following column types should be used: • Restek – Rxi-17 Sil-Ms, or • DB-EUPAH, or 19 BS EN 16143:2013 EN 16143:2013 (E) • Agilent Select PAH GC columns It is important to note that the naming of these columns does not constitute a formal recommendation, as other columns from other manufacturers showing the same performance may also be used In any case, if the separation is not performed properly, the concentration of chrysene would be overestimated, but it would not directly influence the precision of the method, since the response factors for chrysene and triphenylene are similar B.3 Improved choice of internal standard Because of the risks for peak-overlap described above, it is strongly recommended to replace the original chrysene-d12 with benzo[a]anthracene-d12 as internal standard for 3+ ring systems In addition, it is also recommended to use benzo[b]fluoranthene-d12 instead of perylene-d12 as internal standard for 4+ ring systems B.4 Preparation of PAHs standard solutions for GC-MS calibration For GC-MS stock solutions, the following examples may be used a) b) c) Deuterated stock solution, of the following nature: 1) PI-1: 10 mg of each deuterated compound in mL Toluene (some PAHs are only partially soluble in cyclohexane (e.g chrysene); for improving their solubility, it is recommended to add some mL of toluene to stock solution) (2 000 mg/L), 2) PI-2: 1,25 mL PI-1 in 25 mL cyclohexane (100 mg/L), or 3) PI-3: mL PI-2 in 25 mL cyclohexane (20 mg/L) Stock solution recovery 4,4´,5,5´,6,6´-Decafluorobiphenyl (DF), of the following nature: 1) DF-1: 10 mg DF in 50 mL cyclohexane (200 mg/L), or 2) DF-2: 2,5 mL DF-1 in 25 mL cyclohexane (20 mg/L) PAHs Standard solution, of the following types: 1) PAH-1: mg each PAH in 50 mL de cyclohexane (100 mg/L), or 2) PAH-2: 500 µL PAH-1 in 25 mL cyclohexane (10 mg/L) This results in the following examples of PAHs solutions for GC-MS calibration: P1: 0,01 mg/L PAH, 0,4 mg/L PAH deuterated and 0,4 mg/L DF P2: 0,025 mg/L PAH, 0,4 mg/L PAH deuterated and 0,4 mg/L DF P3: 0,10 mg/L PAH and 0,4 mg/L PAH deuterated and 0,4 mg/L DF P4: 0,25 mg/L PAH and 0,4 mg/L PAH deuterated and 0,4 mg/L DF P5: 0,50 mg/L PAH and 0,4 mg/L PAH deuterated and 0,4 mg/L DF 20 BS EN 16143:2013 EN 16143:2013 (E) P6: 1,00 mg/L PAH and 0,4 mg/L PAH deuterated and 0,4 mg/L DF Table B.2 gives an example of how to combine the three stock solutions to obtain the required concentrations for the PAHs solutions P1 – P6 Table B.2 — Preparation of PAHs solutions from Stock solutions for calibration PAHs Solution P1 P2 P3 P4 P5 P6 Solution A: PAH-2 10 µl 25 µl 100 µl 250 µl 500 µl 1000 µl Solution B: PI-3 200 µl 200 µl 200 µl 200 µl 200 µl 200 µl Solution C: DF-2 200 µl 200 µl 200 µl 200 µl 200 µl 200 µl 21 BS EN 16143:2013 EN 16143:2013 (E) Bibliography [1] M/413 standardisation mandate addressed to CEN for methods of analysis to detect polycyclic aromatic hydrocarbons (PAH) in extender oils, 25 June 2007 [2] Directive 2005/69/EC on the approximation of the laws, regulations and administrative provisions of the Member States relating to restrictions on the marketing and use of certain dangerous substances and preparations (polycyclic aromatic hydrocarbons in extender oils and tyres), 16 November 2005 [3] Directive 67/548/EEC on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances, 27 June 1967 [4] EN ISO 4259, Petroleum products — Determination and application of precision data in relation to methods of test (ISO 4259) 22 This page deliberately left blank BS 2000 Series Energy Institute Buying Parts of BS 2000 Orders for BS 2000 publications should be addressed to either: Energy Institute – Library and Information Service 61 New Cavendish Street London W1G 7AR Tel: +44 (0)20 7467 7100 Fax: +44 (0)20 7255 1472 www.energyinst.org.uk Order standards securely via: www.energyinstpubs.org.uk or: British Standards Institution – Customer Services 389 Chiswick High Road London W4 4AL Tel: +44 (0)20 8996 9001 Fax: +44 (0)20 8996 7001 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