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

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 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 necessary 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 range. 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 (ω).

Mineralölerzeugnisse - Bestimmung des Gehaltes an Benzo(a)pyren (BaP) und ausgewählten polycyclischen Kohlenwasserstoffen (PAH) in Extenderölen - Verfahren mittels doppelter LC-Vorreinigung und GC/MS-Analyse

Diese Europäische Norm legt ein Verfahren zur Bestimmung des Gehaltes an Benzo[a]pyren (BaP) in Extenderölen fest, die in der Gummiindustrie üblicherweise zur Produktion von Reifen oder Reifenteilen benutzt werden. Dieses Verfahren ergibt auch die Summe der acht einzelnen polycyclischen Kohlenwasserstoffe (PAKs), die in der Tabelle 1 enthalten sind.
Dieses Verfahren wurde für die von der Europäischen Kommission [1] geforderten PAKs in Tabelle 1 und die zusätzlichen PAKs in Tabelle A.2 geprüft und verifiziert.
Die Bestimmung anderer PAKs ist grundsätzlich möglich, eine hinreichende Qualitätskontrolle durch den Anwender ist jedoch zur Absicherung der Analyse erforderlich.
Der Anwendungsbereich dieser Methode reicht von 4 mg/kg bis etwa 15 mg/kg für die acht einzelnen PAKs und von 0,5 mg/kg bis etwa 2 mg/kg für BaP.
ANMERKUNG 1   Der beabsichtigte Arbeitsbereich für diese Methode liegt von 0,1 mg/kg bis 15 mg/kg. Für die unteren Ebenen wurde jedoch keine Präzision ermittelt.  
ANMERKUNG 2   Für den Zweck dieser Europäischen Norm wird zur Angabe des Massenanteils einer Substanz () der Ausdruck „% (m/m)“ verwendet.

Produits petroliers - Détermination de la teneur en Benzo(a)pyrene (BaP) et polcyclic hydrocarbons aromatique selective en huiles extender - Méthodes par spectrométrie d'absorption atomique (SAA)

La présente Norme européenne prescrit une méthode de détermination de la teneur en benzo[a]pyrène (BaP)
dans les huiles de dilution couramment utilisées dans l’industrie de l’élastomère pour la production des
pneumatiques ou de parties de pneumatiques. Cette méthode permet aussi de déterminer la teneur totale en
les huit hydrocarbures aromatiques polycycliques (HAP) figurant dans le Tableau 1.
Cette procédure a été testée et vérifiée pour les HAP du Tableau 1 (ceux spécifiés par la Commission
européenne [1]) et du Tableau 2 pour d’autres HAP.
NOTE 1 L’analyse d’autres HAP est en principe possible mais il est nécessaire que l’utilisateur mette en place une
assurance qualité suffisante pour sécuriser l’analyse.
Le domaine d’application pour cette méthode est d’environ 4 mg/kg à environ 15 mg/kg pour les huit HAP
individuels et d’environ 0,5 mg/kg à environ 2 mg/kg pour le BaP.
NOTE 2 Cette méthode peut être appliquée sur des échantillons dont la teneur est de 0,1 mg/kg à 15 mg/kg. Cependant,
pour les faibles teneurs, les valeurs de fidélité n’ont pas encore été établies.
NOTE 3 Pour les besoins du présent document, le terme «% (m/m)» représente la fraction massique (ω).

Naftni proizvodi - Določevanje benzo(a)pirena (BaP) in izbranih policikličnih aromatskih ogljikovodikov (PAO) v polnilnih oljih - Postopek uporabe dvojnega LC-čiščenja in analize GC/MS

Ta evropski standard določa postopek za določevanje benzo(a)pirena (BaP) v polnilnih oljih, ki se pogosto uporabljajo v gumarski industriji za izdelavo pnevmatik ali delov pnevmatik. S to metodo dobimo tudi vsoto osmih posameznih policikličnih aromatskih ogljikovodikov (PAH), ki so navedeni v preglednici 1. Postopek je bil preskušen in preverjen za policiklične aromatske ogljikovodike, ki so navedeni v preglednici 1 (tisti, ki jih zahteva Evropska komisija [1]) in dodatne policiklične aromatske ogljikovodike, ki so navedeni v preglednici A.2. Analiza drugih policikličnih aromatskih ogljikovodikov je načeloma mogoča, vendar mora pri tem uporabnik zagotoviti zadostno kakovost, da zaščiti analizo. Obseg uporabe za to metodo je od približno 4 mg/kg do približno 15 mg/kg za osem posameznih policikličnih aromatskih ogljikovodikov in od približno 0,5 mg/kg do približno 2 mg/kg za benzo(a)piren. OPOMBA 1 Predviden delovni obseg za to metodo je od 0,1 mg/kg do 15 mg/kg. Natančnost postopka za nižje stopnje še ni določena. OPOMBA 2 V tem evropskem standardu je uporabljena oznaka »% (m/m)« in pomeni delež mase (ω).

General Information

Status
Published
Public Enquiry End Date
09-Nov-2010
Publication Date
04-Mar-2013
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
13-Feb-2013
Due Date
20-Apr-2013
Completion Date
05-Mar-2013

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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.ROLFLNOLþQLKMineralölerzeugnisse - Bestimmung des Gehaltes an Benzo(a)pyren (BaP) und ausgewählten polycyclischen Kohlenwasserstoffen (PAH) in Extenderölen - Verfahren mittels doppelter LC-Vorreinigung und GC/MS-AnalyseProduits petroliers - Détermination de la teneur en Benzo(a)pyrene (BaP) et polcyclic hydrocarbons aromatique selective en huiles extender - Méthodes par spectrométrie d'absorption atomique (SAA)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 analysis75.100MazivaLubricants, industrial oils and related productsICS:Ta slovenski standard je istoveten z:EN 16143:2013SIST EN 16143:2013en,de01-april-2013SIST EN 16143:2013SLOVENSKI

STANDARD
SIST EN 16143:2013
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE 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 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: ESIST EN 16143:2013

EN 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 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 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 physical chemical data for PAHs ............................................................. 15 Annex B (informative)

Additional user information ................................................................................... 17 Bibliography................................................................................................................................................ 22

SIST EN 16143:2013

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 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. SIST EN 16143:2013

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 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. SIST EN 16143:2013

EN 16143:2013 (E) 5 1 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 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 necessary 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 range. 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 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 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) 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. SIST EN 16143:2013

EN 16143:2013 (E) 6 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 4 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. 5 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® LH201) 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. SIST EN 16143:2013

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 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 µl, 5 µl, 10 µl, 25 µl, 50 µl, 100 µl and 250 µl. 5.9 Volumetric flasks, capacity 1 ml, 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 or 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 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 2. A commonly used liquid phase is 5 % 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). SIST EN 16143:2013

EN 16143:2013 (E) 8 Table 2 — Typical gas chromatographic parameters Parameter Value GC-column 30 m x 0,25 mm x 0,25 µm

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 °C MS Detector temperature

according to the instrument manufacturer Injection volume 1 µl to 3 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 GC-columns (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 Sample concentrator, typically a rotary evaporator or similar digital evaporator device. 7 Sampling and sample handling 7.1 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 5 ml volumetric flask (5.9) and dissolved in 2 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. SIST EN 16143:2013

EN 16143:2013 (E) 9 8 Clean-up procedure 8.1 General Since the extender oils under investigation have a complex matrix which can hide the PAHs of interest, samples shall be submitted to a clean-up procedure before GC separation (see 6.1). The first cleaning step is done with Silica gel (5.2.1).

For quantification a second cleaning step shall be performed on Sephadex LH20 (5.2.2) or equivalent. These procedures are strongly recommended in order to make sure the samples are cleaned thoroughly before analysing them by GC-MS. 8.2 First clean-u

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