CEN TR 15522-2-2012 Oil spill identification - Waterborne petroleum and petroleum products - Part 2 Analytical methodology and interpretation of results based on GC-FID and GC-MS l.pdf

1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationPD CEN/TR 15522-2:2012Oil spill identification Waterborne petroleum andpetroleum productsPart 2: Analytical methodology andinterpretation of results based on GC-FIDand GC-MS low

2、resolution analysesPD CEN/TR 15522-2:2012 PUBLISHED DOCUMENTNational forewordThis Published Document is the UK implementation of CEN/TR15522-2:2012. It supersedes PD CEN/TR 15522-2:2006 which iswithdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee PTI/12, Petroleum Me

3、asurement and Sampling.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2012. Pu

4、blished by BSI StandardsLimited 2012ISBN 978 0 580 78751 5ICS 75.080Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document was published under the authority of theStandards Policy and Strategy Committee on 31 October 2012.Amendments issued since publi

5、cationDate Text affectedPD CEN/TR 15522-2:2012TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 15522-2 October 2012 ICS 75.080 Supersedes CEN/TR 15522-2:2006English Version Oil spill identification - Waterborne petroleum and petroleum products - Part 2: Analytical methodology and interp

6、retation of results based on GC-FID and GC-MS low resolution analyses This Technical Report was approved by CEN on 13 August 2012. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Mace

7、donia, 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 COMIT EUROPEN DE NORMALISATION EUR

8、OPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TR 15522-2:2012: EPD CEN/TR 15522-2:2012CEN/TR 15522-2:2012 (E) 2 Contents Page Foreword 6Introd

9、uction .71 Scope 92 Normative references 93 Terms, definitions and abbreviated terms 93.1 General 93.2 Sample comparison 103.3 Conclusions 113.4 Abbreviated terms 114 Strategy for the identification of oil spills sources . 124.1 Introduction . 124.2 Basis for reliable conclusions Numerical compariso

10、ns 124.3 Overview of the procedure 134.3.1 Sampling and sample preparation 134.3.2 GC-FID and GC-MS analysis 144.3.3 Conclusions and reporting 145 Sample preparation 165.1 General . 165.2 Visual examination and description of samples . 165.3 Preparation 165.3.1 General . 165.3.2 Water samples . 165.

11、3.3 Oil samples from an Ethylene tetrafluoroethylene (ETFE) net 175.3.4 Thick oil and emulsified oil samples 175.3.5 Tar balls and emulsified lumps . 175.3.6 Samples from oiled birds, fish and other animals and vegetation 175.4 Sample clean-up . 185.4.1 General . 185.4.2 Biogenic materials 185.4.3 B

12、lack oil/HFO (removing of asphaltenes and/or soot particles) 185.5 Recommended injection concentration . 186 Characterisation and evaluation of analytical data . 196.1 General . 196.2 Characterisation by GC-FID Level 1 206.2.1 General . 206.2.2 Evaluation of the influence of weathering on sample com

13、parison . 216.2.3 Acyclic isoprenoids ratios . 226.2.4 Level 1 Conclusions . 226.3 Characterisation by GC-MS Level 2 . 226.3.1 General . 226.3.2 Visual inspection and overall characterisation - Level 2.1 . 236.3.3 Treatment of the GC-MS results Level 2.2 236.4 Treatment of the results using the MS-P

14、W-plot Level 2.2 236.4.1 General . 236.4.2 PW-plot calculations 246.4.3 Evaluation of the variability of the analysis and peak integration 246.4.4 Evaluation of weathering . 266.4.5 Evaluation of mixing . 29PD CEN/TR 15522-2:2012CEN/TR 15522-2:2012 (E) 3 6.5 Treatment of the results using ratios Lev

15、el 2.2 . 316.5.1 General . 316.5.2 Diagnostic ratios calculation . 326.5.3 Normative diagnostic ratios . 326.5.4 Analytical error 356.5.5 Match-criterion for ratios 356.5.6 Criteria for selecting, elimination and evaluating diagnostic ratios 366.5.7 Optional: Evaluation of diagnostic ratios using co

16、nventional or multivariate statistics 396.6 Conclusions . 40Annex A (normative) GC-FID analysis 43A.1 General . 43A.2 Analytical standards for GC-FID analyses 43A.2.1 N-alkanes 43A.2.2 Injection concentration of the standard GC-FID 43A.2.3 Storage of standard solutions 44A.3 Suggested instrumental c

17、onditions 44A.4 Measures to improve and verify the accuracy of the method GC-FID 44A.4.1 Mass discrimination 44A.4.2 Column resolution . 45A.4.3 Calibration range . 46A.4.4 Mid-level concentration 46A.4.5 Variance 47A.5 Sample analysis with GC-FID . 47Annex B (normative) GC-MS analysis 48B.1 General

18、 . 48B.2 Analytical standards for GC-MS analyses 48B.2.1 General . 48B.2.2 SINTEF oil mixture . 49B.2.3 Analytical standards for PAH homologues 49B.2.4 Storage of standard solutions 49B.3 Suggested instrumental conditions 49B.3.1 GC conditions for the exchange of analytical results. 49B.3.2 MS condi

19、tions for full-scan analysis . 52B.3.3 MS preparation for selected ion monitoring (SIM) analysis 52B.4 Measures to improve and verify the accuracy of the GC-MS method . 53B.4.1 Relative retention time 53B.4.2 Mass discrimination 53B.4.3 Peak symmetry and column resolution 53B.4.4 Patterns 54B.4.5 Ca

20、libration range . 54B.4.6 Mid-level concentration 54B.4.7 Variance 54B.5 Sample analysis with GC-MS . 54Annex C (informative) List of PAHs and biomarkers analysed by GC-MS-SIM 55Annex D (informative) Alkyl homologue patterns of PAHs 57Annex E (informative) Diagnostic ratios . 65E.1 Diagnostic ratios

21、 of PAHs 65E.2 Diagnostic ratios of biomarkers 69Annex F (informative) General composition of oils chemical groups 76F.1 Introduction 76F.2 Hydrocarbons 76F.3 Paraffins . 76F.4 Naphthenes 77F.5 Aromatics . 77F.6 Heteroatomic organic compounds 77F.7 Resins . 77PD CEN/TR 15522-2:2012CEN/TR 15522-2:201

22、2 (E) 4 F.8 Asphaltenes . 77Annex G (informative) Weathering of oils spilled on water . 79G.1 Introduction . 79G.2 Evaporation . 80G.3 Dissolution 82G.4 Re-distribution of chemical composition . 83G.5 Biodegradation 86G.6 Photooxidation 86G.7 Contamination . 88Annex H (informative) Characteristic Fe

23、atures of Different Oil Types in Oil Spill Identification . 89H.1 Introduction . 89H.2 Light fuel oil (gas oil, diesel, fuel No 2) 89H.2.1 General . 89H.2.2 Analysis, GC screening 90H.2.3 MS analysis (alternative parameters) . 92H.2.4 Addition of biodiesel 94H.3 Lubricating oil . 95H.3.1 General . 9

24、5H.3.2 Analysis . 95H.4 Heavy fuel oil (HFO, Bunker C, Fuel No 6) . 99H.4.1 General . 99H.4.2 Analysis . 99H.5 Waste oil (bilge oil, sludge, slops) 107H.5.1 General . 107H.5.2 Analysis . 108H.6 Crude oil 113H.6.1 General . 113H.6.2 Analysis . 113H.7 Conclusion 118Annex I (informative) Example of int

25、ernal documentation technical report of an oil spill case . 120I.1 General . 120I.2 Sample information 120I.2.1 General . 120I.2.2 Contact information 120I.2.3 Request 120I.2.4 Photo(s) of the samples . 121I.3 Sample preparation and analyses. 121I.4 Quality assurance . 124I.5 GC-FID results . 125I.6

26、 GC-MS results . 128I.6.1 General . 128I.6.2 Comparison of the surface water samples. . 129I.6.3 Comparison of the spill samples with bilge Sample 6. . 130I.7 Conclusions 131I.7.1 Surface water Sample 1 with bilge Sample 6. 131I.7.2 Surface water Sample 2 with bilge Sample 6. 132I.7.3 Final conclusi

27、on: 132Annex J (informative) Example of external documentation identification report of an oil spill identification case. 133J.1 Introduction . 133J.2 Sample information 133J.3 Analytical procedure 133J.3.1 Method . 133J.3.2 Dilution/extraction 133J.3.3 Analyses 133J.4 Results . 133J.5 Interpretatio

28、n . 134PD CEN/TR 15522-2:2012CEN/TR 15522-2:2012 (E) 5 J.5.1 General . 134J.5.2 Positive match . 134J.5.3 Probable match 134J.5.4 Inconclusive . 134J.5.5 Non-match 134J.6 Conclusions . 134Bibliography 135PD CEN/TR 15522-2:2012CEN/TR 15522-2:2012 (E) 6 Foreword This document (CEN/TR 15522-2:2012) sup

29、ersedes CEN/TR 15522-2:2006, which was prepared by CEN/BT/TF 120 “Oil Spill Identification“ (now disbanded). 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 a

30、ll such patent rights. This document supersedes CEN/TR 15522-2:2006. CEN/TR 15522 is composed of the following parts: Part 1: Sampling; Part 2: Analytical methodology and interpretation of results based on GC-FID and GC-MS low resolution analyses (the present document). PD CEN/TR 15522-2:2012CEN/TR

31、15522-2:2012 (E) 7 Introduction This Technical Report describes and recommends a forensic methodology for characterising and identifying the source of waterborne oils resulting from accidental spills or intentional discharges. The methodology may be used in support of the legal process as evidence f

32、or prosecuting offenders (“potential responsible party“ PRP). This methodology is a technical revision of CEN/TR 15522-2 Version 1 published in December 2006. This methodology is composed of two parts that are described by the following CEN documents: Part 1 Sampling: describes sampling techniques a

33、nd the handling of oil samples prior to their arrival at the forensic laboratory; Part 2 Methodology: covers the general concepts and laboratory procedures of oil spill identification methodology, analytical techniques, data processing, data treatment, and interpretation/evaluation and reporting of

34、results. Oil spill source identification is a complex methodology due to the large variation in samples and oil spill situations that can be encountered. Part 1 is a compilation of instructions and experiences from experts all over the world which will guide the user in sampling, storing and deliver

35、ing oil samples for laboratory analysis. Part 2 will guide the reader through the analytical process. It prescribes how to prepare and analyse oil samples using GC-FID and GC-low-resolution mass spectrometry (MS). Any chemical differences found between samples are only relevant if a difference is la

36、rger than the variability of the method itself. Good analytical performance and strict quality assurance are therefore essential. In the Annexes of Part 2, relevant information concerning different types of oil and oil comparison techniques is presented. The main purpose of the methodology described

37、 in this Technical Report (TR) is to defensibly identify the source of oil spills in marine, estuarine and other aquatic environments by comparing the chemical compositions of samples from spills with those of suspected sources. The underlying basis for this method is the widely variable nature of o

38、ils with respect to their specific chemical compositions, which allows oils from different sources to be readily distinguished using the appropriate analytical methods. The method relies upon detailed chemical characterisation and statistical comparison between samples (i.e., a spilled oil and a sus

39、pected source) diagnostic features in order to determine whether they “match”. To minimise the danger of “false positive matches”, good laboratory practices are necessarily maintained. Even so, a “positive match” between a spilled oil and a suspected source may not be used alone to identify the “pot

40、ential responsible party“ (PRP), but this result is often a critical piece of evidence in proving a case within the legal process. However, in some oil spill identification cases, both the oil spill and also suspected source(s) may not necessarily be unique or homogeneous in nature, e.g., due to the

41、 changing/variable nature of oil in the bilge tanks or due to mixing of oils spilled from several sources in a case of a larger incident. The risk therefore exists that the chemical composition of the available source samples may not match to that of the available spill samples. In such cases, oil s

42、pill identification methodologies in general will have limitations and may not necessarily lead to unequivocal conclusions. In other words, the success of this methodology in defensibly identifying a spilled oils source depends upon the samples available for chemical study. To minimise the danger fo

43、r “false positive” or “false non-matches”, good sampling practice, and particularly the need to obtain appropriate reference/suspect source samples, is crucial (as described in Part 1: Sampling). When oil from suspected sources is not available, this methodology may still be used to characterise the

44、 spilled oil in order to determine the spilled oil type and any specific characteristics. The characterisation of a spilled oil sample can still be useful for several reasons: If the source of an oil pollution event is unknown, the investigating authorities should be advised on the type of oil in or

45、der to aid in the identification of a possible source. For example, in the case of a “mystery” spill, the mere differentiation between pure, unused refined petroleum products (e.g. diesel fuel versus heavy fuel oil) or versus crude oil or waste oil (e.g., bilge residues, sludge, slops) can provide p

46、otentially PD CEN/TR 15522-2:2012CEN/TR 15522-2:2012 (E) 8 valuable information as the possible source(s) for the spill. In such instances, the type of oil spilled should be identified rapidly because the chances of identifying and collecting candidate source oils generally decrease with time. In so

47、me court trials, the differentiation between pure refined products and waste oil may be very important because it allows conclusions to be drawn regarding the cause of an oil discharge, e.g. technical failure, accidental discharge, intentional discharge. In some countries, photos (e.g. taken from an

48、 airplane) from a plume behind a ship, combined with the evidence that the plume contains mineral oil, is enough for a condemnation. Finally, characterisation of the spilled oil provides a baseline against which future impacts to the affected area/environment might be compared. This Technical Report is the result of advancements in the field of oil spill identification e.g., 13, 21, 44, 46 and 50 that have been made since the Nordtest Method 35, 36 was first introduced in 1991. These have included: ad