DIN 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-.pdf

1、Dezember 2012Normenausschuss Materialprfung (NMP) im DINFachausschuss Minerall- und Brennstoffnormung (FAM) des NMPPreisgruppe 33DIN Deutsches Institut fr Normung e. V. Jede Art der Vervielfltigung, auch auszugsweise, nur mit Genehmigung des DIN Deutsches Institut fr Normung e. V., Berlin, gestattet

2、.ICS 75.080; 13.020.40Zur Erstellung einer DIN SPEC knnen verschiedene Verfahrensweisen herangezogen werden: Das vorliegende Dokument wurde nach den Verfahrensregeln eines Fachberichts erstellt.!$m4“1927417www.din.deDDIN CEN/TR 15522-2Identifizierung von lverschmutzungen Rohl und Minerallerzeugnisse

3、 aus dem Wasser Teil 2: Analytische Methodik und Interpretation der Ergebnisse,basierend auf GC-FID- und GC-MS-Analysen bei niedriger Auflsung;Englische Fassung CEN/TR 15522-2:2012Oil spill identification Waterborne petroleum and petroleum products Part 2: Analytical methodology and interpretation o

4、f results based on GC-FID and GC-MSlow resolution analyses;English version CEN/TR 15522-2:2012Identification des pollutions ptrolires Ptrole et produits ptroliers dans leau Partie 2 : Mthodologie analytique et interprtation des rsultats de lanalyse avecrsolution rduite GC-FID et de GC-MS;Version ang

5、laise CEN/TR 15522-2:2012Alleinverkauf der Spezifikationen durch Beuth Verlag GmbH, 10772 Berlin www.beuth.deGesamtumfang 140 SeitenDIN SPEC 192692 Nationales Vorwort Dieses Dokument (CEN/TR 15522-2:2012) wurde vom Technischen Komitee CEN/TC 19 Gasfrmige und flssige Kraft- und Brennstoffe, Schmierst

6、offe und verwandte Produkte mit minerallstmmiger, synthetischer oder biologischer Herkunft“ erarbeitet, dessen Sekretariat vom NEN (Niederlande) gehalten wird. Das zustndige nationale Gremium ist der NA 062-06-42 AA Prfung von flssigen Kraftstoffen und Heiz-len“ im Fachausschuss Minerall- und Brenns

7、toffnormung (FAM) des Normenausschusses Materialprfung (NMP) im DIN. Es wurde keine deutsche bersetzung erstellt, da in den deutschen Fachkreisen das englische Dokument verwendet wird. DIN CEN/TR 15522-2 (DIN SPEC 19269):2012-12 TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 15522-2 O

8、ctober 2012 ICS 75.080 Supersedes CEN/TR 15522-2:2006English Version Oil spill identification - Waterborne petroleum and petroleum products - Part 2: Analytical methodology and interpretation of results based on GC-FID and GC-MS low resolution analyses This Technical Report was approved by CEN on 13

9、 August 2012. 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,

10、Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. 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 15522-2:201

11、2: EEUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG 2 Contents Page Foreword 6 Introduction .7 1 Scope 9 2 Normative references 9 3 Terms, definitions and abbreviated terms 9 3.1 General 9 3.2 Sample comparison 10 3.3 Conclusions 11 3.4 Abbreviate

12、d terms 11 4 Strategy for the identification of oil spills sources . 12 4.1 Introduction . 12 4.2 Basis for reliable conclusions Numerical comparisons 12 4.3 Overview of the procedure 13 4.3.1 Sampling and sample preparation 13 4.3.2 GC-FID and GC-MS analysis 14 4.3.3 Conclusions and reporting 14 5

13、Sample preparation 16 5.1 General . 16 5.2 Visual examination and description of samples . 16 5.3 Preparation 16 5.3.1 General . 16 5.3.2 Water samples . 16 5.3.3 Oil samples from an Ethylene tetrafluoroethylene (ETFE) net 17 5.3.4 Thick oil and emulsified oil samples 17 5.3.5 Tar balls and emulsifi

14、ed lumps . 17 5.3.6 Samples from oiled birds, fish and other animals and vegetation 17 5.4 Sample clean-up . 18 5.4.1 General . 18 5.4.2 Biogenic materials 18 5.4.3 Black oil/HFO (removing of asphaltenes and/or soot particles) 18 5.5 Recommended injection concentration . 18 6 Characterisation and ev

15、aluation of analytical data . 19 6.1 General . 19 6.2 Characterisation by GC-FID Level 1 20 6.2.1 General . 20 6.2.2 Evaluation of the influence of weathering on sample comparison . 21 6.2.3 Acyclic isoprenoids ratios . 22 6.2.4 Level 1 Conclusions . 22 6.3 Characterisation by GC-MS Level 2 . 22 6.3

16、.1 General . 22 6.3.2 Visual inspection and overall characterisation - Level 2.1 . 23 6.3.3 Treatment of the GC-MS results Level 2.2 23 6.4 Treatment of the results using the MS-PW-plot Level 2.2 23 6.4.1 General . 23 6.4.2 PW-plot calculations 24 6.4.3 Evaluation of the variability of the analysis

17、and peak integration 24 6.4.4 Evaluation of weathering . 26 6.4.5 Evaluation of mixing . 29 DIN CEN/TR 15522-2 (DIN SPEC 19269):2012-12 CEN/TR 15522-2:2012 (E) 3 6.5 Treatment of the results using ratios Level 2.2 . 31 6.5.1 General . 31 6.5.2 Diagnostic ratios calculation . 32 6.5.3 Normative diagn

18、ostic ratios . 32 6.5.4 Analytical error 35 6.5.5 Match-criterion for ratios 35 6.5.6 Criteria for selecting, elimination and evaluating diagnostic ratios 36 6.5.7 Optional: Evaluation of diagnostic ratios using conventional or multivariate statistics 39 6.6 Conclusions . 40 Annex A (normative) GC-F

19、ID analysis 43 A.1 General . 43 A.2 Analytical standards for GC-FID analyses 43 A.2.1 N-alkanes 43 A.2.2 Injection concentration of the standard GC-FID 43 A.2.3 Storage of standard solutions 44 A.3 Suggested instrumental conditions 44 A.4 Measures to improve and verify the accuracy of the method GC-

20、FID 44 A.4.1 Mass discrimination 44 A.4.2 Column resolution . 45 A.4.3 Calibration range . 46 A.4.4 Mid-level concentration 46 A.4.5 Variance 47 A.5 Sample analysis with GC-FID . 47 Annex B (normative) GC-MS analysis 48 B.1 General . 48 B.2 Analytical standards for GC-MS analyses 48 B.2.1 General .

21、48 B.2.2 SINTEF oil mixture . 49 B.2.3 Analytical standards for PAH homologues 49 B.2.4 Storage of standard solutions 49 B.3 Suggested instrumental conditions 49 B.3.1 GC conditions for the exchange of analytical results. 49 B.3.2 MS conditions for full-scan analysis . 52 B.3.3 MS preparation for se

22、lected ion monitoring (SIM) analysis 52 B.4 Measures to improve and verify the accuracy of the GC-MS method . 53 B.4.1 Relative retention time 53 B.4.2 Mass discrimination 53 B.4.3 Peak symmetry and column resolution 53 B.4.4 Patterns 54 B.4.5 Calibration range . 54 B.4.6 Mid-level concentration 54

23、B.4.7 Variance 54 B.5 Sample analysis with GC-MS . 54 Annex C (informative) List of PAHs and biomarkers analysed by GC-MS-SIM 55 Annex D (informative) Alkyl homologue patterns of PAHs 57 Annex E (informative) Diagnostic ratios . 65 E.1 Diagnostic ratios of PAHs 65 E.2 Diagnostic ratios of biomarkers

24、 69 Annex F (informative) General composition of oils chemical groups 76 F.1 Introduction 76 F.2 Hydrocarbons 76 F.3 Paraffins . 76 F.4 Naphthenes 77 F.5 Aromatics . 77 F.6 Heteroatomic organic compounds 77 F.7 Resins . 77 DIN CEN/TR 15522-2 (DIN SPEC 19269):2012-12 CEN/TR 15522-2:2012 (E) 4 F.8 Asp

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

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

27、 95 H.3.2 Analysis . 95 H.4 Heavy fuel oil (HFO, Bunker C, Fuel No 6) . 99 H.4.1 General . 99 H.4.2 Analysis . 99 H.5 Waste oil (bilge oil, sludge, slops) 107 H.5.1 General . 107 H.5.2 Analysis . 108 H.6 Crude oil 113 H.6.1 General . 113 H.6.2 Analysis . 113 H.7 Conclusion 118 Annex I (informative)

28、Example of internal documentation technical report of an oil spill case . 120 I.1 General . 120 I.2 Sample information 120 I.2.1 General . 120 I.2.2 Contact information 120 I.2.3 Request 120 I.2.4 Photo(s) of the samples . 121 I.3 Sample preparation and analyses. 121 I.4 Quality assurance . 124 I.5

29、GC-FID results . 125 I.6 GC-MS results . 128 I.6.1 General . 128 I.6.2 Comparison of the surface water samples. . 129 I.6.3 Comparison of the spill samples with bilge Sample 6. . 130 I.7 Conclusions 131 I.7.1 Surface water Sample 1 with bilge Sample 6. 131 I.7.2 Surface water Sample 2 with bilge Sam

30、ple 6. 132 I.7.3 Final conclusion: 132 Annex J (informative) Example of external documentation identification report of an oil spill identification case. 133 J.1 Introduction . 133 J.2 Sample information 133 J.3 Analytical procedure 133 J.3.1 Method . 133 J.3.2 Dilution/extraction 133 J.3.3 Analyses

31、 133 J.4 Results . 133 J.5 Interpretation . 134 DIN CEN/TR 15522-2 (DIN SPEC 19269):2012-12 CEN/TR 15522-2:2012 (E) 5 J.5.1 General . 134 J.5.2 Positive match . 134 J.5.3 Probable match 134 J.5.4 Inconclusive . 134 J.5.5 Non-match 134 J.6 Conclusions . 134 Bibliography 135 DIN CEN/TR 15522-2 (DIN SP

32、EC 19269):2012-12 CEN/TR 15522-2:2012 (E) 6 Foreword This document (CEN/TR 15522-2:2012) supersedes 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

33、 of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all 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

34、-FID and GC-MS low resolution analyses (the present document). DIN CEN/TR 15522-2 (DIN SPEC 19269):2012-12 CEN/TR 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 acci

35、dental spills or intentional discharges. The methodology may be used in support of the legal process as evidence for 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 compose

36、d of two parts that are described by the following CEN documents: Part 1 Sampling: describes sampling techniques and 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 me

37、thodology, analytical techniques, data processing, data treatment, and interpretation/evaluation and reporting of 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 instr

38、uctions and experiences from experts all over the world which will guide the user in sampling, storing and delivering 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-resolut

39、ion mass spectrometry (MS). Any chemical differences found between samples are only relevant if a difference is larger 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 concernin

40、g different types of oil and oil comparison techniques is presented. The main purpose of the methodology described 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 fr

41、om spills with those of suspected sources. The underlying basis for this method is the widely variable nature of oils 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

42、 upon detailed chemical characterisation and statistical comparison between samples (i.e., a spilled oil and a suspected source) diagnostic features in order to determine whether they “match”. To minimise the danger of “false positive matches”, good laboratory practices are necessarily maintained. E

43、ven so, a “positive match” between a spilled oil and a suspected source may not be used alone to identify the “potential 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 t

44、he oil spill and also suspected source(s) may not necessarily be unique or homogeneous in nature, e.g., due to the 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 comp

45、osition of the available source samples may not match to that of the available spill samples. In such cases, oil spill 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

46、identifying a spilled oils source depends upon the samples available for chemical study. To minimise the danger for “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: S

47、ampling). When oil from suspected sources is not available, this methodology may still be used to characterise the 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 sou

48、rce of an oil pollution event is unknown, the investigating authorities should be advised on the type of oil in order 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. diese

49、l fuel versus heavy fuel oil) or versus crude oil or waste oil (e.g., bilge residues, sludge, slops) can provide potentially DIN CEN/TR 15522-2 (DIN SPEC 19269):2012-12 CEN/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 some court trials, the differentiation between pure refined products and wa