1、PUBLISHED DOCUMENT PD CEN/TR 15522-2:2006 Oil spill identification Waterborne petroleum and petroleum products Part 2: Analytical methodology and interpretation of results ICS 13.020.40; 75.080 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/05/2008 08:16, Uncontrolled Copy, (c) BSIPD CEN/
2、TR 15522-2:2006 This Published Document was published under the authority of the Standards Policy and Strategy Committee on 31 March 2008 BSI 2008 ISBN 978 0 580 60617 5 National foreword This Published Document is the UK implementation of CEN/TR 15522-2:2006. The UK participation in its preparation
3、 was entrusted to Technical Committee PTI/12, Petroleum measurement and sampling. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its
4、correct application. Amendments/corrigenda issued since publication Date Comments Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/05/2008 08:16, Uncontrolled Copy, (c) BSI TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 15522-2 November 2006 ICS 75.080 English Version Oil spi
5、ll identification - Waterborne petroleum and petroleum products - Part 2: Analytical methodology and interpretation of results Identification des pollutions ptrolires - Ptrole et produits ptroliers dans leau - Partie 2 : Mthodologie analytique et interprtation des rsultats Identifizierung von lversc
6、hmutzungen - Rohl und Minerallerzeugnisse aus dem Wasser - Teil 2: Analytische Methodik und Interpretation der Ergebnisse This Technical Report was approved by CEN on 25 September 2006. It has been drawn up by the Technical Committee CEN/BT/TF 120. CEN members are the national standards bodies of Au
7、stria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FO
8、R STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TR 15522-2:2006: E Licensed Copy: Wang Bin
9、, ISO/EXCHANGE CHINA STANDARDS, 15/05/2008 08:16, Uncontrolled Copy, (c) BSI2 Contents Page Foreword4 Introduction .5 1 Scope 7 2 Normative references 7 3 Terms and definitions .7 4 Strategy for identification of oil spills .9 4.1 General9 4.2 Procedure .10 4.3 Decision chart of analytical and data
10、treatment levels10 5 Sample preparation .12 5.1 General12 5.2 Visual examination of samples 13 5.3 Preparation .13 5.4 Recommended sample clean up methodology 14 5.5 Recommended injection concentration 15 6 Characterization and evaluation of analytical data15 6.1 General15 6.2 Characterization by GC
11、/FID level 1 .15 6.3 Characterisation by GC/MS level 2 .17 6.4 Treatment of the results level 3.27 6.5 Conclusions .33 7 Reporting 33 8 Quality assurance34 Annex A (informative) Analytical standards 35 A.1 General35 A.2 Recommended standards and concentrations 35 A.3 Analytical standards for PAH hom
12、ologues.36 A.4 Calibration- GC/MS 37 Annex B (informative) Suggested instrument conditions39 B.1 GC/FID conditions39 B.2 GC/MS conditions41 B.3 Sample analysis.42 B.4 Calculations44 B.5 SIM-sections .45 Annex C (informative) List of PAHs and biomarkers analysed by GC/MS-SIM46 Annex D (informative) A
13、lkyl homologues patterns of PAHs49 Annex E (informative) Boiling points of n-alkanes .58 Annex F (informative) General composition of oils chemical groups .59 F.1 Introduction59 F.2 Hydrocarbons.59 F.3 Paraffins59 F.4 Naphthenes 60 F.5 Aromatics .60 F.6 Heteroatomic organic compounds 60 CEN/TR 15522
14、-2:2006 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/05/2008 08:16, Uncontrolled Copy, (c) BSI3 F.7 Resins.60 F.8 Asphaltenes .60 Annex G (informative) Weathering of oils spilled at sea61 G.1 Introduction61 G.2 Evaporation62 G.3 Dissolution .64 G.4 Re-distribution of chemical compositio
15、n65 G.5 Biodegradation 66 G.6 Contamination / in-homogeneity .67 G.7 Evaluation of weathering67 G.8 Optional - Semi-quantitative distribution of PAH homologues - weathering check.69 Annex H (informative) Characteristic Features of Different Oil Types in Oil Spill Identification .70 H.1 Introduction7
16、0 H.2 Light fuel oil (gas oil, diesel, fuel No 2).70 H.3 Lubricating oil75 H.4 Heavy fuel oil (HFO, Bunker C, Fuel No 6)79 H.5 Waste oil (bilge oil, sludge, slops).87 H.6 Crude oil .93 H.7 Conclusion .98 Annex I (informative) Example of the evaluation of an oil case .100 I.1 Introduction100 I.2 GC/F
17、ID results100 I.3 GC/MS results 102 I.4 Conclusion .106 Bibliography107 CEN/TR 15522-2:2006 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/05/2008 08:16, Uncontrolled Copy, (c) BSI4 Foreword This document (CEN/TR 15522-2:2006) has been prepared by CEN/BT/TF 120 “Oil spill identification”,
18、 the secretariat of which is held by SN. CEN/TR 15522-2:2006 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/05/2008 08:16, Uncontrolled Copy, (c) BSI5 Introduction This Technical Report gives a recommendation on a forensic methodology for identifying waterborne oils. The methodology may b
19、e a support to the legal process as evidence for prosecuting offenders (“potential responsible party“ PRP). This methodology is a technical revision of the Nordtest Method NT CHEM 001 (1991) “Oil spill identification“. This methodology is described by the following CEN documents: Part 1 Sampling: de
20、scribes 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 methodology, analytical techniques, data processing, data treatment, and interpretation
21、/evaluation of results. Oil spill identification and oil comparison is a complex methodology due to the large variation in samples and oil spill situations, which can be encountered. Part 1 is a compilation of instructions and experiences from experts all over the world and will guide the user in sa
22、mpling, storing and delivering oil samples. Part 2 will guide the reader through the process by dividing the methodology into 3 tiered levels. It prescribes how to prepare and analyse oil samples with GC/FID and, if necessary, with GC-low-resolution mass spectrometry. Differences found between sampl
23、es are only relevant if a difference is larger than the analytical variance of the method. Therefore good analytical performance and strict quality assurance are essential. In the annexes of part 2, relevant information concerning different types of oil and oil comparison is presented. The main purp
24、ose of the methodology described in this Technical Report (TR) is to identify oil spills in marine, estuarine and other aquatic environments by comparing samples from spills with those of suspected sources. In oil spill identification cases, both the oil spill and also suspected source(s) may not ne
25、cessarily be homogeneous in nature e.g. due to the changing/variable nature of oil in the bilge tanks or e.g. mixing of oil spills from several sources in a case of a larger incident. The risk therefore exists that the chemical composition of the reference samples may not be related to that of the s
26、pill. In such cases oil spill fingerprinting methodologies in general will have its limitations and may not necessarily lead to firm conclusions. To minimise the danger for “false negative” matches, good sampling practice, and particularly the need to obtain appropriate reference/suspect source samp
27、les, is therefore crucial (as described in Part 1 Sampling). When suspected sources are not available, this methodology may be used to characterise the spill as far as possible with respect to oil type. The identification of the type of oil in a sample can be essential for several reasons: if the or
28、igin of an oil pollution event is unknown, the investigating authorities must be advised on where to find a possible source. In case of a “mystery” spill, the mere differentiation between pure, unused products or crude oil and waste oil (bilge residues, sludge, slops) is valuable information. Oils m
29、ust be identified rapidly in such cases because the chances of identifying sources generally decrease with time; meaning of analytical results, i.e. their contribution to the overall evidence in criminal proceedings, depends very much on the types of oil that are involved in oil spills. Depending on
30、 these types, the search can be more or less focused on a few possible sources, or even a single one; in court trials, the differentiation between pure products and waste oil may be highly important because it allows conclusions to be drawn regarding the cause of an oil discharge, e.g. technical fai
31、lure, inadvertence, intention; CEN/TR 15522-2:2006 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/05/2008 08:16, Uncontrolled Copy, (c) BSI6 conclusions obtained from the defensible identification of spilled oil and their correlation to suspected sources will not, however, on their own id
32、entify the “potential responsible party“ (PRP), but is often a critical part of, and a support to, the legal process. In these guidelines, some activities are marked as “Optional”. These are suggestions to supplementary diagnostic documentations, e.g. in cases where there may still be uncertainty in
33、 drawing conclusions based on the “standard” recommended methodology. The first draft of the methodology was evaluated through a Round Robin study organised by the CEN/BT/TF 120 Oil Spill Identification. This test was limited to crude oils and heavy fuel oils. Two more recent Round Robin tests organ
34、ised by RIZA in the Netherlands, where fifteen laboratories participated, covered cases with light fuel oil distillates (diesel oils,) and bilge water samples (a mixture of gas oils and lube oil). Findings from these RR-tests have been taken into account for refining the suggested methodology. CEN/T
35、R 15522-2:2006 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/05/2008 08:16, Uncontrolled Copy, (c) BSI7 1 Scope This Technical Report (TR) describes a methodology to identify waterborne oils spilled in marine, estuarine and aquatic environments by comparing samples from spills with those
36、 of suspected sources . It provides detailed analytical and processing specifications for identifying waterborne oil spills and their correlation to suspected sources. When suspected sources are not available, the methodology may be used to characterise the spill as far as possible with respect to t
37、he oil type. This methodology is restricted to petroleum and petroleum products containing a significant proportion of HC-components with a boiling point above 200 C. Examples are: Crude oils, condensates, light fuel oils, diesel oils, residual bunker oils, lubricants, and mixtures of bilge and slud
38、ge samples. Still, the general concepts described in this methodology have a limited applicability for some kerosenes and some condensates, but may not be applicable for gasoline NOTE This method is not intended for oil spills to groundwater and soil. The chromatograms of oil extracted from soil and
39、 found in ground water may contain reduced and/or additional peaks compared to the source sample. Including such samples in this method makes it necessary to add extraction methods and to describe which compounds are possibly reduced and/or which additional peaks can be expected to change the final
40、conclusion from a probable match into a match. This is beyond the scope of this guideline, however, when case samples completely match according to this method, the method is valid for those samples. 2 Normative references The following referenced documents are indispensable for the application of t
41、his European Standard. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. CEN/TR 15522-1, Oil spill identification Waterborne petroleum and petroleum products Part 1: Sampling 3 Terms and def
42、initions For the purposes of this document, the following terms and definitions apply. 3.1 chain of custody line of actions taken for samples from spill and suspected sources at court for safe surveillance and storing; to ensure that the samples have not been tampered with or altered accidentally 3.
43、2 contamination all changes in oil composition which take place during/after the spillage, by mixing with additional compounds, including natural products 3.3 critical difference (CD) value less than or equal to which the absolute difference between two test results obtained under repeatability cond
44、itions may be expected to be with a probability of 0,95; the critical difference is defined as CD= (mean x r 95% )/(100) 3.4 diagnostic ratios ratios between the peak height or peak area of single compounds or compound groups selected by their diversity in chemical composition in petroleum and petro
45、leum products and on their known behaviour in weathering processes CEN/TR 15522-2:2006 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/05/2008 08:16, Uncontrolled Copy, (c) BSI8 3.5 identity no differences observed in the chromatographic patterns of GC/FID and GC/MS apart from those change
46、s introduced after the spill (weathering, degradation etc.) 3.6 inconclusive when differences in chromatographic patterns and diagnostic ratios of the samples submitted for comparison are larger than the analytical variance of the method and may only, to some extent, be explained by external factors
47、 like weathering, contamination, heterogeneity of the samples or too low an amount of sample material NOTE Differences may be due to e.g. heterogeneities of the oil either within the spill or within the suspected source (e.g. within the ship tank), that is not reflected in the available samples anal
48、ysed, or differences are present because the samples do not originate from the same source. 3.7 non-match when differences in chromatographic patterns and diagnostic ratios of the samples submitted for comparison are distinct and larger than the analytical variance of the method and they cannot be e
49、xplained by external factors like weathering, contamination and heterogeneity. The samples are distinctly different 3.8 positive match when differences in chromatographic patterns and diagnostic ratios of the samples submitted for comparison are lower than the analytical variance of the method or can clearly be explained by weathering. The samples are identical beyond reasonable doubt 3.9 probable match when differences in chromatographic patterns and diagnostic ratios of t
