SIST-TP CEN/TR 15522-2:2013

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 (TR) describes a methodology to firstly identify the specific nature of oils spilled in marine, estuarine and aquatic environments and secondly compare the chemical composition of spilled oil or oily samples with that of suspected sources. Specifically, the TR describes the detailed analytical methods and data processing specifications for identifying the specific nature of waterborne oil spills and establishing their correlation to suspected sources. Even when samples or data from suspected sources are not available for comparison, establishing the specific nature (e.g., refined petroleum, crude oil, waste oil, etc.) of the spilled oil may still help constrain the possible source(s) of the spilled oil. This methodology is restricted to petroleum and petroleum products containing a significant proportion of hydrocarbon-components with a boiling point above 200°C. Examples are: crude oils, higher boiling condensates, diesel oils, residual bunker or heavy fuel oils, lubricants, and mixtures of bilge and sludge samples. While the specific analytical methods may not be appropriate for lower boiling oils (e.g. kerosenes, jet fuels, or gasoline), the general concepts described in this methodology, i.e., statistical comparison of weathering-resistant diagnostic ratios, may have applicability in spills involving lower boiling oils. This method is not directly intended for oil spills impacting groundwater, vegetation, wildlife/tissues, soils, or sediments, and although its application in these matrices is not precluded, it requires caution. The reason for caution is that the extractable compounds in these matrices may alter and/or contribute additional compounds compared to the source sample, which if left unrecognised, can lead to “false non-matches”. Including these “non-oil” matrices in this oil spill identification method may require additional sample preparation (e.g. cleanup) in the laboratory prior to analysis and consideration of the extent to which the matrix may affect the correlation achieved. Evaluating the possible effects in these matrices is beyond the scope of this guideline. Whether the method can be used for this kind of “non-oil” matrices may depend on the oil concentration compared to the “matrix concentration” of the samples. In “non-oil” matrices containing a relative high concentration of oil, a positive match can still be concluded. In “non-oil” matrices containing a relative low concentration of spilled oil, a non-match or an inconclusive match could be achieved due to matrix effects.

Identifizierung von Ölverschmutzungen - Rohöl und Mineralölerzeugnisse aus dem Wasser - Teil 2: Analytische Methodik und Interpretation der Ergebnisse, basierend auf GC-FID- und GC-MS-Analysen bei niedriger Auflösung

Prepoznavanje razlitij olj - Nafta in naftni proizvodi v vodi - 2. del: Analizne metode in podajanje rezultatov, izhajajočih iz GC-FID in GC-MS nizke ločljivosti

To tehnično poročilo (TR) opisuje metodologijo za prepoznavanje specifične narave olj, razlitih v morskih okoljih, okoljih rečnih ustij in vodnih okoljih, ter za primerjavo kemične sestave razlitih olj ali oljnih vzorcev s sumljivimi viri. Tehnično poročilo opisuje podrobne analizne metode in specifikacije obdelovanja podatkov za prepoznavanje specifične narave razlitij olj v vodi ter vzpostavljanje korelacije s sumljivimi viri. Tudi če vzorci ali podatki iz sumljivih virov niso na voljo za primerjavo, lahko opredelitev specifične narave (npr. rafinirana nafta, surova nafta, odpadno olje itd.) razlitih olj pomaga pri omejevanju možnih virov razlitih olj. Ta metodologija je omejena na nafto in naftne proizvode z znatnim deležem ogljikovodikovih sestavnih delov z vreliščem nad 200 °C. Primeri vključujejo: surove nafte, kondenzate z višjim vreliščem, dizelska goriva, ostanke goriv iz ladijskih rezervoarjev ali težkih kurilnih olj, maziva ter mešanice vzorcev kaluže in blata. Specifične analizne metode morda niso primerne za olja z nizkim vreliščem (npr. kerozine, goriva za reaktivne letalske motorje ali bencin), vendar se splošni pojmi, opisani v tej metodologiji, npr. statistična primerjava diagnostičnih razmerij odpornosti na pospešeno staranje, lahko uporabijo pri razlitjih olj z nizkim vreliščem. Ta metoda ni neposredno namenjena za uporabo pri razlitjih olj, ki vplivajo na podtalnico, vegetacijo, prostoživeče živali in rastline/tkiva, tla ali sedimente, pri čemer je kljub temu, da njena uporaba v navedenih matricah ni izključena, potrebna previdnost. Razlog za previdnost je dejstvo, da lahko sestavni deli v navedenih matricah, ki jih je mogoče ekstrahirati, spremenijo in/ali prispevajo dodatne sestavne dele v primerjavi z izvirnim vzorcem, kar lahko, če pojav ostane neodkrit, povzroči »lažna neujemanja«. Tudi navedene »neoljne« matrice lahko pri metodi prepoznavanja razlitij olj zahtevajo dodatno pripravo vzorca (npr. čiščenje) v laboratoriju, pred analizo in upoštevanjem obsega vpliva matrice na doseženo korelacijo. Vrednotenje možnih vplivov v navedenih matricah ne spada na področje uporabe teh smernic. Možnost uporabe metode za to vrsto »neoljnih« matric je lahko odvisna od koncentracije olja v primerjavi s »koncentracijo matrice« v vzorcih. Pri »neoljnih« matricah z relativno visoko koncentracijo olja se lahko še vedno ugotovi pozitivno ujemanje. Pri »neoljnih« matricah z relativno nizko koncentracijo razlitih olj se lahko zaradi učinkov matrice doseže neujemanje ali nedoločno ujemanje.

General Information

• Status: Withdrawn
• Public Enquiry End Date: 30-Jun-2012
• Publication Date: 20-Dec-2012
• Withdrawal Date: 12-Apr-2023
• ICS: 13.020.40 - Pollution, pollution control and conservation
• ICS: 13.060.99 - Other standards related to water quality
• Technical Committee: NAD - Petroleum products, lubricants and related products
• Current Stage: 9900 - Withdrawal (Adopted Project)
• Start Date: 12-Apr-2023
• Due Date: 05-May-2023
• Completion Date: 13-Apr-2023
• Ref Project: 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 low resolution analyses

Relations

• Replaced By: SIST EN 15522-2:2023 - Oil spill identification - Petroleum and petroleum related products - Part 2: Analytical method and interpretation of results based on GC-FID and GC-low resolution-MS analyses
• Effective Date: 01-Jun-2023
• Replaces: SIST-TP CEN/TR 15522-2:2008 - Oil spill identification - Waterborne petroleum and petroleum products - Part 2: Analytical methodology and interpretation of results
• Effective Date: 01-Jan-2013

Standards Content (Sample)

SLOVENSKI STANDARD
SIST-TP CEN/TR 15522-2:2013
01-januar-2013
1DGRPHãþD
SIST-TP CEN/TR 15522-2:2008
3UHSR]QDYDQMHUD]OLWLMROM1DIWDLQQDIWQLSURL]YRGLYYRGLGHO$QDOL]QHPHWRGH
LQSRGDMDQMHUH]XOWDWRYL]KDMDMRþLKL]*&),'LQ*&06QL]NHORþOMLYRVWL
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
Identifizierung von Ölverschmutzungen - Rohöl und Mineralölerzeugnisse aus dem
Wasser - Teil 2: Analytische Methodik und Interpretation der Ergebnisse, basierend auf
GC-FID- und GC-MS-Analysen bei niedriger Auflösung
Ta slovenski standard je istoveten z: CEN/TR 15522-2:2012
ICS:
13.020.40 Onesnaževanje, nadzor nad Pollution, pollution control
onesnaževanjem in and conservation
ohranjanje
13.060.99 Drugi standardi v zvezi s Other standards related to
kakovostjo vode water quality
SIST-TP CEN/TR 15522-2:2013 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST-TP CEN/TR 15522-2:2013

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SIST-TP CEN/TR 15522-2:2013


TECHNICAL REPORT
CEN/TR 15522-2

RAPPORT TECHNIQUE

TECHNISCHER BERICHT
October 2012
ICS 75.080 Supersedes CEN/TR 15522-2:2006
English 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 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, 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
© 2012 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 15522-2:2012: E
worldwide for CEN national Members.

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SIST-TP CEN/TR 15522-2:2013
CEN/TR 15522-2:2012 (E)
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 Abbreviated 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 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 emulsified 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 evaluation 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
6.3.1 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 and peak integration . 24
6.4.4 Evaluation of weathering . 26
6.4.5 Evaluation of mixing . 29
2

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SIST-TP CEN/TR 15522-2:2013
CEN/TR 15522-2:2012 (E)
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 diagnostic 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-FID 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-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 . 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 selected 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
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 . 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
3

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SIST-TP CEN/TR 15522-2:2013
CEN/TR 15522-2:2012 (E)
F.8 Asphaltenes . 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 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 . 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) 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 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 Sample 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 . 133
J.4 Results . 133
J.5 Interpretation . 134
4

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SIST-TP CEN/TR 15522-2:2013
CEN/TR 15522-2:2012 (E)
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

5

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SIST-TP CEN/TR 15522-2:2013
CEN/TR 15522-2:2012 (E)
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 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-FID and GC-MS low resolution
analyses (the present document).
6

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SIST-TP CEN/TR 15522-2:2013
CEN/TR 15522-2:2012 (E)
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 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 composed 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
methodology, 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 instructions and experiences from experts all
...

SLOVENSKI STANDARD
kSIST-TP FprCEN/TR 15522-2:2012
01-junij-2012
3UHSR]QDYDQMHUD]OLWLMROM1DIWDLQQDIWQLSURL]YRGLYYRGLGHO$QDOL]QHPHWRGH
LQSRGDMDQMHUH]XOWDWRYL]KDMDMRþLKL]*&),'LQ*&06QL]NHORþOMLYRVWL
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
Ta slovenski standard je istoveten z: FprCEN/TR 15522-2:2012
ICS:
13.020.40 Onesnaževanje, nadzor nad Pollution, pollution control
onesnaževanjem in and conservation
ohranjanje
13.060.99 Drugi standardi v zvezi s Other standards related to
kakovostjo vode water quality
kSIST-TP FprCEN/TR 15522-2:2012 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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kSIST-TP FprCEN/TR 15522-2:2012

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kSIST-TP FprCEN/TR 15522-2:2012


TECHNICAL REPORT
FINAL DRAFT
FprCEN/TR 15522-2
RAPPORT TECHNIQUE

TECHNISCHER BERICHT

April 2012
ICS 75.080 Will supersede CEN/TR 15522-2:2006
English Version
Oil spill identification - Waterborne petroleum and petroleum
products - Part 2: Part 2: Analytical methodology and
interpretation of results based on GC-FID and GC-MS low
resolution analyses



This draft Technical Report is submitted to CEN members for Technical Committee Approval. It has been drawn up by the Technical
Committee CEN/SS S27.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, 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, Turkey and United Kingdom.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are aware and to
provide supporting documentation.

Warning : This document is not a Technical Report. It is distributed for review and comments. It is subject to change without notice and
shall not be referred to as a Technical Report.


EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2012 CEN All rights of exploitation in any form and by any means reserved Ref. No. FprCEN/TR 15522-2:2012:2012: E
worldwide for CEN national Members.

---------------------- Page: 3 ----------------------
kSIST-TP FprCEN/TR 15522-2:2012
FprCEN/TR 15522-2:2012 (E)
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 Abbreviated 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 . 13
4.3.3 Conclusions and reporting . 14
5 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 emulsified 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 Characterization and evaluation of analytical data . 19
6.1 General . 19
6.2 Characterization 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
6.3.1 General . 22
6.3.2 Visual inspection and overall characterization - 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 and peak integration . 24
6.4.4 Evaluation of weathering . 26
6.4.5 Evaluation of mixing . 29
2

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kSIST-TP FprCEN/TR 15522-2:2012
FprCEN/TR 15522-2:2012 (E)
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 diagnostic 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-FID analysis . 42
A.1 General . 42
A.2 Analytical standards for GC-FID analyses . 42
A.2.1 N-alkanes . 42
A.2.2 Injection concentration of the standard GC-FID . 42
A.2.3 Storage of standard solutions. 43
A.3 Suggested instrumental conditions . 43
A.4 Measures to improve and verify the accuracy of the method – GC-FID . 43
A.4.1 Mass discrimination . 43
A.4.2 Column resolution . 44
A.4.3 Calibration range . 45
A.4.4 Mid-level concentration . 45
A.4.5 Variance . 46
A.5 Sample analysis with GC-FID . 46
Annex B (normative) GC-MS analysis . 47
B.1 General . 47
B.2 Analytical standards for GC-MS analyses . 47
B.2.1 General . 47
B.2.2 SINTEF oil mixture . 48
B.2.3 Analytical standards for PAH homologues . 48
B.2.4 Storage of standard solutions. 48
B.3 Suggested instrumental conditions . 48
B.3.1 GC conditions for the exchange of analytical results. . 48
B.3.2 MS conditions for full-scan analysis . 51
B.3.3 MS preparation for selected ion monitoring (SIM) analysis . 51
B.4 Measures to improve and verify the accuracy of the GC-MS method . 52
B.4.1 Relative retention time . 52
B.4.2 Mass discrimination . 52
B.4.3 Peak symmetry and column resolution . 52
B.4.4 Patterns . 53
B.4.5 Calibration range . 53
B.4.6 Mid-level concentration . 53
B.4.7 Variance . 53
B.5 Sample analysis with GC-MS . 53
Annex C (informative) List of PAHs and biomarkers analysed by GC-MS-SIM . 54
Annex D (informative) Alkyl homologue patterns of PAHs . 56
Annex E (informative) Diagnostic ratios . 64
E.1 Diagnostic ratios of PAHs . 64
E.2 Diagnostic ratios of biomarkers . 68
Annex F (informative) General composition of oils – chemical groups . 74
F.1 Introduction . 74
F.2 Hydrocarbons . 74
F.3 Paraffins . 74
F.4 Naphthenes . 75
F.5 Aromatics . 75
F.6 Heteroatomic organic compounds . 75
F.7 Resins . 75
3

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kSIST-TP FprCEN/TR 15522-2:2012
FprCEN/TR 15522-2:2012 (E)
F.8 Asphaltenes . 75
Annex G (informative) Weathering of oils spilled on water . 77
G.1 Introduction . 77
G.2 Evaporation . 78
G.3 Dissolution . 80
G.4 Re-distribution of chemical composition . 81
G.5 Biodegradation . 84
G.6 Photooxidation . 84
G.7 Contamination . 86
Annex H (informative) Characteristic Features of Different Oil Types in Oil Spill Identification . 87
H.1 Introduction . 87
H.2 Light fuel oil (gas oil, diesel, fuel No 2) . 87
H.2.1 General . 87
H.2.2 Analysis, GC screening . 88
H.2.3 MS analysis (alternative parameters) . 90
H.2.4 Addition of biodiesel. . 92
H.3 Lubricating oil . 93
H.3.1 General . 93
H.3.2 Analysis . 93
H.4 Heavy fuel oil (HFO, Bunker C, Fuel No 6) . 97
H.4.1 General . 97
H.4.2 Analysis . 97
H.5 Waste oil (bilge oil, sludge, slops) . 105
H.5.1 General . 105
H.5.2 Analysis . 106
H.6 Crude oil . 111
H.6.1 General . 111
H.6.2 Analysis . 111
H.7 Conclusion . 116
Annex I (informative) Example of internal documentation – technical report of an oil spill case . 118
I.1 General . 118
I.2 Sample information . 118
I.2.1 Contact information . 118
I.2.2 Request . 118
I.2.3 Photo(s) of the samples . 119
I.3 Sample preparation and analyses. 119
I.4 Quality assurance . 120
I.5 GC-FID results . 121
GC-FID conclusions: . 124
I.6 GC-MS results . 124
I.6.1 General . 124
I.6.2 Comparison of the surface water samples. . 125
I.6.3 Comparison of the spill samples with bilge sample 6. . 126
I.7 Conclusions . 127
I.7.1 Surface water sample 1 with bilge sample 6. . 127
I.7.2 Surface water sample 2 with bilge sample 6. . 128
I.7.3 Final conclusion: . 128
Annex J (informative) Example of external documentation – identification report of an oil spill
identification case. 129
J.1 Introduction . 129
J.2 Sample information . 129
J.3 Analytical procedure . 129
J.3.1 Method . 129
J.3.2 Dilution/extraction . 129
J.3.3 Analyses . 129
J.4 Results . 129
J.5 Interpretation. . 130
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FprCEN/TR 15522-2:2012 (E)
J.5.1 Positive match . 130
J.5.2 Probable match . 130
J.5.3 Inconclusive . 130
J.5.4 Non-match . 130
J.6 Conclusions . 130
Bibliography . 131

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kSIST-TP FprCEN/TR 15522-2:2012
FprCEN/TR 15522-2:2012 (E)
Foreword
This document (FprCEN/TR 15522-2:2012) has been prepared by Technical Committee CEN/TC “CSS27”,
the secretariat of which is held by CCMC.
This document is currently submitted to the Technical Committee Approval.
This document will supersede CEN/TR 15522-2:2006.
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kSIST-TP FprCEN/TR 15522-2:2012
FprCEN/TR 15522-2:2012 (E)
Introduction
This Technical Report describes and recommends a forensic methodology for characterizing 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 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 composed 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
methodology, 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 instructions and experiences from experts all
over the world and 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-resolution mass spectrometry (M
...