A Strategy and Methodology for Defensibly Correlating Spilled Oil to Source Candidates

The source of crude oils and petroleum products released into navigable waterways and shipping lanes is not always known. Thus, the defensible identification of spilled crude oils and petroleum products and their correlation to suspected sources is a critical part of many oil spill assessments. Quantitative “fingerprinting” analysis, when evaluated using straightforward statistical and numerical analyses, provides a defensible means to differentiate among qualitatively similar oils and provides the best assessment of the source(s) for spilled oils. Polycyclic aromatic hydrocarbon (PAH) and petroleum biomarker concentration data are a particularly useful quantitative measure that can benefit most oil spill investigations. In this paper the strategy and methodology for correlation analysis that relies upon quantitative gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM) is demonstrated in a case study involving 66 candidate sources for a heavy fuel oil spill of unknown origin. The strategy includes identification of 19 chemical indices (out of 45 evaluated) based upon PAH's and biomarkers that were (1) independent of weathering; and (2) precisely measured, both of which are determined by statistical analysis of the data. The 19 chemical indices meeting these criteria are subsequently analysed using principal component analysis (PCA), which helps to determine defensibly the “prime suspects” for the oil spill under investigation. The strategy and methodology described, which combines statistical and numerical analysis of quantitative chemical data, can be adapted and applied to other environmental forensic investigations with the objective of correlating any form of contamination to its suspected sources.     

Round Robin Study--Oil Spill Identification

As part of the ongoing work to develop new guidelines for oil spill identification for the European Committee for Standardization (CEN), a Round Robin test was arranged by SINTEF in co-operation with the Norwegian General Standardizing Body (NAS). Twelve laboratories from ten countries participated in the Round Robin study. They include: Denmark, Finland, France, Germany, the Netherlands, Norway, Scotland, Sweden, Wales, and the U.S.A. The analytical methodology used for the Round Robin testing is a result of the ongoing project "Revision of the Nordtest Methodology for Oil Spill Identification". The analytical methodology is described in the AMOP proceedings 2002. Seven oil samples (two artificially weathered "spill" samples and five possible sources) were analyzed following the recommended analytical protocols. The Round Robin study was a "difficult case", because the two spill samples and three of the suspected sources were highly correlated to one another. These samples were from the same oil field in the North Sea, but from different production wells. The present paper summarizes the Round Robin study, and demonstrates the potential of this methodology as a strong technically defensible tool in oil spill identification due to its ability to distinguish qualitatively similar oils from a spill and any available candidate source.     

Round Robin Study—Oil Spill Identification

As part of the ongoing work to develop new guidelines for oil spill identification for the European Committee for Standardization (CEN), a Round Robin test was arranged by SINTEF in co-operation with the Norwegian General Standardizing Body (NAS). Twelve laboratories from ten countries participated in the Round Robin study. They include: Denmark, Finland, France, Germany, the Netherlands, Norway, Scotland, Sweden, Wales, and the U.S.A. The analytical methodology used for the Round Robin testing is a result of the ongoing project “Revision of the Nordtest Methodology for Oil Spill Identification”. The analytical methodology is described in the AMOP proceedings 2002. Seven oil samples (two artificially weathered “spill” samples and five possible sources) were analyzed following the recommended analytical protocols. The Round Robin study was a “difficult case”, because the two spill samples and three of the suspected sources were highly correlated to one another. These samples were from the same oil field in the North Sea, but from different production wells. The present paper summarizes the Round Robin study, and demonstrates the potential of this methodology as a strong technically defensible tool in oil spill identification due to its ability to distinguish qualitatively similar oils from a spill and any available candidate source.     

Brazilian Oil Spills Chemical Characterization--Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds--benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

Brazilian Oil Spills Chemical Characterization—Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds—benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

Improved and Standardized Methodology for Oil Spill Fingerprinting

The existing Nordtest methodology for oil spill Identification has over the past 10 years formed an important “platform” for solving oil spill identification cases both in the Scandinavian countries as well as other countries in Europe, the USA and Canada. “Revision of the Nordtest Methodology for Oil Spill Identification” is a cooperative project between the National Oil Spill Identification laboratories in Norway, Sweden, Finland, Denmark and the Battelle Memorial Institute (Duxbury) in the USA. The goals of the project are: (1) to refine the existing Nordtest methodology into a technically more robust and defensible oil spill identification methodology with focus on determination of quantitative diagnostic indices (ratios) and (2) to adjust the revised Nordtest methodology into guidelines for the European Committee for Standardization (CEN). This paper presents the recommended methodology for the analytical oil spill identification part. The sampling techniques and handling of oil samples and background (reference) samples prior to their arrival at the environmental forensic laboratory is not covered in this paper. The recommended methodology approach is a result of documented analytical improvements and a more quantitative treatment of analytical data from gas chromatographic-flame ionization detector (GC/FID) and gas chromatographic-mass spectrometer methods (GC/MS-SIM) and the operational experiences over past few years among the participating forensic laboratories. The experience and literature in the field of oil exploration and production geochemistry have also played an important role for the recommended methodology. The results from a recent Round Robin test carried out among 12 laboratories using this new methodology are presented in a separate paper in this issue (8).     

Improved and Standardized Methodology for Oil Spill Fingerprinting

The existing Nordtest methodology for oil spill Identification has over the past 10 years formed an important "platform" for solving oil spill identification cases both in the Scandinavian countries as well as other countries in Europe, the USA and Canada. " Revision of the Nordtest Methodology for Oil Spill Identification " is a cooperative project between the National Oil Spill Identification laboratories in Norway, Sweden, Finland, Denmark and the Battelle Memorial Institute (Duxbury) in the USA. The goals of the project are: (1) to refine the existing Nordtest methodology into a technically more robust and defensible oil spill identification methodology with focus on determination of quantitative diagnostic indices (ratios) and (2) to adjust the revised Nordtest methodology into guidelines for the European Committee for Standardization (CEN). This paper presents the recommended methodology for the analytical oil spill identification part. The sampling techniques and handling of oil samples and background (reference) samples prior to their arrival at the environmental forensic laboratory is not covered in this paper. The recommended methodology approach is a result of documented analytical improvements and a more quantitative treatment of analytical data from gas chromatographic-flame ionization detector (GC/FID) and gas chromatographic-mass spectrometer methods (GC/MS-SIM) and the operational experiences over past few years among the participating forensic laboratories. The experience and literature in the field of oil exploration and production geochemistry have also played an important role for the recommended methodology. The results from a recent Round Robin test carried out among 12 laboratories using this new methodology are presented in a separate paper in this issue (Faksness et at ., 2002d).     

High-molecular weight sulfur-containing aromatics refractory to weathering as determined by Fourier transform ion cyclotron resonance mass spectrometry

Biomarkers and low-molecular weight polyaromatic compounds have been extensively studied for their fate in the environment. They are used for oil spill source identification and monitoring of weathering and degradation processes. However, in some cases, the absence or presence of very low concentration of such components restricts the access of information to spill source. Here we followed the resistance of high-molecular weight sulfur-containing aromatics to the simulated weathering condition of North Sea crude oil by ultra high-resolution Fourier transform ion cyclotron resonance mass spectrometry. The sulfur aromatics in North Sea crude having double bond equivalents (DBE) from 6 to 14 with a mass range 188-674 Da were less influenced even after 6 months artificial weathering. Moreover, the ratio of dibenzothiophenes (DBE 9)/naphthenodibenzothiophenes (DBE 10) was 1.30 and 1.36 in crude oil and 6 months weathered sample, respectively reflecting its weathering stability. It also showed some differences within other oils. Hence, this ratio can be used as a marker of the studied crude and accordingly may be applied for spilled oil source identification in such instances where the light components have already been lost due to environmental influences.     

Soil Gas Methane at Petroleum Contaminated Sites: Forensic Determination of Origin and Source

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a significant health and safety risk. While petroleum products do not contain a significant amount of methane (CH 4 ), high CH 4 contents in soil gas near petroleum spills have been reported. While CH 4 is nontoxic, its accumulation in shallow soil gas represents a potential explosion and asphyxiation hazard, especially in confined spaces. Identifying the source and origin of shallow CH 4 accumulations is an important part of evaluating potential exposure pathways, selecting appropriate remedial measures, and determining environmental liability. This paper discusses the potential nature and anthropogenic sources for shallow CH 4 and how integration of geological, geochemical, and land use data can be used to determine its origin and identify its source. Two case studies are presented, one where CH 4 associated with a gasoline spill is shown to be derived from a natural source rather than the gasoline, and a second where CH 4 associated with spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil.     

Soil Gas Methane at Petroleum Contaminated Sites: Forensic Determination of Origin and Source

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a significant health and safety risk. While petroleum products do not contain a significant amount of methane (CH₄), high CH₄contents in soil gas near petroleum spills have been reported. While CH₄is nontoxic, its accumulation in shallow soil gas represents a potential explosion and asphyxiation hazard, especially in confined spaces. Identifying the source and origin of shallow CH₄accumulations is an important part of evaluating potential exposure pathways, selecting appropriate remedial measures, and determining environmental liability. This paper discusses the potential nature and anthropogenic sources for shallow CH₄and how integration of geological, geochemical, and land use data can be used to determine its origin and identify its source. Two case studies are presented, one where CH₄associated with a gasoline spill is shown to be derived from a natural source rather than the gasoline, and a second where CH₄associated with spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil.     

不同类型海岸的溢油清理方法

世界石油资源分布和需求的不均衡性,促进了海上石油工业和石油运输业的快速发展,同时也增加了溢油事故的几率.海上溢油污染问题日趋严重,溢油污染对海洋环境、生态、资源、经济及人类生产生活等造成了巨大的影响,日益引起社会各界的关注.海岸溢油污染清理实践表明,正确的溢油清理方案的制定应综合考虑海岸的敏感性指数、溢油的类型、清理方法可能带来的危害以及支际可操作程度等.对包括盐沼地海岸和红树林海岸,沉积海岸,以及岩石海岸三类典型海岸的国内外现有海岸溢油污染清理技术进行了详细的综述,以期为我国的海岸带管理和溢油应急计划的制订提供技术参考.     

The Use of the Isotopic Composition of Individual Compounds for Correlating Spilled Oils and Refined Products in the Environment with Suspected Sources

Correlation of crude oils, or refined products, in the environment with suspected sources is typically undertaken through the use of GC and GCMS and in certain cases bulk carbon isotope compositions. However, with crude condensates, or refined products in particular, the absence, or low concentration, of biomarkers precludes their successful use for making unique correlations. An alternative and, sometimes, complimentary technique for correlation of such products is evolving through the use of combined gas chromatography-isotope ratio mass spectrometry (GCIRMS). This approach permits determination of the carbon and hydrogen isotopic composition of individual compounds in the crude oil or refined product to produce isotopic fingerprints for use in correlation studies. In this paper, it is proposed to review applications of GCIRMS to the correlation of various spilled products with their suspected sources in different environments. Whilst not proposing that this technique will replace GC or GCMS; it is proposed that GCIRMS is a very powerful tool to be used in conjunction with GC and GCMS to make such correlations. Although isotopic fractionation has been observed in some of the lighter components such as benzene and toluene, higher carbon numbered compounds, say above C 10 , do not appear to undergo any significant isotopic fractionation as a result of weathering. Furthermore with refined products, isotopic fractionation of the lighter components has the potential to demonstrate the onset of natural attenuation of refined products in the environment.     

Oil Identification Based on a Goodness-of-Fit Metric Applied to Hydrocarbon Analysis Results

Assessment of environmental damage following accidental oil spills requires reliable oil identification methods. Results from hydrocarbon analyses of environmental samples are often difficult to interpret, because of the changes in oil composition (or weathering) that follows release into the environment, and because of confounding by hydrocarbons from other sources. To a first-order approximation, weathering proceeds according to simple first-order loss-rate (FOLR) kinetics for polycyclic aromatic hydrocarbons (PAH) based on molecular size. This relationship between relative weathering rate and molecular size can be exploited to infer the initial PAH composition of spilled oils, and this information can be combined with results for weathering-invariant analytes to substantially increase the precision and accuracy of hydrocarbon source recognition methods. The approach presented here evaluates a goodness-of-fit metric between the measured hydrocarbon composition of an environmental sample and a suspected source, after correcting for PAR weathering losses based on FOLR kinetics. Variability from analytical and sampling error may thus be accounted for, and source identifications can be expressed as objective probability statements. This approach is illustrated by application to four independent case studies.     

Responses of juvenile sea bass, Dicentrarchus labrax, exposed to acute concentrations of crude oil, as assessed by molecular and physiological biomarkers

In the present study, juvenile sea bass were exposed for 48 and 96 h to an Arabian light crude oil and their responses were assessed at the molecular and physiological levels. The aim of the study was therefore to assess (i) the short term effects of crude oil exposure by the measurement of several molecular biomarkers, (ii) the consequences of this short term exposure on fish health by using growth and condition indices measured after a decontamination period of 28 and 26 d in seawater. Hydrocarbon petroleum concentrations was monitored during the 96 h experiments and an increase of PAH concentrations were found in fish following both exposure times. An 7-ethoxyresorufin-O-deethylase (EROD) induction was observed after 48 h of exposure, while a significant decrease in the sea bass specific growth rate in length and for the RNA:DNA ratio was observed 28 d after that exposure ceased. The EROD induction doubled after the 96 h exposure, and a significant increase in GST activities was observed. A significant decrease in the specific growth rates, the otolith recent growth, the RNA:DNA ratio and the Fulton’s K condition index were then observed in sea bass 26 d after the 96 h exposure to mechanically dispersed crude oil compared to the control. The present study shows that growth and condition indices can prove useful in assessing fish health status following an oil spill. Their complementary analysis with sensitive molecular biomarkers as EROD could improve the determination of oil spill impact on fish populations.     

Environmental photooxidation of dibenzothiophenes following the Amoco Cadiz oil spill

Photooxidation products of dibenzothiophenes (sulfur containing petroleum heteroaromatic hydrocarbons) were characterized in an oil slick sample obtained from a field location following the AMOCO CADIZ oil spill. The same oxidation products were formed in the laboratory by the photooxidation of a medium Arabian crude oil which contained the identical precursor hydrocarbons. Analytical techniques included fractionation by liquid/solid chromatography and characterization using high resolution gas chromatography-mass spectrometry. To the best of the author's knowledge, this represents the first reported instance for the formation of photooxidation products following an actual oil spill. A comparison of the quantities of various oxidation products was carried out by quantitative mass spectrometry using extracted ion current profiles of dibenzothiophenes and their corresponding sulfoxides. The geochemical and physiological implications of such photooxidation processes are also discussed.     

Simulation of interactions between migrating whales and potential oil spills

A numerical model system was developed to quantify the probability of endangered bowhead and gray whales encountering spilled oil in Alaskan waters. Migration and diving-surfacing models for bowhead and gray whales, and an oil spill trajectory model comprise the system. The migration models were developed from conceptual considerations, then calibrated with and tested against observations. The distribution of whales is represented in space and time by discrete points, each of which may represent one or more whales. The movement of a whale point is governed by a random walk algorithm which stochastically follows a migratory pathway. Stochastic diving-surfacing models are used to stimulate surfacing behavior sequences for each species. The oil spill model accounts for oil transport and spreading in open water and in the presence of sea ice. Historical wind records and ice cover data sets provide the environmental conditions to generate stochastic oil spill scenarios. The oil spill, whale migration and diving-surfacing models are linked to provide quantitative estimates of whale-oil interactions. The model system was applied to the Alaskan Beaufort Sea to investigate the probability that bowhead whales would encounter oil spilled in this region.     

Identification of PAHs Sources in Bivalves and Sediments 5 Years After the Sea Prince Oil Spill in Korea

On 23 July 1995, the oil tanker Sea Prince ran aground near Son Island, off the South Coast of Korea and spilled 5040 tons of crude and fuel oil into the marine environment. The effects of the Sea Prince oil spill on the marine environment have been investigated since 1996. The main objectives of this study were to find out the residual effects of beached oil and transport of dispersed oil into the subtidal area. Twenty-four PARs were analyzed and principal component analysis was performed to elucidate weathering status, bioaccumulation pattern, and input sources. There were signs of bioconcentration of oil-derived PAHs in mussels of stranded oil remained sites. However, environmental factors overwhelmed these so that all the bivalves studied showed similar pattern in the last two sampling campaigns. There was no significant evidence of transport of oil-derived PAHs into the subtidal environment. However, one station showed an exceptionally high concentration (923 ng/g dry weight), which implies the limited input of particle-bound PAHs into this confined area.     

Pattern Recognition Based Software for Oil Spills Identification by Gas-Chromatography and IR Spectrophotometry

For environmental control purposes, floating oil spills in harbours, off shore areas and their sources must often be identified. Pattern recognition, applied to JR spectrophotometric data (600-2000 cm m 1 range), and to chromatographic data ( n -alkanes) for the spill and various suspected sources such as oil and fuels from ships bunkers and harbour installations, can lead to definite conclusions; particularly after artificial weathering formula are used. The software application provides quick and accurate identification of the pollution source. The identification algorithm has a learning stage in which the user creates a minimal database. This database has a tree structure with classes (fuels, crude, etc.) and members representing samples from already known sources. A sample contains JR and chromatographic data and information of the originating source. A larger database means more knowledge, which conveys a better identification. When the origin of an unknown sample is searched for, the software looks for the best match through the database and displays the results in two lists; sorted by calculated similarity. One list displays the classes in which the unknown sample could be included and the other displays the possible sources. An extra check can be done by visual inspection of the overlapped graphics (unknown sample and each of the identified sources).     

The Use of the Isotopic Composition of Individual Compounds for Correlating Spilled Oils and Refined Products in the Environment with Suspected Sources

Correlation of crude oils, or refined products, in the environment with suspected sources is typically undertaken through the use of GC and GCMS and in certain cases bulk carbon isotope compositions. However, with crude condensates, or refined products in particular, the absence, or low concentration, of biomarkers precludes their successful use for making unique correlations. An alternative and, sometimes, complimentary technique for correlation of such products is evolving through the use of combined gas chromatography–isotope ratio mass spectrometry (GCIRMS). This approach permits determination of the carbon and hydrogen isotopic composition of individual compounds in the crude oil or refined product to produce isotopic fingerprints for use in correlation studies. In this paper, it is proposed to review applications of GCIRMS to the correlation of various spilled products with their suspected sources in different environments. Whilst not proposing that this technique will replace GC or GCMS; it is proposed that GCIRMS is a very powerful tool to be used in conjunction with GC and GCMS to make such correlations. Although isotopic fractionation has been observed in some of the lighter components such as benzene and toluene, higher carbon numbered compounds, say above C₁₀, do not appear to undergo any significant isotopic fractionation as a result of weathering. Furthermore with refined products, isotopic fractionation of the lighter components has the potential to demonstrate the onset of natural attenuation of refined products in the environment.     

A Holistic Approach to Hydrocarbon Source Allocation in the Subtidal Sediments of Prince William Sound,Alaska, Embayments

Prince William Sound (PWS), Alaska has an extensive history of human and industrial activity that has produced a complex organic geochemistry record in subtidal sediments of embayments throughout the sound. In addition to contributions from recent oil spills and a regional background of natural petroleum hydrocarbons originating from active hydrocarbon systems in the northern Gulf of Alaska (GOA), pyrogenic and petrogenic PAH were, and continue to be introduced to subtidal sediments at numerous sites of past and present human activities. These sites include villages, fish hatcheries, fish camps and recreational campsites in addition to abandoned settlements, canneries, sawmills, and mines. A holistic approach is used to fingerprint and quantify hydrocarbon contributions from multiple sources in a sediment sample. It involves acquiring a comprehensive understanding of the history of the area to identify potential sources, collection of representative samples, and accurate quantitative analyses of the source and sediment samples for a suite of diagnostic PAH analytes and chemical biomarker compounds. Unlike the deepwater sediments of the sound and GOA, the TOC tool, described elsewhere, does not work as well in some restricted embayments due to their high contents of recent organic matter (ROM). The current study employs a constrained least-squares algorithm to allocate hydrocarbon sources contributing to subtidal sediments collected from PWS embayments in 1991, 1999 and 2000. Results show that sources contributing to the natural petrogenic background are present in the embayments, pyrogenic hydrocarbons including combustion products of diesel are important where human activity was high, and petroleum produced from the Monterey Formation (CA) is present locally. Oil and asphalt shipped from California were widely used for fuel and construction prior to development of the Cook Inlet and North Slope fields. In certain locations that were oiled in 1989, low levels of highly degraded Alaska North Slope crude oil residues attributable to the Exxon Valdez spill remain.