Oil Spill Identification Research Articles

Headspace mass spectrometry methodology: application to oil spill identification in soils

In the present work we report the results obtained with a methodology based on direct coupling of a headspace generator to a mass spectrometer for the identification of different types of petroleum crudes in polluted soils. With no prior treatment, the samples are subjected to the headspace generation process and the volatiles generated are introduced directly into the mass spectrometer, thereby obtaining a fingerprint of volatiles in the sample analysed. The mass spectrum corresponding to the mass/charge ratios (m/z) contains the information related to the composition of the headspace and is used as the analytical signal for the characterization of the samples. The signals obtained for the different samples were treated by chemometric techniques to obtain the desired information. The main advantage of the proposed methodology is that no prior chromatographic separation and no sample manipulation are required. The method is rapid, simple and, in view of the results, highly promising for the implementation of a new approach for oil spill identification in soils.

Multibeam backscatter as a tool for sea-floor characterization and identification of oil spills in the Galicia Bank

This study is focused on the potential of using the multibeam acoustic backscatter both for sea-floor characterization of the Galicia Bank and for identification of sea-bottom oil spills. An extended multibeam data set was acquired during the RG-1 and RG-2 surveys aboard RV Hespérides in 2003 for the geological and geophysical characterization of the Galicia Bank, where the oil tanker Prestige wreck is located. 3-D images have been made by integrating bathymetry and backscatter data. Multibeam data have been additionally supported by gravity core information in order to correlate sea-floor acoustic backscatter with the surficial sediments and their physical properties. The major factors that seem to control the zonation of the backscatter intensity images are (i) the type of the sedimentary processes (gravitational, turbiditic, hemipelagic), which control at the same time, the grain size distribution, and (ii) the sea-bottom morphologies, such as basement outcrops. However, there are some backscatter halos that cannot be explained by these processes. In the backscatter maps, the bow and stern of the Prestige wreck are clearly marked by a high-backscatter intensity anomaly, whose existence is discussed.

Assessment of oil weathering by gas chromatography–mass spectrometry, time warping and principal component analysis

Detailed characterization and understanding of oil weathering at the molecular level is an essential part of tiered approaches for forensic oil spill identification, for risk assessment of terrestrial and marine oil spills, and for evaluating effects of bioremediation initiatives. Here, a chemometric-based method is applied to data from two in vitro experiments in order to distinguish the effects of evaporation and dissolution processes on oil composition. The potential of the method for obtaining detailed chemical information of the effects from evaporation and dissolution processes, to determine weathering state and to distinguish between various weathering processes is investigated and discussed. The method is based on comprehensive and objective chromatographic data processing followed by principal component analysis (PCA) of concatenated sections of gas chromatography–mass spectrometry chromatograms containing homologue series of n-alkanes ( m/ z 85) and alkyltoluenes ( m/ z 105). The PCA model based solely on in vitro samples and validated by samples from an authentic marine oil spill gives a detailed description of the temporal changes in n-alkane and alkyltoluene compositions. The PCA model is able to distinguish the two physical weathering processes both with respect to removal rate and relative changes. The model shows that evaporation has a large impact on both the alkyltoluenes and on the n-alkanes (e.g., nC-18 is completely removed after 192 days of in vitro evaporation). Dissolution, however, is shown to be a much slower process for weathering of heavy fuel oils with only limited impact on the alkyltoluenes, and no effects on the n-alkane distribution.

Comparative Analytical Data in the Source Determination of Unknown Spilled Oil in the Haydarpaşa Port (Marmara Sea), Turkey

The coasts of Marmara Sea are continually affected by heavy crude oil and heavy fuel oil pollution. In addition to the coastal pollution, some point sources such as ports and oil terminals have serious effects. The Haydarpasa Port is the most important port situated on the Anatolian side of the Strait of Istanbul (Bosphorus) (Fig. 1). It has two breakwaters about 1,700 and 600 m long (Fig. 1). The pollution of the maritime, coastal and harbor environments continues to be an issue around the globe. In the Haydarpasa Port, fuel oil spillage from ships and vehicles and conventional shipping activities such as tank cleaning and de-ballasting operations and bilge waste waters are the main sources of PAHs in the vicinity. All crude oils and petroleum products, to some extent, have chemical compositions that differ from each other. This variability in chemical compositions results in unique chemical fingerprints for each oil and provides a basis for identifying the source(s) of the spilled oil (Wang 2003). In recent years, numerous studies concerned with the origin type, fate and behavior of spilled oils in various environments have been published. Great advances have been made on both interpretive and analytical methods for fingerprinting oil hydrocarbons. Flexible, tiered analytical approaches, which facilitate the detailed compositional analyses based primarily upon GC/MS has been developed in response to the oil spill identification (Wang 2003). An important discovery is that the diagnostic indices in a vessel’s bilge contents and its discharges could also constitute fingerprints for the ships. In so that, by comparing the fingerprints of different spilled oils with the material from the bilges of ships, it would be possible to determine the source of spill oil. In this study SUVF and GC/MS analysis were used to characterize the chemical composition of the unknown oil spilled from the Haydarpasa Port by using advanced fingerprinting techniques and diagnostic ratios.

Monitoring of Oil Spill Using Ultra-Violet Laser

We have developed the helicopter-based fluorescence imaging LIDAR (Light Detection and Ranging) for the monitoring of oil spills. This is an active, remote sensing system which shoots a UV pulsed laser beam to an oil spill on the sea's surface, the fluorescence image is then observed. Compared to other techniques, this monitoring method has the merit of a high reliability of oil spill identification. And also high observability, even in nighttime, or rainfall and in high-wave conditions.In the helicopter flight experiments, the detection and identification of sea water and light fuel oil has been successful. In addition, the area of light fuel oil film was estimated by the fluorescence 2-D image observations.In this technical report, we describe the details of this system and the results of the performance evaluation so far and by experimentation using helicopters.

Slicks Detection on the Sea Surface Based Upon Polarimetric SAR Data

This letter proposes a generalized-likelihood ratio test-based edge detector to be fed by possibly polarimetric synthetic aperture radar (SAR) data. It can be used to detect dark spots on the sea surface and, hence, as the first stage of a system for identification and monitoring of oil spills. The proposed constant false alarm rate (CFAR) detector does not require secondary data (namely pixels from a slick-free area); remarkably, a preliminary performance assessment, carried out by resorting to real SAR recordings, shows that it guarantees detection capabilities comparable to those of previously proposed polarimetric CFAR detectors (which though make use of secondary data). The preliminary performance assessment also seems to indicate that processing polarimetric data does not ensure improved detection capabilities.

Automatic identification of oil spills on satellite images

A fully automated system for the identification of possible oil spills present on Synthetic Aperture Radar (SAR) satellite images based on artificial intelligence fuzzy logic has been developed. Oil spills are recognized by experts as dark patterns of characteristic shape, in particular context. The system analyzes the satellite images and assigns the probability of a dark image shape to be an oil spill. The output consists of several images and tables providing the user with all relevant information for decision-making. The case study area was the Aegean Sea in Greece. The system responded very satisfactorily for all 35 images processed. The complete algorithmic procedure was coded in MS Visual C++ 6.0 in a stand-alone dynamic link library (dll) to be linked with any sort of application under any variant of MS Windows operating system.

Identifying the Source of Mystery Waterborne Oil Spills—A Case for Quantitative Chemical Fingerprinting

Oil spills of unknown origin, so-called “mystery” spills, occur routinely in rivers, open water, and navigable coastal waterways. The natural resources damage (NRD) liability associated with even a small volume of oil released into the environment warrants that a thorough chemical characterization of the spilled oil be conducted by agencies and potentially responsible parties (PRPs). Chemical fingerprinting methods have played an important role in the identification of mystery oil spills. These methods fall into two categories, viz., qualitative and quantitative. The qualitative approach relies upon visual comparison of various chromatographic fingerprints obtained by GC/FID and GC/MS analysis of spill and candidate source oils and are represented ASTM methods. The quantitative approach relies upon measurements of the concentrations (relative or absolute) of dozens of diagnostic chemicals, typically PAHs and biomarkers, and a subsequent statistical or numerical analysis of various diagnostic parameters calculated from these concentrations. The quantitative approach is represented by the revised Nordtest methodology. The quantitative approach is preferable for most oil spill investigations since the means of interpretation are objective, whereas the ASTM methods are subjective. Quantitative fingerprinting data are particularly important when the mystery spill and source oils are qualitatively similar and are required when mystery spills may include mixed sources or prespill oil signatures.

Integrated methodology for forensic oil spill identification.

A new integrated methodology for forensic oil spill identification is presented. It consists of GC-MS analysis, chromatographic data processing, variable-outlier detection, multivariate data analysis, estimation of uncertainties, and statistical evaluation. The methodology was tested on four groups of diagnostic ratios composed of petroleum biomarkers and ratios within homologous PAH categories. Principal component analysis (PCA) was employed and enabled the simultaneous analysis of many diagnostic ratios. Weathering was taken into account by considering the sampling uncertainties estimated from replicate spill samples. Statistical evaluation ensured an objective matching of oil spill samples with suspected source oils as well as classification into positive match, probable match, and nonmatch. The data analysis is further refined if two or more source oils are classified as probable match by using weighted least squares fitting of the principal components, local PCA models, and additional information relevant to the spill case. The methodology correctly identified the source of two spill samples (i.e., crude oils from Oseberg East and Oseberg Field Centre) and distinguished them from closely related source oils.

Characterization and identification of the Detroit River mystery oil spill (2002)

In this paper, a case study of the Detroit River mystery oil spill (2002) is presented that demonstrates the utility of detailed and integrated oil fingerprinting in investigating unknown or suspected oil spills. The detailed diagnostic oil fingerprinting techniques include determination of hydrocarbon groups and semi-quantitative product screening, analysis of oil-characteristic biomarkers and the extended suite of parent and alkylated polycyclic aromatic hydrocarbons (PAHs), and quantitative determination of a variety of diagnostic ratios of “source-specific marker” compounds. The detailed chemical fingerprinting data and results highlight the followings: (1) The spill samples were largely composed of used lube oil mixed with smaller portion of diesel fuel. (2) The diesel in the samples had been weathered and degraded. (3) Sample 3 collected from N. Boblo Island on 14 April was more weathered (most probably caused by more evaporation and water-washing) than samples 1 and 2. (4) All fingerprinting results clearly demonstrated oils in three samples were the same, and they came from the same source. (5) Most PAH compounds were from the diesel portion in the spill samples, while the biomarker compounds were largely from the lube oil. (6) Input of pyrogenic PAHs to the spill samples was clearly demonstrated. The pyrogenic PAHs were most probably produced from combustion and motor lubrication processes, and the lube oil in these spill samples was waste lube oil.

Development of oil hydrocarbon fingerprinting and identification techniques

Oil, refined product, and pyrogenic hydrocarbons are the most frequently discovered contaminants in the environment. To effectively determine the fate of spilled oil in the environment and to successfully identify source(s) of spilled oil and petroleum products is, therefore, extremely important in many oil-related environmental studies and liability cases. This article briefly reviews the recent development of chemical analysis methodologies which are most frequently used in oil spill characterization and identification studies and environmental forensic investigations. The fingerprinting and data interpretation techniques discussed include oil spill identification protocol, tiered analytical approach, generic features and chemical composition of oils, effects of weathering on hydrocarbon fingerprinting, recognition of distribution patterns of petroleum hydrocarbons, oil type screening and differentiation, analysis of “source-specific marker” compounds, determination of diagnostic ratios of specific oil constituents, stable isotopic analysis, application of various statistical and numerical analysis tools, and application of other analytical techniques. The issue of how biogenic and pyrogenic hydrocarbons are distinguished from petrogenic hydrocarbons is also addressed.

Oil-spill identification by gas chromatography-mass spectrometry.

Two approaches are proposed for the identification of a contaminant caused by the spilling of oil or oil products in water. A capillary gas chromatography (CGC)-mass spectrometry (MS) method for oil spill identification is applied. The presented approaches describe the use of MS data of 18 selective ions of spilled product and the probable pollutant. The spill identification is accomplished on the bases of a quantitative comparison between the ion chromatograms of the samples taken from the probable pollutant and from the spill itself. The other approach is made by chemometric treatment of complete CGC-MS data.

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).

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.

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).

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

Round Robin Study--Oil Spill Identification

Star Evviva Spill: Oiled Waterfowl But no Oil

ABSTRACT In January 1999, over 200 oiled waterfowl were recovered from the coastal beaches of South Carolina and North Carolina. A large, multiagency response effort was mounted to collect and rehabilitate these birds, and to identify the source of the damaging oil spill. This was the first time on record that the Oil Spill Liability Trust Fund (OSLTF) was used on the East Coast of the Unite States to clean wildlife in the absence of any known spill. A temporary rehabilitation center was established for the bird rescue and recovery operation under the direction of the U.S. Fish and Wildlife Service (USFWS) and the South Carolina Department of Natural Resources (SCDNR), while the U.S. Coast Guard spearheaded efforts to determine the cause and source of the damaging spill. Representatives from a number of government agencies located up and down the eastern seaboard and Gulf Coast worked together to respond to this wildlife damage and identify the source of the spill: the Star Evviva, which discharged 24,700 gallons of heavy fuel oil approximately 30 miles off the coast of South Carolina. Responding agencies used a unified response and innovative techniques to deal with the unusual challenges presented by this event. This paper summarizes the “lessons learned” in that response effort and attempts to provide useful advice concerning wildlife contingency planning and oil spill investigation and identification.

IMAGEJTOOLBOX FOR OCEANOGRAPHY

The oil dischargesin marinas and coastal areas has adversely affected the marine environment thathas becomethe driving force for the early detection of oil spills to allow timely intervention.Synthetic Aperture Radar (SAR) data represents an effective tool that is extensively used for the detection and identification of oil spills in the marine envir

Development of a Simple Gas Chromatographic Method for Differentiation of Spilled Oils

An approach for the fast, preliminary identification and differentiation of fresh oil spills is proposed. Capillary gas chromatography with flame ionization detection for the determination of n-alkane and isoprenoid distribution in oil spill samples is applied. An internal standard method is used for the quantitation of the selected compounds. Five characteristic parameters are checked for adequate presentation. n-Alkanes and isoprenoids are chosen as the most suitable structures for the identification and differentiation of fresh oil spills. In many cases, this information is sufficient to eliminate most of the oils as potential sources of the pollution.