Compound-specific stable carbon isotopic composition of petroleum hydrocarbons as a tool for tracing the source of oil spills

With the increasing demand for and consumption of crude oils, oil spill accidents happen frequently during the transportation of crude oils and oil products, and the environmental hazard they pose has become increasingly serious in China. The exact identification of the source of spilled oil can act as forensic evidence in the investigation and handling of oil spill accidents. In this study, a weathering simulation experiment demonstrates that the mass loss of crude oils caused by short-term weathering mainly occurs within the first 24h after a spill, and is dominated by the depletion of low-molecular weight hydrocarbons (相似文献   

Identification of source of a marine oil-spill using geochemical and chemometric techniques

The current work aimed to identify the source of an oil spill off the coast of Maranhão, Brazil, in September 2005 and effect a preliminary geochemical survey of this environment. A combination of bulk analytical parameters, such as carbon isotope (δ¹³C) and Ni/V ratios, and conventional fingerprinting methods (High Resolution Gas Chromatography and Mass Spectrometry) were used. The use of bulk methods greatly speeded source identification for this relatively unaltered spill: identification of the likely source was possible at this stage. Subsequent fingerprinting of biomarker distributions supported source assignment, pointing to a non-Brazilian oil. Steranes proved the most useful biomarkers for sample correlation in this work. Distribution patterns of environmentally more resilient compound types, such as certain aromatic structures, proved inconclusive for correlation, probably in view of their presence in the background.     

The aegean sea oil spill in the Galicia Coast (NW Spain). I. Distribution and fate of the crude oil and combustion products in subtidal sediments.

The spatial distribution and fate of petrogenic and pyrogenic hydrocarbons in coastal sediments following the Aegean Sea oil spill (Galicia, NW Spain) was investigated through a detailed study of chemical markers. Alkanes and acyclic isoprenoid hydrocarbons were degraded within six months of the accident, but triterpane and sterane distributions were still detectable and were useful in monitoring, respectively, the oil source and weathering. Aromatic steranes were also useful source indicators, and oil degradation was clear from the decrease of certain alkyl dibenzothiophene and phenanthrene isomers. The pyrogenic polycyclic aromatic hydrocarbons produced in the tanker wreck were found more persistent than the petrogenic ones. However, the presence of the oil in the sediments was recognized even one year after the accident and was found particularly preserved in the subsurface layers.     

Oil spill treatment products approval: the UK approach and potential application to the Gulf region

The environmental threat from oil spills remains significant across the globe and particularly in regions of high oil production and transport such as the Gulf. The ultimate damage caused can be limited by mitigation actions that responders deploy. The responsible and appropriate use of oil spill treatment products (e.g. dispersants, sorbents etc.) can offer response options that can result in substantial net environmental benefit. However, the approval and choice of what products to use needs careful consideration. The United Kingdom has had in place a statutory approval scheme for oil spill treatment products for 30 years. It is based on measures of efficiency and environmental acceptability. Two toxicity tests form an integral part of the assessment, the Sea test and the Rocky Shore test, and work on the premise that approved products will not make the situation significantly worse when added to spilled oil. This paper outlines the UK approach and how its rationale might be applied to the approval of products specific for the Gulf region. Issues such as species choice, higher temperatures and salinity and regional environmental conditions are considered.     

Petroleum biodegradation and oil spill bioremediation

Hydrocarbon-utilizing microorganisms are ubiquitously distributed in the marine environment following oil spills. These microorganisms naturally biodegrade numerous contaminating petroleum hydrocarbons, thereby cleansing the oceans of oil pollutants. Bioremediation, which is accomplished by adding exogenous microbial populations or stimulating indigenous ones, attempts to raise the rates of degradation found naturally to significantly higher rates. Seeding with oil degraders has not been demonstrated to be effective, but addition of nitrogenous fertilizers has been shown to increase rates of petroleum biodegradation. In the case of the Exxon Valdez spill, the largest and most thoroughly studied application of bioremediation, the application of fertilizer (slow release or oleophilic) increased rates of biodegradation 3–5 times. Because of the patchiness of oil, an internally conserved compound, hopane, was critical for demonstrating the efficacy of bioremediation. Multiple regression models showed that the effectiveness of bioremediation depended upon the amount of nitrogen delivered, the concentration of oil, and time.     

Integrated assessment for establishing an oil environmental vulnerability map: Case study for the Santos Basin region,Brazil

The growth of maritime transport and oil exploitation activities may increase the risk of oil spills. Thus, plans and actions to prevent or mitigate impacts are needed to minimize the effects caused by oil. However, tools used worldwide to support contingency plans have not been integrated, thus leading to failure in establishing priority areas. This investigation aimed to develop indices of environmental vulnerability to oil (IEVO), by combining information about environmental sensibility to oil and results of numerical modeling of spilled oil. To achieve that, a case study concerning to oil spills scenarios in a subtropical coastal area was designed, and IEVOs were calculated and presented in maps, in order to make the information about the areas’ vulnerability more easily visualized. For summer, the extension of coastline potentially affected by oil was approximately 150 km, and most of the coastline presented medium to high vulnerability. For winter, 230 km coastline would be affected, from which 75% were classified as medium to high vulnerability. Thus, IEVO maps allowed a rapid and clearer interpretation of the vulnerability of the mapped region, facilitating the planning process and the actions in response to an oil spill.     

Extent and frequency of vessel oil spills in US marine protected areas

Little is known about how marine protected areas (MPAs) may be vulnerable to vessel oil spills in the United States. This study investigated individual size, frequency, and total amount of vessel oil spilled in US MPAs, and how characteristics of MPAs and individual spill events influenced spills. Vessel oil spills in US waters (2002-06) and MPA boundaries were mapped. Total number and volume of oil spills inside and outside MPAs were computed. Results show that the presence of a MPA does not seem to prevent vessel oil spills or reduce the amount of oil spilled, and that a variety of MPA attributes (e.g., scale of protection, fishing restrictions, and others) and spill event characteristics (e.g., vessel type, year of spill, and others) affect oil spills inside and outside MPAs. These results can be used to develop MPA rules and marine transportation policies that reduce the vulnerability of sensitive resources to oil spills.     

Long-term biological effects of petroleum residues on fiddler crabs in salt marshes

In September 1969, the Florida barge spilled 700,000L of No. 2 fuel oil into the salt marsh sediments of Wild Harbor (Buzzards Bay, MA). Today the aboveground environment appears unaffected, but a substantial amount of moderately degraded petroleum still remains 8-20cm below the surface. The salt marsh fiddler crabs, Uca pugnax, burrow into the sediments at depths of 5-25cm, and are chronically exposed to the spilled oil. Behavioral studies conducted with U. pugnax from Wild Harbor and a control site, Great Sippewissett marsh, found that crabs exposed to the oil avoided burrowing into oiled layers, suffered delayed escape responses, lowered feeding rates, and achieved lower densities. The oil residues are therefore biologically active and affect U. pugnax populations. Our results add new knowledge about long-term consequences of spilled oil, a dimension that should be included when assessing oil-impacted areas and developing management plans designed to restore, rehabilitate, or replace impacted areas.     

Review of the development of laser fluorosensors for oil spill application

As laser fluorosensors provide their own source of excitation, they are known as active sensors. Being active sensors, laser fluorosensors can be employed around the clock, in daylight or in total darkness. Certain compounds, such as aromatic hydrocarbons, present in petroleum oils absorb ultraviolet laser light and become electronically excited. This excitation is quickly removed by the process of fluorescence emission, primarily in the visible region of the spectrum. By careful choice of the excitation laser wavelength and range-gated detection at selected emission wavelengths, petroleum oils can be detected and classified into three broad categories: light refined, crude or heavy refined.

This paper will review the development of laser fluorosensors for oil spill application, with emphasis on system components such as excitation laser source, and detection schemes that allow these unique sensors to be employed for the detection and classification of petroleum oils. There have been a number of laser fluorosensors developed in recent years, many of which are strictly research and development tools. Certain of these fluorosensors have been ship-borne instruments that have been mounted in aircraft for the occasional airborne mission. Other systems are mounted permanently on aircraft for use in either surveillance or spill response roles.     

Significance of cytochrome P450 system responses and levels of bile fluorescent aromatic compounds in marine wildlife following oil spills

The relationships among cytochrome P450 induction in marine wildlife species, levels of fluorescent aromatic compounds (FAC) in their bile, the chemical composition of the inducing compounds, the significance of the exposure pathway, and any resulting injury, as a consequence of exposure to crude oil following a spill, are reviewed. Fish collected after oil spills often show increases in cytochrome P450 system activity, cytochrome P4501A (CYP1A) and bile fluorescent aromatic compounds (FAC), that are correlated with exposure to polycyclic aromatic hydrocarbons (PAH) in the oil. There is also some evidence for increases in bile FAC and induction of cytochrome P450 in marine birds and mammals after oil spills. However, when observed, increases in these exposure indicators are transitory and generally decrease to background levels within one year after the exposure. Laboratory studies have shown induction of cytochrome P450 systems occurs after exposure of fish to crude oil in water, sediment or food. Most of the PAH found in crude oil (dominantly 2- and 3-ring PAH) are not strong inducers of cytochrome P450. Exposure to the 4-ring chrysenes or the photooxidized products of the PAH may account for the cytochrome P450 responses in fish collected from oil-spill sites. The contribution of non-spill background PAH, particularly combustion-derived (pyrogenic) PAH, to bile FAC and cytochrome P450 system responses can be confounding and needs to be considered when evaluating oil spill effects. The ubiquity of pyrogenic PAH makes it important to fully characterize all sources of PAH, including PAH from natural resources, e.g. retene, in oil spill studies. In addition, such parameters as species, sex, age, ambient temperature and season need to be taken into account. While increases in fish bile FAC and cytochrome P450 system responses, can together, be sensitive general indicators of PAH exposure after an oil spill, there is little unequivocal evidence to suggest a linkage to higher order biological effects, e.g. toxicity, lesions, reproductive failure.     

Potential for photoenhanced toxicity of spilled oil in Prince William Sound and Gulf of Alaska waters

Photoenhanced toxicity is the increase in the toxicity of a chemical in the presence of ultraviolet light (UV) compared to a standard laboratory test conducted with fluorescent lighting (minimal UV). Oil products, weathered oil, and specific polycyclic aromatic compounds present in oil are 2 to greater than 1000 times more toxic in the presence of UV. The photoenhanced toxicity of oil to fish and aquatic invertebrates appears to occur through a process of photosensitization, rather than photomodification of the aqueous phase oil. In photosensitization, the bioaccumulated chemical transfers light energy to other molecules causing toxicity through tissue damage rather than a narcosis mechanism. The available evidence indicates that phototoxic components of oil are specific 3-5 ring polycyclic aromatic hydrocarbons (PAHs) and heterocycles. Determinants of photoenhanced toxicity include the extent of oil bioaccumulation in aquatic organisms and the spectra and intensity of UV exposure. No studies have specifically investigated the photoenhanced toxicity of spilled oil in Alaska waters. Although there are substantial uncertainties, the results of this evaluation indicate there is potential for photoenhanced toxicity of spilled oil in Prince William Sound and the Gulf of Alaska. The potential hazard of photoenhanced toxicity may be greatest for embryo and larval stages of aquatic organisms that are relatively translucent to UV and inhabit the photic zone of the water column and intertidal areas. Photoenhanced toxicity should be considered in oil spill response because the spatial and temporal extent of injury to aquatic organisms may be underestimated if based on standard laboratory bioassays and existing toxicity databases. Additionally, the choice of counter measures and oil removal operations may influence the degree of photoenhanced toxicity.     

An empirical analysis of IOPCF oil spill cost data

This paper reports on recent analysis of oil spill cost data assembled by the International Oil Pollution Compensation Fund (IOPCF). Regression analyses of clean-up costs and total costs have been carried out, after taking care to convert to current prices and remove outliers. In the first place, the results of this analysis have been useful in the context of the ongoing discussion within the International Maritime Organization (IMO) on environmental risk evaluation criteria. Furthermore, these results can be useful in estimating the benefit of regulations that deal with the protection of marine environment and oil pollution prevention.     

Effect of an oil spill from M V Sea Transporter on intertidal meiofauna at Goa,India

Short and long term effects of a fuel oil spill from a grounded ship "M V Sea Transporter" on meiofauna of a sandy beach of central West Coast of India were investigated. A significant reduction in the absolute abundance of meiofauna was observed immediately after 3 days of spillage particularly at Sinquerim beach, the site of spillage. The reduction was most pronounced in density of nematodes and harpacticoid copepods, which were the most dominant groups. Long-term response showed no apparent oil-induced changes at major taxa levels. The population density improved considerably after the cessation of monsoons with a parallel decrease in petroleum hydrocarbon concentration in the sediment. Nematodes recovered more quickly than benthic copepods. No evidence for this could be due to reproductive dynamics in meiobentos. Although the effect of the oil on meiofauna could be seen initially it could not be proved conclusively on a long-term basis. The effects of the oil spill were confounded with seasonal monsoon effects and beach dynamics. The nematode:copepod ratio and the index of trophic diversity (ITD) were inadequate for detecting oil pollution effects. Therefore it may be concluded that in the presence of other environmental factors acting strongly, the effects of oil on meiofauna was strong but of a temporary nature.     

A new technique to estimate initial spill size using a modified fay-type spreading formula

Estimating oil spill size is important for a variety of economic, environmental and legal reasons. One attempt to determine oil spill size by visually assessing the extent of colour regimes in the spill and multiplying the areas of these regimes by thickness values leads to unsatisfactory results. Previous efforts to estimate oil spill size by inverting spreading using formulae like those of Blokker and Fay have also incurred difficulties related to environmental conditions which influence spill spread rate. Data obtained during a series of field experiments, conducted off the Saudi Arabian coastline during the fall of 1982, were used to devise a modification of Fay's spreading formula. The results agree significantly better with the observed areas of the oil spill than Fay's original formula. The modified area formula is then inverted to obtain a formula for initial volume spilled.     

Modeling oil spill trajectory in coastal waters based on fractional Brownian motion

This paper proposes a numerical method to simulate oil spill trajectories, which are affected by the combination of advection, turbulent diffusion and mechanical spreading process, based on a particle tracking algorithm. Recent studies have shown that the trajectories of drifters on the ocean surface have a fractal structure that is far from being described using ordinary Brownian motion. Thus, in modeling the diffusion process, a discrete method has been employed for the generation of fractional Brownian motion (fBm) to illustrate superdiffusive transport. The algorithm is implemented to predict oil slick trajectories following the “Arteaga” oil spill accident that occurred near the Dalian coastal region in 2005. When compared with the observed data and the results of traditional diffusion modeling, the numerical results based on the fBm model are encouraging.     

Review of behaviour of oil in freezing environments

The current knowledge of the physical fate and behaviour of crude oil and petroleum products spilled in Arctic situations is reviewed. The fate and final deposition of oil in marine conditions is presented as based on the extant literature.

Spreading models were evaluated for oil on ice, under ice, in snow, in brash ice, and between blocks of ice. Models of oil transport under sheet and broken ice were considered, both for sea and river conditions. The ability of ice sheets to trap oil is discussed in relation to oil storage capacity. The effects of oil on a growing ice sheet were examined, both in terms of ice formation and the thermal effects of oil inclusions in ice. The migration of oil through ice was reviewed, focussing primarily on the movement through brine channels. The effects of oil on the surface of ice were considered, with emphasis on the effects of surface pools on ice melt. Similar consideration was given to the effects of oil on snow on the surface of ice.

The few quantitative studies of oil in open and dynamic ice conditions are reviewed. Observations of intentional small-scale spills in leads and ice fields are reviewed and compared with observations from real spills. The conditions under which “oil pumping” from leads occurs were quantified. The most common ultimate fate of oil in an ice field is to be released onto the water surface.     

Evaluation of two direct immunoassays for rapid detection of petroleum products on marine birds

To reduce rehabilitation time and improve survival, a practical, objective test is needed to determine if marine birds are contaminated with oil before they enter captivity. The RaPID Assays and EnviroGard immunoassays for detection of polycyclic aromatic hydrocarbons (PAHs) in soil were evaluated for their ability to detect petroleum on feather samples from 30 intermediate fuel oil contaminated and 30 uncontaminated common murres (Uria aalge). Sensitivity, specificity, positive and negative predictive value, precision, and time required to run each assay were determined. The RaPID Assays was 96.7% sensitive and specific, while the EnviroGard assay was 93.3% sensitive, and 90.0% specific. Sensitivity decreased at higher dilutions for both assays. Intra-replicate variation was less than 20%. Our evaluation showed that these immunoassays are rapid and cost-effective methods for detecting oil-contamination on the plumage of seabirds, with the EnviroGard assay being more practical in most oil spill response situations due to ease of use and rapidity of results.     

Scientific management of Mediterranean coastal zone: a hybrid ocean forecasting system for oil spill and search and rescue operations

The oil spill from Prestige tanker showed the importance of scientifically based protocols to minimize the impacts on the environment. In this work, we describe a new forecasting system to predict oil spill trajectories and their potential impacts on the coastal zone. The system is formed of three main interconnected modules that address different capabilities: (1) an operational circulation sub-system that includes nested models at different scales, data collection with near-real time assimilation, new tools for initialization or assimilation based on genetic algorithms and feature-oriented strategic sampling; (2) an oil spill coastal sub-system that allows simulation of the trajectories and fate of spilled oil together with evaluation of coastal zone vulnerability using environmental sensitivity indexes; (3) a risk management sub-system for decision support based on GIS technology. The system is applied to the Mediterranean Sea where surface currents are highly variable in space and time, and interactions between local, sub-basin and basin scale increase the non-linear interactions effects which need to be adequately resolved at each one of the intervening scales. Besides the Mediterranean Sea is a complex reduced scale ocean representing a real scientific and technological challenge for operational oceanography and particularly for oil spill response and search and rescue operations.     

Visualization of spatial patterns and temporal trends for aerial surveillance of illegal oil discharges in western Canadian marine waters

This paper examines the use of exploratory spatial analysis for identifying hotspots of shipping-based oil pollution in the Pacific Region of Canada’s Exclusive Economic Zone. It makes use of data collected from fiscal years 1997/1998 to 2005/2006 by the National Aerial Surveillance Program, the primary tool for monitoring and enforcing the provisions imposed by MARPOL 73/78. First, we present oil spill data as points in a “dot map” relative to coastlines, harbors and the aerial surveillance distribution. Then, we explore the intensity of oil spill events using the Quadrat Count method, and the Kernel Density Estimation methods with both fixed and adaptive bandwidths. We found that oil spill hotspots where more clearly defined using Kernel Density Estimation with an adaptive bandwidth, probably because of the “clustered” distribution of oil spill occurrences. Finally, we discuss the importance of standardizing oil spill data by controlling for surveillance effort to provide a better understanding of the distribution of illegal oil spills, and how these results can ultimately benefit a monitoring program.     

Offshore experiments on styrene spillage in marine waters for risk assessment

Within the context of risk evaluation of chemical spillages into the marine environment, this paper reports on an offshore experiment to study the behaviour of styrene spilled into sea under natural conditions and discusses theoretical approaches. Floating structures were used to enclose the spillage and the gaseous cloud formation, and dissolution processes were in situ monitored. The identification of spill risks for man and marine environment through GESAMP's hazard profile is described for styrene: Styrene is rated as a chemical with a significant health hazard that will float but also evaporate. However, monitoring of the water column in the experiments showed that the concentration of styrene in water during the first hour represents 50% of the product spilled. For the potentially exposed public, the GESAMP hazard rating recommends the closure of beaches and evacuation. The risk assessment developed from experimental data confirms this safety advice.