Large-scale cold water dispersant effectiveness experiments with Alaskan crude oils and Corexit 9500 and 9527 dispersants

There continues to be reluctance in some jurisdictions to use chemical dispersants as a viable countermeasure for accidental oil spills. One argument used by some opponents to dispersant use is that “chemical dispersants do not work effectively in cold water”. To address this issue, the U.S. Minerals Management Service (MMS) funded and conducted two series of large-scale dispersant experiments in very cold water at Ohmsett - The National Oil Spill Response Test Facility, located in Leonardo, New Jersey in February-March 2006 and January-March 2007. Alaska North Slope, Endicott, Northstar and Pt. McIntyre crude oils and Corexit 9500 and Corexit 9527 dispersants were used in the two test series. The crude oils were tested both when fresh and after weathering. Results demonstrated that both Corexit 9500 and Corexit 9527 dispersants were 85-99% effective in dispersing the fresh and weathered crude oils tested at cold temperatures. The MMS expects that results from these test series will assist government regulators and responders in making science based decisions on the use of dispersants as a response tool for oil spills in the Arctic.     

Superhydrophobic and superoleophillic surface of porous beaded electrospun polystrene and polysytrene-zeolite fiber for crude oil-water separation

This research presents a cheap route procedure for the preparation of a potential adsorbent with superhydrophobic/superoleophillic properties for selective removal of crude oil from water. In this study, expanded polystyrene (EPS) was electrospun to produce beaded fibers in which zeolite was introduced to the polymer matrix in order to impart rough surface to non-beaded fiber. Films of the EPS and EPS/Zeolite solutions were also made for comparative study. The electrospun fibers EPS, EPS/Zeolite and resultant films were characterized using SEM, BET, FTIR and optical contact angle. The fibers exhibited superhydrophobic and superoleophillic wetting properties with water (>150⁰) and crude oil (0⁰). The selective removal of crude oil presents new opportunity for the re-use of EPS as adsorbent in petroleum/petrochemical industry.     

Plasmid incidence in marine bacteria isolated from petroleum polluted sites on different petroleum hydrocarbons

Oil-degrading bacteria isolated from oil spills, an industrial bay, and an offshore oil field by liquid enrichment on crude oils and polynuclear aromatic hydrocarbon compounds were screened for extra-chromosomal DNA. Plasmids were detected in 21% of the strains isolated on whole crude oil and in 17% of the strains isolated on polynuclear aromatic hydrocarbons. Multiple plasmids were observed in 50% of the plasmid-containing strains. Pseudomonas was the predominant genus isolated during the study. Plasmids do not appear to be of importance to these strains during degradation of freshly introduced oil at a nonpolluted site such as might be the case in an ocean oil spill. Plasmids do appear to be significant in the adaptation of Pseudomonas species to chronic petroleum pollution.     

Nanoporous polystyrene fibers for oil spill cleanup

The development of oil sorbents with high sorption capacity, low cost, scalable fabrication, and high selectivity is of great significance for water environmental protection, especially for oil spillage on seawater. In this work, we report nanoporous polystyrene (PS) fibers prepared via a one-step electrospinning process used as oil sorbents for oil spill cleanup. The oleophilic-hydrophobic PS oil sorbent with highly porous structures shows a motor oil sorption capacity of 113.87 g/g, approximately 3-4 times that of natural sorbents and nonwoven polypropylene fibrous mats. Additionally, the sorbents also exhibit a relatively high sorption capacity for edible oils, such as bean oil (111.80 g/g) and sunflower seed oil (96.89 g/g). The oil sorption mechanism of the PS sorbent and the sorption kinetics were investigated. Our nanoporous material has great potential for use in wastewater treatment, oil accident remediation and environmental protection.     

Measuring ignitability for in situ burning of oil spills weathered under Arctic conditions: from laboratory studies to large-scale field experiments

This paper compares the ignitability of Troll B crude oil weathered under simulated Arctic conditions (0%, 50% and 90% ice cover). The experiments were performed in different scales at SINTEF’s laboratories in Trondheim, field research station on Svalbard and in broken ice (70-90% ice cover) in the Barents Sea. Samples from the weathering experiments were tested for ignitability using the same laboratory burning cell. The measured ignitability from the experiments in these different scales showed a good agreement for samples with similar weathering. The ice conditions clearly affected the weathering process, and 70% ice or more reduces the weathering and allows a longer time window for in situ burning. The results from the Barents Sea revealed that weathering and ignitability can vary within an oil slick. This field use of the burning cell demonstrated that it can be used as an operational tool to monitor the ignitability of oil spills.     

Oil viscosity limitation on dispersibility of crude oil under simulated at-sea conditions in a large wave tank

This study determined the limiting oil viscosity for chemical dispersion of oil spills under simulated sea conditions in the large outdoor wave tank at the US National Oil Spill Response Test Facility in New Jersey. Dispersant effectiveness tests were completed using crude oils with viscosities ranging from 67 to 40,100 cP at test temperature. Tests produced an effectiveness-viscosity curve with three phases when oil was treated with Corexit 9500 at a dispersant-to-oil ratio of 1:20. The oil viscosity that limited chemical dispersion under simulated at-sea conditions was in the range of 18,690 cP to 33,400 cP. Visual observations and measurements of oil concentrations and droplet size distributions in the water under treated and control slicks correlated well with direct measurements of effectiveness. The dispersant effectiveness versus oil viscosity relationship under simulated at sea conditions at Ohmsett was most similar to those from similar tests made using the Institut Francais du Pétrole and Exxon Dispersant Effectiveness (EXDET) test methods.     

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.     

On the SAR derived alert in the detection of oil spills according to the analysis of the EGEMP

Satellite services that deliver information about possible oil spills at sea currently use different labels of “confidence” to describe the detections based on radar image processing. A common approach is to use a classification differentiating between low, medium and high levels of confidence. There is an ongoing discussion on the suitability of the existing classification systems of possible oil spills detected by radar satellite images with regard to the relevant significance and correspondence to user requirements. This paper contains a basic analysis of user requirements, current technical possibilities of satellite services as well as proposals for a redesign of the classification system as an evolution towards a more structured alert system. This research work offers a first review of implemented methodologies for the categorisation of detected oil spills, together with the proposal of explorative ideas evaluated by the European Group of Experts on satellite Monitoring of sea-based oil Pollution (EGEMP).     

The Dona Marika oil spill

Last August, 3,000 tons of petrol (gasolene) was spilled in Milford Haven when the tanker, Dona Marika, ran aground. Since most documented oil spills in British waters have been of crude oil, there is considerable interest in knowing the damage caused by this spillage of a refined oil product.     

Regularities in the transformation of oil pollution in watercourses based on long-term observational data

Results of long-term studies of crude oil transformations in water and bottom sediments of river ecosystems polluted as a result of oil spills are presented. Regularities in changes in the concentration ratio of hydrocarbon and resinous components of oil in water and bottom sediments under the effect of natural selfpurification processes of aquatic ecosystems are found out.     

Used Motor Oil as a Source of MTBE, TAME, and BTEX to Ground Water

Methyl tert-butyl ether (MTBE), the widely used gasoline oxygenate, has been identified as a common ground water contaminant, and BTEX compounds (benzene, toluene, ethylbenzene, and xylenes) have long been associated with gasoline spills. Because not all instances of ground water contamination by MTBE and BTEX can be attributed to spills or leaking storage tanks, other potential sources need to be considered. In this study, used motor oil was investigated as a potential source of these contaminants. MTBE in oil was measured directly by methanol extraction and gas chromatography using a flame ionization detector (GC/FID). Water was equilibrated with oil samples and analyzed for MTBE, BTEX, and the oxygenate tert-amyl methyl ether (TAME) by purge- and-trap concentration followed by GC/FID analysis. Raoult's law was used to calculate oil-phase concentrations of MTBE, BTEX, and TAME from aqueous-phase concentrations. MTBE, TAME, and BTEX were not detected in any of five new motor oil samples, whereas these compounds were found at significant concentrations in all six samples of the used motor oil tested for MTBE and all four samples tested for TAME and BTEX. MTBE concentrations in used motor oil were on the order of 100 mg/L. TAME concentrations ranged from 2.2 to 87 mg/L. Concentrations of benzene were 29 to 66 mg/L, but those of other BTEX compounds were higher, typically 500 to 2000 mg/L.     

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.     

A Dynamic Model to Simulate Spills of Fuel and Diesel Oil in the Terrestrial Environment during Extreme Fluvial Floods

Extreme fluvial floods may cause severe contamination with fuel oil and diesel, originating from gasoline pipes and tanks in private households and industrial areas, respectively. Geo‐referenced oil spills in the region of Bitterfeld (Germany) after extreme flood events, such as in August 2002, were simulated using the two‐dimensional (2D) Finite Element model system Telemac2D, which is subdivided into a hydrodynamic (Telemac‐2D) and a transport module (Subief2D). Fuel oil settled via adhesion showed a thickness of less than 1.0 mm. Fuel oil concentrations on the flood wave amounted up to 80 g m^–3 in the vicinity of the point sources. At a distance of several hundred meters downstream of the point sources, the fuel oil concentrations were calculated to be zero. Settled areas were only partially contaminated with fuel oil. While one village experienced severe oil contamination, the town of Bitterfeld was almost unaffected by oil spills. It was demonstrated that the 2D transport model applied is capable of simulating fuel oil spills during extreme high waters in the terrestrial environment. Such simulations of fuel oil spills will feed into a GIS‐based decision support system of flood protection.     

Inhibition of Fertilization and Larval Metamorphosis of the Coral Acropora millepora (Ehrenberg, 1834) by Petroleum Products

Accidental oil spills from ships or rigs and inputs of effluent such as production formation water (PFW) are key perceived threats to tropical biota from industry activities. Scleractinian corals are an important functional component of tropical reefs and the abundance, diversity and resilience of coral communities can be used as an indicator of ecosystem health. In this paper, we report the effects of petroleum products, including water accommodated fractions (WAF) of crude oil, PFW and dispersant (Corexit 9527), on fertilization and larval metamorphosis of the widespread scleractinian coral, Acropora millepora (Ehrenberg, 1834) in laboratory-based assays. At 20% v/v PFW fertilization was inhibited by 25%. This concentration was equivalent 0.0721 mg l⁻¹ total hydrocarbon (THC). In contrast, larval metamorphosis was more sensitive to this effluent, with 98% metamorphosis inhibited at the same concentration. Crude oil WAF did not inhibit fertilization of gametes until dispersant was introduced. Dispersed oil was slightly more toxic to fertilization than dispersant alone, suggesting toxicity to that event may be additive. The minimum concentration of dispersed oil which inhibited fertilization was 0.0325 mg l⁻¹ THC. Larval metamorphosis was more sensitive than fertilization to crude oil. Although crude oil and dispersant inhibited larval metamorphosis individually, this toxicity was magnified when larvae were exposed to combinations of both. Crude oil inhibited metamorphosis at 0.0824 mg l⁻¹ THC and at 0.0325 mg l⁻¹ THC when dispersed in 10% v/v (dispersant/oil). Management of petroleum-related risks to spawning corals should consider not only the occurrence of the annual coral spawning event, but also the subsequent 1–3-week period during which most larval metamorphosis and recruitment occur.     

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.     

Critical evaluation of CROSERF test methods for oil dispersant toxicity testing under subarctic conditions

The aquatic organisms toxicity testing protocols developed by the chemical response to oil spills: Ecological Research Forum (CROSERF) were evaluated for applicability to assessing chemical dispersant toxicity under subarctic conditions. CROSERF participants developed aquatic toxicity testing protocols with the foremost objective of standardizing test methods and reducing inter-laboratory variability. A number of refinements are recommended to adapt the CROSERF protocols for testing with subarctic species under conditions of expected longer oil persistence. Recommended refinements of the CROSERF protocols include testing fresh and moderately weathered oil under conditions of moderate mixing energy, preparing toxicity test solutions using variable dilutions rather than variable loading, performing tests with subarctic species using static exposures in open chambers, increasing the duration of tests from 4 to 7 days, quantifying approximately 40 PAHs and their alkyl homologs, assessing the potential for photoenhanced toxicity, and incorporating a bioaccumulation endpoint by measuring tissue concentrations of PAHs. Refinements in the preparation of oil dosing solutions, exposure and light regimes, and analytical chemistry should increase the utility of the test results for interpreting the toxicity of chemically dispersed oil and making risk management decisions regarding dispersant use under subarctic conditions.     

Superoleophillic electrospun polystrene/exofoliated graphite fibre for selective removal of crude oil from water

During oil spills, the aquatic environment is greatly endangered because oil floats on water making the penetration of sunlight difficult therefore primary productivity is compromised, birds and aquatic organisms are totally eliminated within a short period. It is therefore essential to remove the oil from the water bodies after the spillage. This work reports on the fabrication of oil loving electrospun polystyrene-exofoliated graphite fibre with hydrophobic and oleophillic surface properties. The fibre was applied for the selective adsorption of crude oil from simulated crude oil spillage on water. The maximum oil adsorption capacity of the EPS/EG was 1.15 kg/g in 20 min while the lowest oil adsorption capacity was 0.81 kg/g in 10 min. Cheap oil adsorbent was developed with superoleophillic and superhydrophobic properties.     

Characterization of alkanes, hopanes, and polycyclic aromatic hydrocarbons (PAHs) in tar-balls collected from the East Coast of Peninsular Malaysia

The East Coast of Peninsular Malaysia faces the South China Sea and is vulnerable to oil pollution because of intense petroleum production activities in the area. The South China Sea is also a favored route for supertankers carrying crude oil to the Far East. Consequently, oil spills can occur, causing pollution and contamination in the surrounding areas. Residual oil spills stranded on coastal beaches usually end up as tar-balls. Elucidating the sources of tar-balls using a molecular marker approach is essential in assessing environmental impacts and perhaps settling legal liabilities for affected parties. This study utilizes a multimodal molecular marker approach through the use of diagnostic ratios of alkanes, hopanes, and polycyclic aromatic hydrocarbons (PAHs) to determine the source, distribution and weathering of tar-balls. Hopane ratios (e.g., C29/C30, and summation C31-C35/C30 ratios) were used to identify the sources of tar-balls. The weathering effects were distinguished by using alkanes, namely the unresolved complex mixture (UCM) and low molecular weight/high molecular weight (L/H) ratios. Similarly, PAHs were also used for the determination of weathering processes undergone by the tar-balls. This multimodal molecular marker gave a very strong indication of the sources of tar-balls in this study. For example, 16 out of 17 samples originated from South East Asian Crude Oil (SEACO) with one sample from Merang, Terengganu originating from North Sea Oil (Troll). The TRME-2 sample may have come from a supertanker's ballast water discharge. The second possibility is that the tar-ball may have been transported via oceanographic currents. All 'weathered' sample characterizations were based on the presence of UCM and other ratios. The multimodal molecular marker approach applied in this study has enabled us to partially understand the transport behavior of tar-balls in the marine environment and has revealed insights into the weathering process of tar-balls.     

Influence of illumination on phytotoxicity of crude oil

Petroleum products discharged at the water surface are rapidly modified under the effect of physico-chemical and biological transformations, themselves closely dependent on ecological factors. The rôle of some of these, such as illumination, may be particularly significant. This report deals with the effect of this parameter on the phytotoxicity of Kuwait crude oil on the primary production of a microalga: (Phaeodactylum tricornutum) and marine plankton communities.The result of these investigations indicates that the toxicity of extracts made from a crude oil is about two to three times greater when the latter is previously subjected to illumination of sufficient intensity and duration. The incorporation of a chemical dispersant (Corexit 8666) magnifies this phenomenon. In the case of a weathered crude oil mixed in equal parts with the dispersant, illumination raises the toxicity of the extracts by a factor of about 30.     

Use of a by-product of peat excavation, cotton grass fibre, as a sorbent for oil-spills

The sorbents used to collect oil in case of oil-spills are mostly synthetic, which limits the possibilities of their disposal. We studied the absorption capacities and rates of cotton grass fibre, a by-product of peat excavation, and cotton grass mats for several oil types and compared them with a synthetic, commercially available oil sorbent. We found cotton grass fibre to have superior absorption properties: Cotton grass sorbent absorbed oil approximately two to three times as much, and two to three times as fast as the synthetic one. Cotton grass fibre absorbed no measurable amount of water in the conditions used in the tests making it ideal for absorbing oil from the surface of water. In removing diesel oil from the surface of water, the efficiency was over 99% up to an absorbing factor of 20 times its own weight. The biodegradable cotton grass fibre proved to be an effective oil sorbent with low raw-material costs.