Stimulating the Biodegradation of Crude Oil with Biodiesel Preliminary Results

Experiments using biodiesel derived from vegetable oils have demonstrated the considerable potential for removing crude oil from contaminated beaches. During laboratory studies in small boxes, contaminated sand treated with biodiesel also demonstrated the rapid biodegradation of the crude oil. Water soluble components were washed through the sand columns and these components subsequently precipitated with cold storage. This solid fraction was not soluble in organic solvents but could be re-dissolved in dilute acid. The sediments after four weeks were black in colour due to the precipitation of metal sulphides although no H₂S was generated because the pH of the seawater kept the sulphides in solution. Further work is investigating which components of the oil were degraded and what products were formed.     

Estimating Time Windows for Burning Oil at Sea: Processes and Factors

This paper discusses processes and factors for estimating time period windows of in situ burning of spilled oil at sea. Time-periods of in situ burning of Alaska North Slope (ANS) crude oil are estimated using available data. Three crucial steps are identified. The First Step is to determine the time it takes for the evaporative loss to reach the known or established limitation for evaporation and compare this time-period with estimated time of ignition at the ambient wind and sea temperatures. The Second Step is to determine the water up-take of the spilled oil and compare it with the known or established limitation for water-in-oil content. The Third Step is to determine the necessary heat load from the igniter to bring the surface temperature of the spilled oil to its flash point temperature so that it will burn at the estimated time period for ignition of the slick.     

Oil and water separation in marine oil spill clean-up operations

This paper discusses the changes in spilled oil properties over time and how these changes affect differential density separation. It presents methods to improve differential density, and operational effectiveness when oil-water separation is incorporated in a recovery system. Separators function because of the difference in density between oil and seawater. As an oil weathers this difference decreases, because the oil density increases as the lighter components evaporate. The density also increases as the oil incorporates water droplets to form a water-in-oil emulsion. These changes occur simultaneously during weathering and reduce the effectiveness of separators. Today, the state-of-the-art technologies have limited capabilities for separating spilled marine oil that has weathered.For separation of emulsified water in an emulsion, the viscosity of the oil will have a significant impact on drag forces, reducing the effect of gravity or centrifugal separation. Since water content in an emulsion greatly increases the clean up volume (which can contain as much as two to five times as much water as the volume of recovered oil), it is equally important to remove water from an emulsion as to remove free water recovered owing to low skimmer effectiveness. Removal of both free water and water from an emulsion, has the potential to increase effective skimming time, recovery effectiveness and capacity, and facilitate waste handling and disposal. Therefore, effective oil and water separation in marine oil spill clean-up operations may be a more critical process than credited because it can mean that fewer resources are needed to clean up an oil spill with subsequent effects on capital investment and basic stand-by and operating costs for a spill response organization.A large increase in continuous skimming time and recovery has been demonstrated for total water (free and emulsified water) separation. Assuming a 200 m³ storage tank, 100 m³ h⁻¹ skimmer capacity, 25% skimmer effectiveness, and 80% water content in the emulsion, the time of continuous operation (before discharge of oil residue is needed), increases from 2 to 40 h and recovery of oil residue from 10 to 200 m³.Use of emulsion breakers to enhance and accelerate the separation process may, in some cases, be a rapid and cost effective method to separate crude oil emulsions. Decrease of water content in an emulsion, by heating or use of emulsion breakers and subsequent reduction in viscosity, may improve pumpability, reduce transfer and discharge time, and can reduce oily waste handling, and disposal costs by a factor of 10. However, effective use of emulsion breakers is dependant on the effectiveness of the product, oil properties, application methods and time of application after a spill.     

A Numerical Simulation of an Oil Spill in Tokyo Bay

An oil spill accident happened in Tokyo Bay on 2 July 1997. About 1500 m³ of crude oil was released on the sea surface from the Japanese tanker Diamond Grace. An oil spill model is applied to simulate the fate of spilled oil. The Lagrangian discrete-parcel method is used in the model. The model considers current advection, horizontal diffusion, mechanical spreading, evaporation, dissolution and entrainment in simulating the oil slick transformation. It can calculate the time evolution of the partition of spilled oil on the water surface, in the water column and the sedimentation on the bottom. A continuous source at constant rate is set up as a tanker off the coast of Yokohama. The grid size is 1 km in the calculation domain. The residual flow simulated by a 3-D hydraulic model and observed wind data are used for advection. The simulated distribution of oil spreading agrees well with observations from satellite remote-sensing.     

Oil/Suspended Particulate Material Interactions and Sedimentation

The interactions of physically dispersed oil droplets with suspended particulate material (SPM) can be important for the transport of bulk quantities of spilled crude oil and polycyclic aromatic hydrocarbons (PAH) to subtidal sediments. The literature regarding oil/SPM interactions is reviewed, and results from whole-oil droplet/SPM interaction kinetics and pure-component (Prudhoe Bay crude oil distillate cut) equilibrium partitioning experiments are presented. The effects of oil type, SPM characteristics, and salinity on the interaction rates are examined, and the importance of whole-oil droplet/SPM interactions on particle agglomeration and settling behavior are discussed. Whole-oil droplet/SPM interactions are retarded as oil droplet dispersion into the water column is inhibited by oil viscosity increases due to evaporation weathering and water-in-oil emulsification. Compared to whole oil droplet/SPM interactions, dissolved-component/SPM adsorption is not as significant for transport of individual components to sediments. The information presented in this paper can be used to augment computer-based models designed to predict oil-spill trajectories, oil-weathering behavior, and spilled oil impacts to the marine environment.     

Oil Erosion in an Annular Flume by Seawater of Varying Turbidities: A Critical Bed Shear Stress Approach

Laboratory experiments were conducted in an annular flume using Hibernia crude oil to determine: (1) the critical shear stress (τ_c) necessary to remove stranded oil from a surface by resuspension and (2) the effect of suspended sediment concentrations (SSCs) on the oil erosion processes. Two types of erosion were evident: Type I––solution and erosion of soluble aromatics; and Type II––mass erosion of visible droplets. In particulate free seawater at 13 °C, the Type II erosion threshold τ_cII is 5.0 Pa. This is equivalent to a mean current velocity (U_y) of 0.55 m s⁻¹. At U_y values <0.55 m s⁻¹, Type I erosion occurred as shown by the increase of oil concentrations without visible erosion of the oil surface. Temperature has a strong control on the threshold and rate of oil erosion: the threshold for Type I erosion at 4 °C was higher and erosion rate lower than at 13 °C. No Type II erosion was observed at 4 °C. SSCs also affects the entrainment of oil. Oil erosion was most efficient at moderate SSCs. At very high SSCs, turbulence suppression and drag reduction became effective and oil erosion rate decreased. SSC at 200–250 mg l⁻¹ were observed to give maximum erosion efficiency and is therefore suggested as the optimal concentration for erosion and elimination of heavy crude oil at a water temperature of 13 °C.     

Norwegian Testing of Emulsion Properties at Sea--The Importance of Oil Type and Release Conditions

This paper is a review of the major findings from laboratory studies and field trials conducted in Norway in recent years on the emulsification of oils spilled at sea. Controlled bench-scale and meso-scale basin experiments using a wide spectrum of oils have revealed that both the physico-chemical properties of the oils and the release conditions are fundamental determinants of the rate of emulsion formation, for the rheological properties of the emulsion formed and for the rate of natural dispersion at sea.During the last decade, several series of full-scale field trials with experimental releases of various crude oils have been undertaken in the North Sea and the Norwegian Sea. These have involved both sea surface releases, underwater pipeline leak simulations (release of oil under low pressure and no gas) and underwater blowout simulations (pressurized oil with gas) from 100 and 850 m depth. The field trials have been performed in co-operation with NOFO (Norwegian Clean Seas Association for Operating Companies), individual oil companies, the Norwegian Pollution Control Authority (SFT) and Minerals Management Services (MMS). SINTEF has been responsible for the scientific design and monitoring during these field experiments. The main objectives of the trials have been to study the behaviour of different crude oils spilled under various conditions and to identify the operational and logistical factors associated with different countermeasure techniques.The paper gives examples of data obtained on the emulsification of spilled oil during these field experiments. The empirical data generated from the experimental field trials have been invaluable for the validation and development of numerical models at SINTEF for predicting the spreading, weathering and behaviour of oil released under various conditions. These models are extensively used in contingency planning and contingency analysis of spill scenarios and as operational tools during spill situations and combat operations.     

Value addition of vegetable wastes by solid-state fermentation using Aspergillus niger for use in aquafeed industry

Vegetable waste typically has high moisture content and high levels of protein, vitamins and minerals. Its value as an agricultural feed can be enhanced through solid-state fermentation (SSF). Two experiments were conducted to evaluate the nutritional status of the products derived by SSF of a mixture of dried vegetable waste powder and oil cake mixture (soybean flour, wheat flour, groundnut oil cake and sesame oil cake at 4:3:2:1 ratio) using fungi Aspergillus niger S₁4, a mangrove isolate, and A. niger NCIM 616. Fermentation was carried out for 9 days at 35% moisture level and neutral pH. Significant (p < 0.05) increase in crude protein and amino acids were obtained in both the trials. The crude fat and crude fibre content showed significant reduction at the end of fermentation. Nitrogen free extract (NFE) showed a gradual decrease during the fermentation process. The results of the study suggest that the fermented product obtained on days 6 and 9 in case of A. niger S₁4 and A. niger NCIM 616 respectively contained the highest levels of crude protein.     

Toxicity Evaluation with the Microtox Test to Assess the Impact of In Situ Oiled Shoreline Treatment Options: Natural Attenuation and Sediment Relocation

Changes in the toxicity levels of beach sediment, nearshore water, and bottom sediment samples were monitored with the Microtox^® Test to evaluate the two in situ oil spill treatment options of natural attenuation (natural recovery--no treatment) and sediment relocation (surf washing). During a series of field trials, IF-30 fuel oil was intentionally sprayed onto the surface of three mixed sediment (pebble and sand) beaches on the island of Spitsbergen, Svalbard, Norway (78°56^′ N, 16°45^′ E). At a low wave-energy site (Site 1 with a 3-km wind fetch), where oil was stranded within the zone of normal wave action, residual oil concentrations and beach sediment toxicity levels were significantly reduced by both options in less than five days. At Site 3, a higher wave-energy site with a 40-km wind fetch, oil was intentionally stranded on the beach face in the upper intertidal/supratidal zones, above the level of normal wave activity. At this site under these experimental conditions, sediment relocation was effective in accelerating the removal of the oil from the sediments and reducing the Microtox^® Test toxicity response to background levels. In the untreated (natural attenuation) plot at this site, the fraction of residual oil remaining within the beach sediments after one year (70%) continued to generate a toxic response. Chemical and toxicological analyses of nearshore sediment and sediment-trap samples at both sites confirmed that oil and suspended mineral fines were effectively dispersed into the surrounding environment by the in situ treatments. In terms of secondary potential detrimental effects from the release of stranded oil from the beaches, the toxicity level (Microtox^® Test) of adjacent nearshore sediment samples did not exceed the Canadian regulatory limit for dredged spoils destined for ocean disposal.     

Biodegradation of Dispersed Forties Crude and Alaskan North Slope Oils in Microcosms Under Simulated Marine Conditions

For oil spills in the open sea, operational experience has found that conventional response techniques, such as mechanical recovery, tend to remove only a small fraction of oil during major spills, a recent exception being the Mississippi River spill in Louisiana [Spill Sci. Technol. Bull. 7 (2002) 155]. By contrast, the use of dispersants can enable significant fractions of oil to be removed from the sea surface by dispersing the oil into the water column. It is thought that once dispersed the oil can biodegrade in the water column, although there is little information on the mechanism and rate of biodegradation. Two studies were undertaken on dispersion, microbial colonisation and biodegradation of Forties crude and Alaskan North Slope (ANS) oils under simulated marine conditions. The study using the Forties crude lasted 27 days and was carried out in conditions simulating estuarine and coastal conditions in waters around the UK (15 °C and in the presence of nutrients, 1 mg N-NO₃/l), while the ANS study simulated low temperature conditions typical of Prince William Sound (8 °C) and took place over 35 days. The results of both studies demonstrated microbial colonisation of oil droplets after 4 days, and the formation of neutrally buoyant clusters consisting of oil, bacteria, protozoa and nematodes. By day 16, the size of the clusters increased and they sank to the bottom of the microcosms, presumably because of a decrease in buoyancy due to oil biodegradation, however biodegradation of n-alkanes was confirmed only in the Forties study. No colonisation or biodegradation of oil was noted in the controls in which biological action was inhibited. Oil degrading bacteria proliferated in all biologically active microcosms. Without dispersant, the onset of colonisation was delayed, although microbial growth rates and population size in ANS were greater than observed with the Forties. This difference reflected the greater droplet number seen with ANS at 8 °C than with Forties crude at 15 °C. Although these studies differed by more than one variable, complicating comparison, the findings suggest that dispersion (natural or chemical) changes the impact of the oil on the marine environment, potentially having important implications for management of oil spills in relation to the policy of dispersant use in an oil spill event.     

Determination of the Burning Characteristics of a Slick of Oil on Water

The burning rate of a slick of oil on a water bed is characterized by three distinct processes, ignition, flame spread and burning rate. Although all three processes are important, ignition and burning rate are critical. The former, because it defines the potential to burn and the latter because of the inherent possibility of boilover. Burning rate is calculated by a simple expression derived from a one-dimensional heat conduction equation. Heat feedback from the flame to the surface is assumed to be a constant fraction of the total energy released by the combustion reaction. The constant fraction (χ) is named the burning efficiency and represents an important tool in assessing the potential of in situ burning as a counter-measure to an oil spill. By matching the characteristic thermal penetration length scale for the fuel/water system and an equivalent single layer system, a combined thermal diffusivity can be calculated and used to obtain an analytical solution for the burning rate. Theoretical expressions were correlated with crude oil and heating oil, for a number of pool diameters and initial fuel layer thickness. Experiments were also conducted with emulsified and weathered crude oil. The simple analytical expression describes well the effects of pool diameter and initial fuel layer thickness permitting a better observation of the effects of weathering, emulsification and net heat feedback to the fuel surface. Experiments showed that only a small fraction of the heat released by the flame is retained by the fuel layer and water bed (of the order of 1%). Ignition has been studied to provide a tool that will serve to assess a fuels ease to ignite under conditions that are representative of oil spills. Two different techniques are used, piloted ignition when the fuel is exposed to a radiant heat flux and flash point as measured by the ASTM D56 Tag Closed Cup Test. Two different crude oils were used for these experiments, ANS and Cook Inlet. Crude oils were tested in their natural state and at different levels of weathering, showing that piloted ignition and flash point are strong functions of weathering level.     

Determination of the Thermal Efficiency of Pre-boilover Burning of a Slick of Oil on Water

The burning rate of a slick of oil on a water bed is calculated by a simple expression derived from a one-dimensional heat conduction equation. Heat feedback from the flame to the surface is assumed to be a constant fraction of the total energy released by the combustion reaction. The constant fraction (χ) is named the burning efficiency and represents an important tool in assessing the potential of in situ burning as a counter-measure to an oil-spill. The total heat release, as a function of the pool diameter, is obtained from an existing correlation. It is assumed that radiative heat is absorbed close to the fuel surface, that conduction is the dominant mode of heat transfer in the liquid phase and that the fuel boiling temperature remains constant. By matching the characteristic thermal penetration length scale for the fuel/water system and an equivalent single layer system, a combined thermal diffusivity can be calculated and used to obtain an analytical solution for the burning rate. Theoretical expressions were correlated with crude oil and heating oil, for a number of pool diameters and initial fuel layer thickness. Experiments were also conducted with emulsified and weathered crude oil. The simple analytical expression describes well the effects of pool diameter and initial fuel layer thickness permitting a better observation of the effects of weathering, emulsification and net heat feedback to the fuel surface. Experiments showed that only a small fraction of the heat released by the flame is retained by the fuel layer and water bed (of the order of 1%). The effect of weathering on the burning rate decreases with the weathering period and that emulsification results in a linear decrease of the burning rate with water content.     

Effect of polyethylene terephthalate (PET) on the pyrolysis of brominated flame retardant-containing high-impact polystyrene (HIPS-Br)

Pyrolysis of brominated flame retardant-containing high-impact polystyrene (HIPS-Br) was performed at 430°C in the presence of 0.1 wt% of polyethylene terephthalate (PET) in a Pyrex glass reactor. Two different types of brominated flame retardants (decabromodiphenyl ether and decabromodiphenyl ethane) with or without antimony trioxide (as synergist) 5 wt% were used. The presence of PET had a significant effect on the material balance, decreasing the gaseous product and increasing the residue. The type of flame retardant had no effect on the yield of liquid product; however, the presence of Sb resulted in a marked difference in the distribution of decomposition products. Analysis by a gas chromatograph equipped with a flame ionization detector showed that the hydrocarbons were distributed in the range n-C₇ to n-C₂₅ with major peaks at n-C₉ and n-C₁₇. The presence of PET increased the formation of brominated compounds by several times and affected both the type and quantity of polybrominated compounds. The liquid products obtained from the pyrolysis of HIPS-Br/PET have to be treated before they can be used     

Composition and Toxicity of Residual Bunker C Fuel Oil in Intertidal Sediments After 30 Years

In 1970, approximately 2000 m³ of Bunker C crude oil impacted 300 km of Nova Scotia’s coastline following the grounding of the tanker Arrow. Only 10% of the contaminated coast was subjected to cleanup, the remainder was left to cleanse naturally. To determine the long-term environmental impact of residual oil from this spill event, samples of sediment and interstitial water were recovered in 1993, 1997 and 2000 from a sheltered lagoon in Black Duck Cove. This heavily oiled site was intentionally left to recover on its own. Visual observations and chemical analysis confirmed that substantial quantities of the weathered cargo oil were still present within the sediments at this site. However, direct observations of benthic invertebrate abundance suggest that natural processes have reduced the impacts of the residual oil. To confirm this hypothesis, sediment and interstitial water samples from Black Duck Cove were assessed with a comprehensive set of biotests and chemical assays.Residual oil in the sediments had limited effect on hepatic CYP1A protein levels and mixed function oxygenase (MFO) induction in winter flounder (Pleuronectes americanus). No toxicity was detected with the Microtox solid phase test (Vibrio fischeri). Significant sediment toxicity was detected by the amphipod survival test (Eohaustorius estuarius) in four out of the eight contaminated sediments. Interstitial water samples were deemed non-toxic by the Microtox 100% test (Vibrio fischeri) and the echinoid fertilization test (Lytechinus pictus). Sediment elutriates were also found to be non-toxic in the grass shrimp embryo-larval toxicity (GSELTOX) test (Palaemonetes pugio).Recovery at this contaminated site is attributed to natural processes that mediated biodegradation and physical removal of oil from the sediments. In support of the latter mechanism, mineralization experiments showed that all test sediments had the capacity for hexadecane, octacosane and naphthalene degradation, while chemical analysis confirmed that the Bunker C oil from the Arrow had undergone substantial biodegradation.     

Removal of Oil from the Sea Surface through Particulate Interactions: Review and Prospectus

The fate of oil spilled in coastal zones depends in large part on the interactions with environmental factors existing within a short time of the spill event. In addition to weathering which produces changes in the chemistry of the hydrocarbon stock, physical interactions between oil and suspended particulate matter (SPM), both organic and inorganic, play a role in determining the dispersal and sedimentation rates of the spill. This in turn affects the degradation rate of the oil. This paper provides a comprehensive literature review of the role of oil–particle interactions in removal of petroleum hydrocarbons from the sea surface and provides estimates of the degree to which SPM may augment the deposition of oil. Both field and laboratory observations have shown widely varying rates of oil removal due to particulate interactions. The discussion covers the interaction between oil weathering, injection, sinking, adsorption, microbial processes, flocculation and ingestion by zooplankton, which all contribute to packaging oil and SPM into settling aggregates.     

The technology windows-of-opportunity for marine oil spill response as related to oil weathering and operations

This paper identifies and estimates time periods as ‘windows-of-opportunity’ where specific response methods, technologies, equipment, or products are more effective in clean-up operations for several oils. These windows have been estimated utilizing oil weathering and technology performance data as tools to optimize effectiveness in marine oil spill response decision-making. The windows will also provide data for action or no-action alternatives. Crude oils and oil products differ greatly in physical and chemical properties, and these properties tend to change significantly during and after a spill with oil aging (weathering). Such properties have a direct bearing on oil recovery operations, influencing the selection of response methods and technologies applicable for clean up, including their effectiveness and capacity, which can influence the time and cost of operations and the effects on natural resources.The changes and variations in physical and chemical properties over time can be modeled using data from weathering studies of specific oils. When combined with performance data for various equipment and materials, tested over a range of weathering stages of oils, windows-of-opportunity can be estimated for spill response decision-making. Under experimental conditions discussed in this paper, windows-of-opportunity have been identified and estimated for four oils (for which data are available) under a given set of representative environmental conditions. These ‘generic’ windows have been delineated for the general categories of spill response namely: (1) dispersants, (2) in situ burning, (3) booms, (4) skimmers, (5) sorbents, and (6) oil-water separators. To estimate windows-of-opportunity for the above technologies (except booms), the IKU Oil Weathering Model was utilized to predict relationships—with 5 m s⁻¹ wind speed and seawater temperatures of 15°C.The window-of-opportunity for the dispersant (Corexit 9527^®) with Alaska North Slope (ANS) oil was estimated from laboratory data to be the first 26 h. A period of ‘reduced’ dispersibility, was estimated to last from 26–120 h. The oil was considered to be no longer dispersible if treated for the first time after 120 h. The most effective time window for dispersing Bonnic Light was 0–2 h, the time period of reduced dispersibility was 2–4 h, and after 4 h the oil was estimated to be no longer dispersible. These windows-of-opportunity are based on the most effective use of a dispersant estimated from laboratory dispersant effectiveness studies using fresh and weathered oils. Laboratory dispersant effectiveness data cannot be directly utilized to predict dispersant performance during spill response, however, laboratory results are of value for estimating viscosity and pour point limitations and for guiding the selection of an appropriate product during contingency planning and response. In addition, the window of opportunity for a dispersant may be lengthened if the dispersant contains an emulsion breaking agent or multiple applications of dispersant are utilized. Therefore, a long-term emulsion breaking effect may increase the effectiveness of a dispersant and lengthen the window-of-opportunity.The window-of-opportunity of in situ burning (based upon time required for an oil to form an emulsion with 50% water content) was estimated to be approximately 0–36 h for ANS oil and 0–1 h for Bonnie Light oil after being spilled. The estimation of windows-of-opportunity for offshore booms is constrained by the fact that many booms available on the market undergo submergence at speeds of less than 2 knots. The data suggest that booms with buoyancy to weight ratios less than 8:1 may submerge at speeds within the envelope in which they could be expected to operate. This submergence is an indication of poor wave conformance, caused by reduction of freeboard and reserve net buoyancy within the range of operation. The windows-of-opportunity for two selected skimming principles (disk and brush), were estimated using modeled oil viscosity data for BCF 17 and BCF 24 in combination with experimental performance data developed as a function of viscosity. These windows were estimated to be within 3–10 h (disk skimmer) and after 10 h (brush skimmer) for BCF 17. Whereas for BCF 24, it is within 2–3 d (disk skimmer) and after 3 d (brush skimmer).For sorbents, an upper viscosity limit for an effective and practical use has in studies been found to be approximately 15,000 cP, which is the viscosity range of some Bunker C oils. Using viscosity data for the relative heavy oils, BCF 17 and BCF 24 (API gravity 17 and 24), the time windows for a sorbent (polyamine flakes) was estimated to be 0–4 and 0–10 d, respectively. With BCF 24, the effectiveness of polyamine flakes, was reduced to 50% after 36 h, although it continued to adsorb for up to 10 d. For BCF 17, the effectiveness of polyamine flakes was reduced to 50% after 12 h, although it continued to adsorb for up to 4 d. The windows-of-opportunity for several centrifuged separators based upon the time period to close the density gap between weathered oils and seawater to less than 0.025 g ml⁻¹ (which is expected to be an end-point for effective use of centrifugal separation technology), were estimated to be 0–18 (ANS) and 0–24 h (Bonnie Light) after the spill. Utilizing the windows-of-opportunity concept, the combined information from a dynamic oil weathering model and a performance technology data base can become a decision-making tool; identifying and defining the windows of effectiveness of different response methods and equipment under given environmental conditions. Specific research and development needs are identified as related to further delineation of windows-of-opportunity.     

Introduction/Overview to In Situ Burning of Oil Spills

In situ burning is an oil spill response technique or tool that involves the controlled ignition and burning of the oil at or near the spill site on the surface of the water or in a marsh (see Lindau et al., this volume). Although controversial, burning has been shown on several recent occasions to be an appropriate oil spill countermeasure. When used early in a spill before the oil weathers and releases its volatile components, burning can remove oil from the waters surface very efficiently and at very high rates. Removal efficiencies for thick slicks can easily exceed 95% (Advanced In Situ Burn Course, Spiltec, Woodinville, WA, 1997). In situ burning offers a logistically simple, rapid, inexpensive and if controlled a relatively safe means for reducing the environmental impacts of an oil spill. Because burning rapidly changes large quantities of oil into its primary combustion products (water and carbon dioxide), the need for collection, storage, transport and disposal of recovered material is greatly reduced. The use of towed fire containment boom to capture, thicken and isolate a portion of a spill, followed by ignition, is far less complex than the operations involved in mechanical recovery, transfer, storage, treatment and disposal (The Science, Technology, and Effects of Controlled Burning of Oil Spills at Sea, Marine Spill Response Corporation, Washington, DC, 1994).However, there is a limited window-of-opportunity (or time period of effectiveness) to conduct successful burn operations. The type of oil spilled, prevailing meteorological and oceanographic (environmental) conditions and the time it takes for the oil to emulsify define the window (see Buist, this volume and Nordvik et al., this volume). Once spilled, oil begins to form a stable emulsion: when the water content exceeds 25% most slicks are unignitable. In situ burning is being viewed with renewed interest as a response tool in high latitude waters where other techniques may not be possible or advisable due to the physical environment (extreme low temperatures, ice-infested waters), or the remoteness of the impacted area. Additionally, the magnitude of the spill may quickly overwhelm the deployed equipment necessitating the consideration of other techniques in the overall response strategy (The Science, Technology, and Effects of Controlled Burning of Oil Spills at Sea, Marine Spill Response Corporation, Washington, DC, 1994; Proceedings of the In Situ Burning of Oil Spills Workshop. NIST. SP934. MMS. 1998, p. 31; Basics of Oil Spill Cleanup, Lewis Publishers, Washington, DC, 2001, p. 233). This paper brings together the current knowledge on in situ burning and is an effort to gain regulatory acceptance for this promising oil spill response tool.     

The weathering properties of four unique crude oils from Australia

This paper reports on the results of weathering studies conducted on four light crude oils from production platforms on the northwest shelf of Australia. The laboratory weathering included both evaporative weathering and emulsification studies. The fresh oils and their topped residues were subjected to a battery of physical and chemical characterization analyses. Detailed analyses were performed for n-alkanes by GC/FID and for mono- and polycyclic aromatic hydrocarbons and phenols by GC/MS. The water-in-oil emulsion formation properties of these oils and their topped residues were investigated at two environmentally significant temperatures (13 and 20°C). The results of the analyses indicate that these oils are very different compositionally and have a wide range of physical and chemical properties. The emulsification properties of these oils and their weathered residues ranged from oils that have very rapid water uptake to oils having no water uptake. Unexpectedly, the very waxy oils had very little water uptake and did not form stable water-in-oil emulsions.     

Agents Which Promote and Stabilize Water-in-Oil Emulsions

A number of research groups have investigated the formation and stabilization of water-in-oil emulsions. A variety of compounds and mixtures have been shown to promote and stabilize these emulsions, including sea water particulates, as well as fractions or compounds found in crude oil. Asphaltenes, resins and waxes in crude oil contribute to the formation of stable oil-in-water emulsions. Within the asphaltene fraction, the nickel porphyrins appear to play an essential role in emulsion formation. The vanadium porphyrins, although more abundant than nickel porphyrins in most crude oils, do not play an important role in emulsion formation, possibly because of their higher polarity. It appears that compounds with higher solubility in the oil phase than in the aqueous phase are the emulsifying agents that can promote stable water-in-oil emulsions. Crude oils that form very unstable emulsions, e.g. Gullfaks crude oil from the North Sea, require weathering as well as the addition of nickel porphyrins before a stable emulsion will form. The weathering may cause the formation of colloidal asphaltene particles and highly polar compounds that contributes to emulsion stabilization. Essential to the formation of stable water-in-oil emulsions are sufficient amounts of certain polar compounds. If there are insufficient amounts of these compounds, then even the presence of particles and waxes will not lead to the formation of stable emulsions.     

A bibliometric analysis of biodiesel research during 1991–2015

A bibliometric analysis based on the Science Citation Index Expanded (SCI-EXPANDED) from the Web of Science was carried out to provide insights into research activities and tendencies of the global biodiesel from 1991 to 2015. The document type and language, characteristics of publication outputs, Web of Science categories, journals, countries, institutions, author keyword and most cited articles were emphasized. The results indicated that annual output of the related scientific articles increased steadily. The top six categories focus on different aspects of biodiesel research. Bioresource Technology and Fuel were the two most frequent journals in the field of biodiesel research. The USA took a leading position and had the highest h-index (108) out of 122 countries/territories, followed by China and Brazil. Finally, author keywords and most cited articles were analyzed, indicating that microalgae, Jatropha curcas, vegetable oil and waste cooking oil are the most general raw materials for biodiesel production.