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 Spill Modeling towards the Close of the 20th Century: Overview of the State of the Art

The state-of-the-art in oil spill modeling is summarized, focusing primarily on the years from 1990 to the present. All models seek to describe the key physical and chemical processes that transport and weather the oil on and in the sea. Current insights into the mechanisms of these processes and the availability of algorithms for describing and predicting process rates are discussed. Advances are noted in the areas of advection, spreading, evaporation, dispersion, emulsification, and interactions with ice and shorelines. Knowledge of the relationship between oil properties, and oil weathering and fate, and the development of models for the evaluation of oil spill response strategies are summarized. Specific models are used as examples where appropriate. Future directions in these and other areas are indicated     

Weathering of Oils at Sea: Model/Field Data Comparisons

The SINTEF Oil Weathering Model (OWM) has been extensively tested with results from full-scale field trials with experimental oil slicks in the Norwegian NOFO Sea trials in 1994 and 1995 and the AEA 1997 trials in UK. The comparisons between oil weathering values predicted by the model and ground-truth obtained from the field trials are presented and discussed. Good laboratory weathering data of the specific oil as input to the model is essential for obtaining reliable weathering predictions. Predictions provided by the SINTEF-OWM enable oil spill personnel to estimate the most appropriate “window of opportunity” for use of chemical dispersants under various spill situations. Pre-spill scenario analysis with the SINTEF Oil Spill Contingency and Response (OSCAR) model system, in which the SINTEF-OWM is one of several components, has become an important part of contingency plans as well as contingency training of oil spill personnel at refineries, oil terminals and offshore installations in Norway.     

Biodegradation of Crude Oil Contaminating Marine Shorelines and Freshwater Wetlands

This paper is a summary of the various factors influencing weathering of oil after it has been released into the environment from a spill incident. Special emphasis has been placed on biodegradation processes. Results from two field studies conducted in 1994 and 1999 involving bioremediation of an experimental oil spill on a marine sandy shoreline in Delaware and a freshwater wetland on the St. Lawrence River in Quebec, Canada have been presented in the paper.     

Quantitative analysis of alternate oil spill response strategies using OSCAR

A three-dimensional numerical model of the physical and chemical behavior and fate of spilled oil has been coupled to a model of oil spill response actions. This coupled system of models for Oil Spill Contingency and Response (OSCAR), provides a tool for quantitative, objective assessment of alternative oil spill response strategies. Criteria for response effectiveness can be either physical (‘How much oil comes ashore?’ or ‘How much oil have we recovered?’) or biological (‘How many biologically sensitive areas were affected?’ or ‘What exposures will fish eggs and larvae experience in the water column?’). The oil spill combat module in the simulator represents individual sets of equipment, with capabilities and deployment strategies being specified explicitly by the user. The coupling to the oil spill model allows the mass balance of the spill to be affected appropriately in space and time by the cleanup operation as the simulation proceeds. An example application is described to demonstrate system capabilities, which include evaluation of the potential for both surface and subsurface environmental effects. This quantitative, objective approach to analysis of alternative response strategies provides a useful tool for designing more optimal, functional, rational, and cost-effective oil spill contingency solutions for offshore platforms, and coastal terminals and refineries.     

Comparative occurrence rates for offshore oil spills

Estimates of occurrence rates for offshore oil spills are useful for analysis of potential oil spill impacts and for oil spill response contingency planning. As the Oil Pollution Act of 1990 (U.S. Public Law 101–380, 18 August 1990) becomes fully implemented, estimates of oil spill occurrence will become even more important to natural resource trustees and to responsible parties involved in oil and gas activities. Oil spill occurrence rate estimates have been revised based on U.S. Outer Continental Shelf platform and pipeline spill data (1964–1992) and worldwide tanker spill data (1974–1992). These spill rates are expressed and normalized in terms of number of spills per volume of crude oil handled. The revisions indicate that estimates for the platform spill occurrence rates declined, the pipeline spill occurrence rates increased, and the worldwide tanker spill occurrence rates remained unchanged. Calculated for the first time were estimates of tanker and barge spill rates for spills occuring in U.S. waters, and spill occurrence rates for spills of North Slope crude oil transported by tanker from Valdez, Alaska. All estimates of spill occurrence rates were restricted to spills greater than or equal to 159 m³ (1000 barrels).     

Photo-oxidation and Photo-toxicity of Crude and Refined Oils

The fate and effects of an oil spill are effected by solar radiation through the action of photo-oxidation and photo-toxicity. Photo-oxidation, an important process in the weathering of oil, produces a variety of oxidized compounds, including aliphatic and aromatic ketones, aldehydes, carboxylic acids, fatty acids, esters, epoxides, sulfoxides, sulfones, phenols, anhydrides, quinones and aliphatic and aromatic alcohols. Some of these compounds contribute to the marine biota toxicity observed after an oil spill. Photo-toxicity occurs when uptake of certain petroleum compounds, e.g. certain polycyclic aromatic hydrocarbons and benzothiophenes, is followed by solar exposure which results in much greater toxicity than after dark uptake. The mechanism of PAH photo-toxicity includes absorbance of solar radiation by the PAH which produces a free radical and this free radical in turn reacts with oxygen to produce reactive oxygen species that can damage DNA and other cellular macromolecules. While most studies on photo-toxicity have been carried out in the laboratory, there are studies showing that water from an oil spill is photo-toxic to bivalve embryos for at least a few days after the spill. Other studies have found that oil contaminated sediments are photo-toxic to several marine invertebrates. More studies are required to determine if marine fauna at an oil spill site are effected by the action of photo-toxicity and photo-oxidation.     

Real time oil spill forecasting during an experimental oil spill in the arctic ice

The oil spill trajectory and weathering model OILMAP was used to forecast spill trajectories for an experimental oil spill in the Barents Sea marginal ice zone. The model includes capabilities to enter graphically and display environmental data governing oil behavior: ice fields, tidal and background current fields, and wind time series, as well as geographical map information. Forecasts can also be updated from observations such as airplane overflights. The model performed well when wind was ‘off-ice’ and speeds were relatively low (3–7 m s⁻¹), with ice cover between 60 and 90%. Errors in forecasting the trajectory could be directly attributed to errors in the wind forecasts. Appropriate drift parameters for oil and ice were about 25% of the wind speed, with an Ekman veering angle of 35° to the right. Ice sheets were typically 1 m thick. When the wind became ‘on-ice’, wind speeds increased to about 10 m s⁻¹ and trajectory simulations began to diverge from the observations, with observed drift parameters being 1.5% of the wind speed, with a 60° veering angle. Although simple assumptions for the large scale movement of oil in dense ice fields appear appropriate, the importance of good wind forecasts as a basis for reliable trajectory prognoses cannot be overstated.     

Enhanced oil biodegradation with mineral fine interaction

During recent oil spill clean-up operations, residual oils stranded in the intertidal environment were successfully dispersed into the sea by physically accelerating the natural interaction between oil and mineral fines. Oil-mineral fine interaction reduces the adhesion of oil to solid surfaces and promotes the formation of stable micron-sized oil droplets in the water column. By increasing the oil-in-water interface, i.e. the oil becomes more accessible to nutrients, oxygen and bacteria, this interaction becomes a key factor in enhancing oil biodegradation. There is, however, concern that this technique merely transports the oil from one compartment of the environment to another. In our study, controlled laboratory shaker-flask experiments showed that oil-mineral fine interactions stimulates microbial activity by enhancing both the rate and extent of oil degradation by stimulating microbial activity. These results support the application of shoreline oil spill clean-up techniques based on the acceleration of oil-mineral fine interactions.     

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.     

Past in situ Burning Possibilities

This study evaluated the feasibility of conducting in situ burning (ISB) using current technology on post-1967 major oil spills over 10 000 barrels in North America and over 50 000 barrels in South America and Europe. A diverse set of 141 spills representing various combinations of parameters affecting spill responses (e.g., spill size, oil type, weather conditions, sea temperature, and geographic location) were evaluated using four “Phase I” criteria: Distance to populated area, oil weathering, logistics, and weather conditions. In Phase I, a spill that failed to meet one of the four criteria was considered an “unsuccessful” candidate for ISB. In total, 47 of the 141 spills passed the Phase I analysis. The potential effect of the plume on populated areas was the most significant of the four Phase I criteria; 59 of the 141 spills did not pass Phase I because the incident occurred near a sizable city. Spills that met all four criteria were further evaluated using a “Phase II” analysis that applied additional criteria and considered individual spill circumstances to determine if the spill should be rated as a “successful”, “marginal call”, or “unsuccessful” ISB candidate. Fourteen spills were ultimately determined successful in the Phase II analysis, and 12 were designated marginal calls.     

Update of Comparative Occurrence Rates for Offshore Oil Spills

Estimates of occurrence rates for offshore oil spills are useful for analyzing potential oil-spill impacts and for oil-spill response contingency planning. With the implementation of the Oil Pollution Act of 1990 (US Public Law 101-380, August 18, 1990), estimates of oil-spill occurrence became even more important to natural resource trustees and to responsible parties involved in oil and gas activities.Oil-spill occurrence rate estimates have been revised based on US Outer Continental Shelf (US OCS) platform and pipeline spill data (1964 through 1999), worldwide tanker spill data (1974 through 1999), and barge spill data for US waters (1974–1999). These spill rates are expressed and normalized in terms of number of spills per volume of crude oil handled. All estimates of spill occurrence rates were restricted to spills greater than or equal to 1000 barrels (159 m³, 159 kl, 136 metric tonnes, 42,000 US gallons).The revisions compared to the previously published rates calculated through 1992 (Anderson and LaBelle, 1994) indicate that estimates for the US OCS platform spill occurrence rates continue to decline, primarily because no spills have occurred since 1980. The US OCS pipeline spill occurrence rates for spills greater than or equal to 1000 barrels remained essentially unchanged. However, the rate for larger OCS pipeline spills (greater than or equal to 10,000 barrels) has decreased significantly. Worldwide tanker spill rates, rates for tanker spills in US waters, and rates for barge spills in US waters decreased significantly. The most recent 15-year estimates for 1985–1999 (compared to rates for the entire data series) showed that rates for US OCS platforms, tankers, and barges continued to decline.     

Modeling the fate of oil spills at sea

A numerical model for the simulation of the physicochemical weathering processes of an oil spill at sea is presented based on state-of-the-art models. The model includes the most significant processes: spreading, evaporation, dispersion into the water column, emulsification and the change in viscosity and density. These processes depend on each other and are allowed to vary simultaneously since processes are described by a set of differential equations, solved by a fourth-order Runge-Kutta method. Numerical examples are given, in order to test the results obtained, and compared with available experimental data in the literature. The model predicts well the variation of water incorporation, density and viscosity but seems to overestimate the fraction evaporated. However more experimental data are needed to calibrate and validate the model since differences in the composition of the simulated oil and the samples from which experimental data are taken may occur in evaporation studies. The model is suitable to join other modules for the prediction of the spill trajectory by advection due to winds and currents and sub-sea transport.     

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.     

The 1993 oil spill of Tampa Bay,a scenario for burning?

This viewpoint paper considers the potential of offshore burning of oil in the recent Tampa Bay spill as a generic oil spill response option. While the oil spilled might not have been amenable to burning, the physical constraints of the spill and subsequent environmental conditions provide a scenario for future consideration of this option.     

The effect of biodiesel on the rate of removal and weathering characteristics of crude oil within artificial sand columns

The physical and chemical properties of crude oils differ greatly, and these properties change significantly once oil is spilled into the marine environment as a result of a number of weathering processes. Quantitative information on the weathering of spilled crude is a fundamental requirement for a fuller understanding of the fate and behaviour of oil in the environment. Additionally, such data are also essential for estimating windows-of-opportunities, where specific response methods, technologies, equipment or products are most effective in clean-up operations. In this study, the effects of a relatively low toxicity compound, biodiesel (rape seed oil methyl ester) on the rate of removal and weathering characteristics of crude oil within artificial sand columns are thoroughly investigated using GC/MS techniques. In the absence of the biodiesel, the crude oil exhibits low mobility and a slow rate of microbial degradation within the sediment and as a result, a high degree of persistance. Brent crude oil was subject to a progressive loss of the low molecular weight n-alkanes with respect to time through evaporation and a preferential migration of these fractions through the sediment to depth. The addition of the biodiesel led to greater recovery of oil from the sediment if applied to relatively unweathered crude oil. This was as the result of the crude oil dissolving within the more mobile biodiesel. The negligible concentration of the n-C₁₀ to n-C₂₁ fraction in surface sediment samples suggests a greater solubility of these fractions within the biodiesel and that their subsequent adsorption onto subsurface sediment particles was responsible for their absence from water flushed through the sands. These results suggest that biodiesel may have an active role in the beach clean-up of spilt crude oil.     

The Application of Strict Criminal Liabilities to Spillage of Oil: The Practical Impact on Effective Spill Response

The Federal Water Pollution Control Act as amended by the Oil Pollution Act of 1990 provides criminal penalties in oil spills that result from criminal activity, gross negligence or willful misconduct on the part of the spiller. Nevertheless, the Department of Justice has seen fit to reach into unrelated legislation to potentially apply strict criminal liability to any oil spill regardless of intent.Strict criminalization of accidental oil spills is demonstrably counterproductive to effective protection of the environment from the effect of spills since it poses a serious impediment to cooperation and coordination by and between those charged by law to respond to them. This impediment is particularly dangerous since it threatens the proper functioning of the inherently sensitive “troika” Unified Command Structure that has evolved in spill response management in response to OPA-90 management requirements.Introduction of strict criminal liability for accidental spills is also particularly troublesome in that it must enlist unrelated law to influence an area that has been addressed specifically by legislation designed for that purpose; legislation that has worked well in the past 30 years to both regulate the target activities while successfully achieving the objective of protecting and improving environment quality.     

溢油监测技术在石油石化企业环境风险防控中的应用

针对石油石化企业的溢油风险,提出企业在厂区雨水系统、外排口、涉水生产设施、环境敏感受体、溢油事故应急处置5类场景下的溢油监测需求,总结了溢油监测技术的类型和特点,介绍了可见光、红外、紫外、荧光、高光谱、微波辐射、雷达、电磁能量吸收等溢油监测技术的应用现状和优缺点。提出:企业溢油监测系统可分为企业内部溢油风险分级管控监测、企业边界的溢油风险报警监测、敏感环境监视的风险预警监测、溢油事故应急救援的溢油处置监测4个层次的运行模式。     

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.