The Significance of Oil Spill Dispersants

There is growing acceptance worldwide that use of dispersants to counter the effects of an oil spill offers many advantages and can often result in a net environmental benefit when considered in relation to other response options. A major reason for this growing support and increased reliance on dispersants is the advent of improved dispersant products that are low in toxicity to marine life and more effective at dispersing heavy and weathered oils – oils previously believed to be undispersible. This capability has been demonstrated through extensive laboratory testing, field trials, and dispersant application on actual spills. This paper summarizes recent advances in dispersant R&D and reviews the implications of technology advances.     

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.     

The application of ecological risk assessment principles to dispersant use planning

Ecological risk assessment is a formal process, either quantitative or semi-quantitative, to evaluate the possible ecological consequences of human activities and natural catastrophes. While formal risk assessments have been used for years when dealing with risks to human health, the application of such structured analyses is less common for environmental issues. It is, however, an area of intense interest, both scientifically and technically, in the United States at the present time. This paper suggests a methodology for applying ecological risk assessment protocols to the oil spill response planning process, which should improve our ability to compare and evaluate response options, especially controversial options such as the use of dispersants.     

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).     

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.     

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.     

Bioremediation of Stranded Oil on an Arctic Shoreline

The application of slow-release and soluble fertilizers proved to be an effective and environmentally benign way of stimulating oil biodegradation on an Arctic shoreline. Fertilizer application to the surface of the beach delivered nutrients to the oiled sediment beneath the beach surface. There was no significant run-off of this fertilizer to either the nearshore water or to unfertilized plots, and there were no adverse toxicological effects of the fertilizer application. The fertilizer application was followed by an increase in oxygen consumption and carbon dioxide evolution from the beach, increased microbial biomass, and significantly greater biodegradation of oil on the plots that had received fertilizer. The rate of oil biodegradation was approximately doubled over the course of a year by fertilizer applications in the first two months after the spill.Simple test kits proved adequate to monitor the fertilizer-application process in the field in a time frame that would allow the application process to be fine-tuned during treatment on a real spill. Simple test kits and portable instrumentation were useful in demonstrating the initial success of the bioremediation strategy.     

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.     

In-situ Treatment of Oiled Sediment Shorelines

Experimental oil spill studies were conducted to quantify the effectiveness of selected in-situ shoreline treatment options to accelerate natural oil removal processes on mixed-sediment (sand and pebble) shorelines. At each of three distinct shoreline sites, treatment test plots and control plots were established within a 40-, 80- and 143-m continuous stretch of oiled shoreline. A total of 5500 l of oil was deposited along a 3-m wide swath in the upper intertidal zone at each site. Approximately one week after oiling, a different treatment technique was applied to each plot. The treatment techniques were: sediment relocation (surf washing), mixing (tilling), bioremediation (fertilizer application), and bioremediation combined with mixing. One plot at each site was monitored for natural attenuation. The quantity of oil removed from the plots was measured six times up to 60 days post-treatment and then again one year later. Changes in the physical character of the beach, oil penetration, movement of oil to the subtidal environment, toxicity, and biodegradation were monitored over the 400-day period.The results verified quantitatively that relocation of oiled sediments significantly accelerated the rate of oil removal from the shoreline by more than one year. Microscopic observations and image analyses confirmed that the oil-mineral aggregate formation process was active and was increased by sediment relocation. Oil biodegradation occurred in this arctic environment, both in the oiled sediments and on the fine mineral particles removed from the sediment by natural physical processes. The biodegradation of oil in sediment was significantly stimulated by simple bioremediation protocols. Mixing (by tilling) did not clearly stimulate oil loss and natural recovery in the context of this experimental design. None of the treatment techniques elevated toxicity in the nearshore environment to unacceptable levels, nor did they result in consequential alongshore or nearshore oiling.     

Influence of Salinity on Petroleum Accommodation by Dispersants

The effect of receiving water salinity on the effectiveness of two oil dispersants, Corexits^® 9527 and 9500, was investigated using a recently implemented modified version of the Swirling Flask efficacy test. The dispersants were tested with ten different oils, representing a wide range of physical–chemical properties. Test salinities ranged from 0 to 35 ppt, with temperature held constant at 15°C. Results showed Corexit 9500 to be generally more effective on most of the dispersible oils at most salinities, but performance of both products was significantly affected by salinity. Both dispersants performed best at salinities above 25 ppt, with Corexit 9500 maintaining its effectiveness over a fairly wide range of salinities. Correlations between dispersant effectiveness and various oil physical/chemical properties were highly variable.     

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.     

Looking to the Future––Setting the Agenda for Oil Spill Prevention,Preparedness and Response in the 21st Century

The Oil Pollution Act of 1990 (OPA 90) was largely driven by the catastrophic EXXON VALDEZ tanker spill and several other major tanker spills that followed in 1989. Under the OPA 90 mandate, the US Coast Guard, in partnership with other Federal agencies and industry have implemented a number of initiatives that have significantly enhanced the national oil spill prevention, preparedness and response capability. Declining trends in the volume of oil spilled into US waters indicates that these initiatives are at least in some measure successful.The Coast Guard is now concerned about what the future may hold in terms of oil pollution threats, and prevention, preparedness and response program shortcomings and opportunities in the future. To address this issue, the Coast Guard, in partnership with other National Response Team agencies and industry, is conducting a Broad-Based Programmatic Risk Assessment to develop a comprehensive vision and strategy for the Oil Spill Prevention, Preparedness and Response (OSPPR) Program in the 21st Century. This study will characterize the current and emerging oil spill threats by source category, assess the potential impacts of these threats to define overall risk, and examine the current and projected effectiveness of OSPPR initiatives in minimizing these risks. Key issues, problems and focus areas will be identified and targeted for follow-on risk analysis and management activities by the Coast Guard and agency and industry stakeholders.     

The Relation of Langmuir Circulation Processes to the Standard Oil Spill Spreading,Dispersion, and Transport Algorithms

Most standard oil spill modeling programs neglect the effects of Langmuir circulation (LC). The authors have identified three areas where LC effects may be important in spill behavior. These three areas are spreading, dispersion, and transport. LC will cause the slick to break into windrows when the wind-row formation velocity is comparable to Fay and other spreading forces. Oil dispersion is likely to be enhanced, with droplets carried to greater depth and distributed non-uniformly. Transport velocities for different parts of the slick will vary because of LC, a phenomenon that also occurs because of other factors.     

Modeling natural attenuation of petroleum hydrocarbon contamination using alternate electron acceptors: Case study comparing bioplume iii with BIOSCREEN

Natural attenuation holds great promise as a cost‐effective means of remedying groundwater contamination at petroleum spill sites: this is particularly true at sites with sufficient background concentrations of alternate electron acceptors (nitrate and/or sulfate). The study reported in this article compared the results of a new Environmental Protection Agency (EPA) numerical model (BIOPLUME III) with an updated EPA analytical model (BIOSCREEN Version 1.4) used to predict natural attenuation at an underground fuel spill site in Oklahoma. High background sulfate concentrations were shown to result in unrealistic predictions from both BIOSCREEN and BIOPLUME III. BIOSCREEN could be easily used with a data set not significantly enlarged from that used in a routine leaking fuel tank investigation. BIOPLUME III was much more difficult to use and did not yield reliable results. Results of this study indicate that the additional complexity of the BIOPLUME III model is not justified for simple sites.     

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.     

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。     

Oil Spill Contingency and Response (OSCAR) Analysis in Support of Environmental Impact Assessment Offshore Namibia

The work reported here encompasses analyses of specific potential spill scenarios for oil exploration activity planned offshore of Namibia. The analyses are carried out with the SINTEF Oil Spill Contingency and Response (OSCAR) 3-dimensional model system. A spill scenario using 150 m³ of marine diesel demonstrates the rapidity with which such a spill will dissipate naturally, even in light winds. Vertical and horizontal mixing bring subsurface hydrocarbon concentrations to background levels within a few days. A hypothetical 10 day blowout scenario releasing 11,000 bbl per day of light crude oil is investigated in terms of the potential for delivering oil to selected bird and marine mammal areas along the Namibian coast. Worst case scenarios are selected to investigate the potential mitigating effects of planned oil spill response actions. Mechanical recovery significantly reduces, and in some cases eliminates, potential environmental consequences of these worst case scenarios. Dispersant application from fixed wing aircraft further reduces the potential surface effects. The analysis supplies an objective basis for net environmental analysis of the planned response strategies.