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.     

Overview and future trends in oil spill remote sensing

Remote sensing has great potential to provide data to improve oil spill response efforts. There are a number of sensors available that have been proven capable of detecting oil on water and measuring some of its properties. There is no single sensor that provides all the data needed, and hence a combination of sensors must be used. Even if finances and aircraft load capacity were unlimited, there are still many parameters of an oil slick that cannot be measured by remote sensing. This paper describes the cyrrently available sensors and their method of operation and outlines some new developments that have the potential to increase the amount of data available from an airborne remote sensing operation.     

The role of wind and emulsification in modelling oil spill and surface drifter trajectories

Laboratory and field data suggest that the movement of spilled oil at sea is in general a three-dimensional phenomenon in physical space, whereas trajectories of undrogued surface drifters are more susceptible to two-dimensional analysis. These conclusions are consistent with the intermittent failure of two-dimensional surface models to simulate the trajectories of spilled oil, although such models may be more successful with data from surface drifters. A physical explanation is presented, and a model that incorporates the key portions of the governing processes is described and tested against data from experimental oil spills at sea. Observations suggest that emulsified surface oil will drift down wind at speeds in excess of 3% of the windspeed. When surface turbulence drives oil subsurface for a significant fraction of time, however, net transport speeds are considerably less and significantly to the right of the wind in the northern hemisphere.     

Application of Poly(styrene-co-divinylbenzene) Macroporous Microparticles as a Catalyst Support in the Enzymatic Synthesis of Biodiesel

Macroporous poly(styrene-co-divinylbenzene) microparticles, with three different structural characteristics, have been synthesized and used as supports in the immobilization of lipase from Burkholderia cepacia. The best immobilization yield was found upon using microparticles with 35 % of divinylbenzene and the immobilized lipase on this type of particles was used as a catalyst to obtain biodiesel from soybean oil and ethanol. From the experimental results of the transesterification reaction, an empirical model quantitatively relating the temperature, the concentration of the enzyme and the transesterification yield was obtained. Statistical analysis of this model indicated that within the range of values of the variables studied (35–47 °C and 231–788 U/mg respectively) only the enzyme concentration exerted a significant influence on the reaction yield. Additionally, the good fit of a Michaelis–Menten-type model to the experimental results suggests that the limiting step of the reaction was the formation of the enzyme-substrate complex.     

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.     

A Review of the Status of Advanced Technologies for the Detection of Oil in and with Ice

Remote sensors for application to oil in ice and oil with ice are assessed. Radio-frequency methods to detect oil in ice depend on the difference in dielectric properties between oil and water. Freshwater ice is relatively transparent to frequencies below about 200 MHz. Despite extensive theoretical studies, there is a lack of experimental evidence to support the notion that radio-frequency methods have potential.Acoustic methods for the detection of oil in ice show promise. Regular metal inspection equipment is capable of detecting oil layers under ice. Oil propagates shear waves and detection methods based on this unique property are capable of identifying oil in ice. One unit has been built and tested in the field based on this principle.Oil with ice detection is a well developed technology. A common sensor is an infrared camera or an IR/UV (infrared/ultraviolet) system. The inherent weaknesses include the inability to discriminate oil on beaches, among weeds or debris. The laser fluorosensor is a most useful instrument because of its unique ability to identify oil on backgrounds that include water, soil, ice and snow. It is the only sensor that can positively discriminate oil on most backgrounds. Radar offers the only potential for large area searches and foul weather remote sensing, however, there is little potential to detect oil in the immediate vicinity of ice. A major weakness of radar is that it is limited to operation over seas with winds of about 2–8 m/s.Equipment operating in the visible region of the spectrum, such as cameras and scanners, is useful for documentation or providing a basis for the overlay of other data. It is not useful beyond this because oil shows no spectral characteristics in the visible region that can be used to discriminate oil.     

Physical Properties and Processes that Influence the Clean Up of Oil Spills in the Marine Environment

Based on a study carried out by the Versuchsanstalt für Wasserbau und Schiffbau, Berlin – VWS for the German Environmental Agency, this report represents an attempt to summarize the knowledge in the Federal Republic of Germany and world-wide concerning the control of hazards from discharged oil and other liquid chemicals after casualties on and in the hydrosphere. Because of technical reasons, control measures can be classified into passive and active types; this classification has been adopted for this report in the following order:

• •Part 1: Passive mechanisms: Booms and barriers.
• •Part 2: Active mechanisms: Recovery devices.
• •Part 3: Other means: Dispersion.
• •Part 4: Control of sinking and/or sunken chemicals.

Part 1 not only evaluates the behaviour of liquid chemicals on water, but also considers the physical fundamentals underlying the functioning of booms and barriers. Some widely used definitions and relations (such as the relationship between the blocking of liquid chemicals and boom draught or efficiency) will be refined. The discussion of the physical fundamentals is presented in the broadest sense and concludes with practical advice on the deployment of booms.Part 2 attempts to standardize recovery devices based on the application of fundamental physical principles. Four classes were identified and have been used to classify pick-up devices. Once again basic physical fundamentals have been presented in a way that facilitates deductions on application possibilities. The evaluation showed that practically only those methods that utilize adhesion and “hole-in-the-water” principles can be operated with sufficient efficiency which, in turn, reflects the world-wide state-of-the-art in equipment development. Special attention has been paid to hybrid systems which utilize both passive and active methodologies.In Part 3, the basics of dispersion of oil and other floating liquid chemicals are considered. It can be shown that mechanical dispersion has the same effect as its chemical counterpart. This relationship recognizes the necessity for applying a mechanical agitator for using dispersants effectively. This strategy calls into question the efficiency of chemical dispersion.Part 4 deals with the behaviour and control options for sinking and/or sunken liquid chemicals. Contrary to the general opinion that liquid chemicals which have disappeared from the surface cannot be controlled, it has been found that, under certain conditions, even these chemicals can be “herded” and recovered. It will be shown that practically the same techniques can be applied to submerged chemicals as has been used for the recovery of floating hazardous substances.     

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.     

The Svalbard Intertidal Zone: A Concept for the Use of GIS in Applied Oil Sensitivity,Vulnerability and Impact Analyses

Historical oil spills have shown that environmental damage on the seashore can be measured by acute mortality of single species and destabilisation of the communities. The biota, however, has the potential to recover over some period of time. Applied to the understanding of the fate of oil and population and community dynamics, the impact can be described by the function of the following two factors: the immediate extent and the duration of damage. A simple and robust mathematical model is developed to describe this process in the Svalbard intertidal. Based on the integral of key biological and physical factors, i.e., community specific sensitivity, oil accumulation and retention capacity of the substrate, ice-cover and wave exposure, the model is implemented by a Geographical Information System (GIS) for characterisation of the habitat’s sensitivity and vulnerability. Geomorphologic maps and georeferenced biological data are used as input. Digital maps of intertidal zone are compiled, indicating the shoreline sensitivity and vulnerability in terms of coastal segments and grid aggregations. Selected results have been used in the national assessment programme of oil development in the Barents Sea for priorities in environmental impact assessments and risk analyses as well as oil spill contingency planning.     

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.     

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.     

Pyrolysis of waste tyres: A review

Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H₂, C₁–C₄ hydrocarbons, CO₂, CO and H₂S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.     

Obtaining Approvals for Oil and Gas Projects in Shallow Water Marine Areas in Western Australia using an Environmental Risk Assessment Framework

The oil and gas industry is of major economic importance to the state of Western Australia. The majority of its activities are offshore, some occurring in shallow marine areas adjacent to sensitive resources such as coral reefs and mangroves. One of the main issues for the oil and gas industry is continued access to marine acreage. Increasing public concern about the environmental protection of the coastal and marine environment has increased the focus on the various users. This has resulted in the development of statutory and administrative processes, more stringent environmental assessment and operating conditions, and greater scrutiny on the issue of access of proposals to some areas. Detailed environmental assessment and management plans are generated for all drilling and development projects. An environmental risk assessment approach utilising computer modelling, habitat mapping, research and monitoring is used to evaluate the risk of a project on adjacent resources and to obtain government approval. The Wonnich appraisal drilling program, which consisted of two wells drilled from the same surface location situated one kilometre away from an area of high conservation value, will be used as a case study of the risk assessment procedure used by one oil and gas company.     

Comparison of slope stability in two Brazilian municipal landfills

The implementation of landfill gas to energy (LFGTE) projects has greatly assisted in reducing the greenhouse gases and air pollutants, leading to an improved local air quality and reduced health risks. The majority of cities in developing countries still dispose of their municipal waste in uncontrolled 'open dumps.' Municipal solid waste landfill construction practices and operating procedures in these countries pose a challenge to implementation of LFGTE projects because of concern about damage to the gas collection infrastructure (horizontal headers and vertical wells) caused by minor, relatively shallow slumps and slides within the waste mass. While major slope failures can and have occurred, such failures in most cases have been shown to involve contributory factors or triggers such as high pore pressures, weak foundation soil or failure along weak geosynthetic interfaces. Many researchers who have studied waste mechanics propose that the shear strength of municipal waste is sufficient such that major deep-seated catastrophic failures under most circumstances require such contributory factors. Obviously, evaluation of such potential major failures requires expert analysis by geotechnical specialists with detailed site-specific information regarding foundation soils, interface shearing resistances and pore pressures both within the waste and in clayey barrier layers or foundation soils. The objective of this paper is to evaluate the potential use of very simple stability analyses which can be used to study the potential for slumps and slides within the waste mass and which may represent a significant constraint on construction and development of the landfill, on reclamation and closure and on the feasibility of a LFGTE project. The stability analyses rely on site-specific but simple estimates of the unit weight of waste and the pore pressure conditions and use "generic" published shear strength envelopes for municipal waste. Application of the slope stability analysis method is presented in a case study of two Brazilian landfill sites; the Cruz das Almas Landfill in Maceio and the Muribeca Landfill in Recife. The Muribeca site has never recorded a slope failure and is much larger and better-maintained when compared to the Maceio site at which numerous minor slumps and slides have been observed. Conventional limit-equilibrium analysis was used to calculate factors of safety for stability of the landfill side slopes. Results indicate that the Muribeca site is more stable with computed factors of safety values in the range 1.6-2.4 compared with computed values ranging from 0.9 to 1.4 for the Maceio site at which slope failures have been known to occur. The results suggest that this approach may be useful as a screening-level tool when considering the feasibility of implementing LFGTE projects.     

The Oil Pollution Act of 1990: A Decade Later

Analysis of oil spills data confirms that accidental oil spills are natural phenomenon and that there is a relationship between accidental oil spills and variables like vessel size, vessel type, time and region of spill. The volume of oil spilled bears relationship with the volume of petroleum imports and domestic movement of petroleum and proportion of large oil spills. Finally, navigational risk increases with increase in marine traffic and is also determined by variables like hydrographic and meteorological conditions, water configuration, maneuvering space, obstructions and nuisance vessels. The Oil Pollution Act, 1990 (OPA 90) was passed by the US Congress in the aftermath of 11 million gallon spill of crude oil in Prince William Sound, Alaska. The objective of OPA 90 was to minimize marine casualties and oil spills by addressing preventive, protective, deterrent and performance aspects of accidental oil spills. The arm of various regulations like double-hull tankers and vessel response plans extended to both US flagged and foreign-flagged tank vessels. The cost–benefit analysis of major regulations shows that the estimated costs exceed estimated benefits. We observe from USCG data on oil spills by size, by vessel type, Coast guard district and type of petroleum product that there have been significant reductions in the number and the quantity of oil spills. Our regression results show that the quantity of oil spilled increases with increase in oil imports but increases at a decreasing rate. The quantity of oil spilled decreases with increases in the domestic oil movements. Furthermore, percent of oil spills larger than 10,000 gallons also increases the potential quantity of oil spilled. OPA 90 has been a deterrent to accidental oil spills but the finding is not conclusive.     

Probable Effects of Langmuir Circulation Observed on Oil Slicks in the Field

Although the presence of Langmuir circulation (LC) cells is evident from observations in lakes, ponds, and coastal waters, the effects of these cells on oil slicks have received less attention. This paper considers the effects as inferred from field data of LC cells on oil slicks. Examples from observed experimental oil slicks in the field are presented. The importance of these LC cells is discussed from the point of view of oil spill contingency.     

Dynamic modelling of oil boom failure using computational fluid dynamics

The common response to an oil spill on water is to contain the oil with booms and recover it with skimming devices. In some situations, however, the booms cannot hold the oil and the oil will escape underneath the boom due to hydrodynamic forces. Computational fluid dynamics (CFD) is a powerful modelling tool combining fluid dynamics and computer technology. We have utilized a commercial CFD program, Fluent, to simulate the oil-water flow around a boom. The studies accurately model channel experiments conducted in recent years. The studies show that the flow patterns around booms are modified by the presence of oil and, therefore, suggest that towing and wave-conformity tests of booms will not be meaningful unless they are undertaken with the presence of oil.     

Evaluation of a vertical frozen soil barrier at oak ridge national laboratory

Arctic Foundations, Inc. (AFI), of Anchorage, Alaska, has developed a freeze barrier system designed to hydraulically isolate a contaminant source area. The system can be used for long‐term or temporary containment of groundwater until appropriate remediation techniques can be applied. The technology was evaluated under the United States Environmental Protection Agency's (EPA's) Superfund Innovative Technology Evaluation (SITE) program at the United States Department of Energy's (DOE's) Oak Ridge National Laboratory (ORNL) facility in Oak Ridge, Tennessee. For the demonstration, an array of freeze pipes called “thermoprobes” was installed to a depth of 30 feet below ground surface around a former waste collection pond and keyed into bedrock. The system was used to establish an impermeable frozen soil barrier to hydraulically isolate the pond. Demonstration personnel collected independent data to evaluate the technology's performance. A variety of evaluation tools were used—including a groundwater dye tracing investigation, groundwater elevation measurements, and subsurface soil temperature data—to determine the effectiveness of the freeze barrier system in preventing horizontal groundwater flow beyond the limits of the frozen soil barrier. Data collected during the demonstration provided evidence that the frozen soil barrier was effective in hydraulically isolating the pond.