Water-in-oil emulsion formation: A review of physics and mathematical modelling

A literature review of the physics and modelling of water-in-oil emulsification is presented. The understanding of the physics of emulsion formation is still incomplete, but developing. The formation of emulsions is due to the surfactant-like action of polar compounds (resins) and asphaltenes in oil. These compounds act to maintain small (1–20 μm) droplets of water in oil. Volatile aromatic compounds in crude oils solubilize asphaltenes and resins. Crude oils containing lower quantities of these volatile compounds or BTEX (benzene, toluene, ethylbenzene, xylenes) will form emulsions given sufficient turbulent sea energy. Oils may lose the BTEX component by weathering before being capable of forming stable emulsions. The kinetics and energy of formation of emulsions is not well understood. Emulsions are often reported to form rapidly after the necessary chemical conditions are achieved and where there is significant wave action or other turbulent energy. Oil spill models generally employ a first-order rate law (exponential) to predict emulsion formation.     

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.     

Heat and chemical treatment of mechanically recovered w/o emulsions

Nearly all crude oils and some heavier refined products form stable water-in-oil (w/o) emulsions when spilled and weathered at sea. Breaking these emulsions and discarding the separated water allow more oil to be recovered and stored by OSRVs (Oil Spill Recovery Vessels) and make the handling of oily waste easier due to viscosity reduction. This study was conducted to determine whether a combination of heat and emulsion breaker is more effective than either technique used alone. The results will be used to prepare guidelines for treatment of w/o emulsions and planning of large-scale tests.A bench-scale laboratory study was carried out using emulsions prepared from different crude oil residues (BCF-17, Alaskan North Slope and Bonny Light) and a Bunker C fuel oil/gas oil blend (IF-80). Tubes containing w/o emulsions, with or without emulsion breaker added, were partially submerged in a water bath at different temperatures to simulate the heating system of the recovered oil tanks onboard the OSRVs. The effectiveness of the emulsion breaking was measured by recording settled water over a 24 h period. The results showed that:

• •• The stability of a w/o emulsion and its response to heat and emulsion breaker is highly dependent on different characteristics of the oil from which it is formed.
• •• Stable w/o emulsions that can be slowly broken by heat alone were, in general, broken much more rapidly if emulsion breaker was added in addition to heat.
• •• The w/o emulsions formed from relatively paraffinic crude oil (e.g. ANS) exhibit faster breaking rates than w/o emulsions formed from crude oils with high asphaltene content, such as BCF-17.
• •• All w/o emulsions formed from the crude oil residues could be broken by the application of moderate amounts of heat. W/o emulsions produced from Bunker C/Diesel oil blend were not broken at all by relatively high heat inputs (up to 100°C) and required both the addition of heat and emulsion breaker to obtain partially breaking.

     

Studies of water-in-oil emulsions: Stability studies

Rheological studies were conducted on the water-in-oil emulsions of three crude oils: Arabian Light; Green Canyon; and Sockeye. The emulsions were found to fall into three categories on the basis of both rheological properties and visual appearance: stable; mesostable; and unstable. Stable emulsions are characterized by high viscosities and elasticities and are indefinitely stable. In this study stable emulsions showed true viscosities (viscosity with elasticity separated) approximately 700 times that of the starting oil and mesostable emulsions approximately 50 times that of the starting oil. Mesostable emulsions break into water, oil and sometimes emulsion within about 3 d.     

The Long Term Weathering of Water-in-Oil Emulsions

This paper summarizes studies to determine the long-term stability of water-in-oil emulsions in the laboratory and in large tanks. The long-term stability of emulsions was investigated in the laboratory for up to 9 years and by studying emulsion formation in a large test tank over a period of 2-10 days.Two stable emulsions, formed in the laboratory, had been preserved for 5 and 9 years and remained stable despite a small water loss. The long-term stability appears to be similar to that for the short-term stability. Stable emulsion breakdown processes remain poorly understood, because these emulsions do not generally breakdown, but the primary processes may be mechanical break-up and water evaporation.The water-in-oil states produced were found to have analogous properties between the laboratory and two sets of experiments at a large test tank. No fundamental differences in states or properties were observed over the time periods studied (up to 222 h). The state of the oil was found to correlate well with a stability index as defined by the complex modulus divided by the oil viscosity. It is shown that this stability index becomes more useful when the viscosity of the oil is taken at the same time as the complex modulus measurement.The studies show that meso-stable emulsions will break down within 3 days, generally within 1 day and that those emulsions classified as stable remain up to 9 years under laboratory conditions. These studies also show that meso-stable emulsions do not reform, once broken.     

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.     

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 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.     

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.     

In situ burning of emulsions R&D in Norway

SINTEF Applied Chemistry has been working in the field of in situ burning since 1988, beginning with the first open water testing of the 3M fire proof boom which took place on Spitsbergen. In recent years, the focus of SINTEF's research activities in this area has been on the burning of emulsions. An experimental programme was initiated by NOFO in 1990 to study the in situ burning of water-in-oil (w/o) emulsions, as part of a wider NOFO programme ‘Oil spill contingency in Northern and Arctic waters’ (ONA). The research conducted under this programme has addressed many areas of in situ burning including:

• •• study of processes governing burning emulsions
• •• development of ignition techniques for emulsions
• •• effect of environmental conditions on burning
• •• burning crude oil and emulsions in broken ice
• •• uncontained burning of crude oil and emulsions.

     

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.     

聚合物驱采油污水稳定性的影响因素

研究了聚合物质量浓度、分子量及原油族组分对模拟含油污水油水界面性质的影响。实验结果表明：聚合物驱采油污水的稳定性不但与聚合物含量、分子量有关,还与原油中沥青质、胶质的含量有关;随着含油污水中阴离子型聚丙烯酰胺（APAM）质量浓度的增加,油水界面张力逐渐下降,Zeta电位绝对值和油水界面剪切黏度逐渐上升;APAM分子量越小,油水界面张力降低的程度越大;随剪切速率的增加,油水界面剪切黏度均逐渐降低;当剪切速率小于0.30 s-1时,4种原油族组分对污水稳定性影响的大小顺序为沥青质>胶质>芳香分>饱和分;随沥青质、胶质含量的增加,油水界面张力明显降低,Zeta电位的绝对值显著增大。     

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.     

Enhanced anaerobic bioremediation of chlorinated solvents utilizing vegetable oil emulsions

The use of vegetable oil as an electron donor to enhance the reductive dechlorination of chlori‐nated solvents as an in situ remediation technology is gaining significant traction. Vegetable oil is a cost‐effective slow‐release electron donor with greater hydrogen‐release efficiency than other electron‐donor products. However, neat vegetable oil can inhibit distribution in aquifers due to the oil droplets blocking the flow of groundwater through the smaller pore spaces in the aquifer materials. This issue has been partially overcome by applying the vegetable oil as an oil‐water emulsion, which typically is created in the field. However, the field preparation results in a mixture of droplet sizes, including larger droplets that can make the emulsions unstable and reduce the soil permeability by blocking soil‐pore throats with oil. RNAS, Inc., has developed a kinetically sta‐ble soybean oil emulsion (“Newman Zone”) consisting of submicron droplets with less droplet‐size variation than field‐prepared emulsions. This product is composed of a blend of fast‐release (sodium lactate) and slow‐release (soybean oil) electron donors. The emulsion is produced in a stable factory environment in which it is pasteurized and packaged in sterile packaging. This ma‐terial can be utilized as an electron donor without further treatments or amendments in the field. This article discusses factors associated with selecting electron donors and the development of vegetable oil–based products. A case study of an application of Newman Zone at a former adhe‐sives manufacturing facility is then presented. The case study demonstrates the effect of Newman Zone in reducing chlorinated solvent concentrations in groundwater by both rapidly stimulating initial microbial activity and supporting long‐term reductive dechlorination with a slow‐release electron donor. © 2006 Wiley Periodicals, Inc.     

Storage stability of biocrude oils from fast pyrolysis of poultry litter

The unstable nature of biocrude oils produced from conventional pyrolysis of biomass is one of the properties that limits its application. In the disposal of poultry litter via pyrolysis technology, the biocrude oil produced as a value-added product can be used for on farm applications. In this study, we investigated the influence of bedding material (wood shavings) on the storage stability of biocrude oils produced from the fast pyrolysis of poultry litter. The biocrude oils produced from manure, wood (pine and oak), and mixtures of manure and wood in proportions (75:25 50:50, and 25:75 w/w%) were stored under ambient conditions in sealed glass vials for a period of 6 months and their stability were monitored by measuring the changes in viscosity over time. The manure oil had the lowest rate of viscosity change and thus was relatively the most stable and the oils from the 50:50 w/w% litter mixtures were the least stable. The rate of viscosity change of the manure biocrude oil was 1.33 cP/day and that of the 50/50 litter mixture was 7.6 cP/day for pine and 4.17 cP/day for oak.The spectrometric analyses of the biocrude oils showed that the presence of highly reactive oxygenated functionalities in the oil were responsible for the instability characteristic of the litter biocrude oils. The poor stability of the biocrude oil from the 50:50 w/w% litter mixtures was attributed to reactions between nitrogenous compounds (amides) from protein degradation and oxygenated compounds from the decomposition of polysaccharides and lignin. The addition of 10% methanol and 10% ethanol to the oil from 50% manure and 50% pine reduced the initial viscosity of the oil and was also beneficial in slowing down the rate of viscosity change during storage.     

过氧化氢、过碳酸钠活化过硫酸钠氧化—微生物降解联用技术修复原油污染土壤

分别以H₂O₂和Na₂CO₃·1.5H₂O₂活化Na₂S₂O₄降解原油污染土壤,考察氧化后土壤的原油降解率、pH、微生物含量以及原油组分的变化,比较两种活化剂对过硫酸钠氧化—微生物降解联用技术修复原油污染土壤效果的影响。实验结果表明：两种活化剂氧化处理7 d后的最大原油降解率分别达到42.94%和44.07%;氧化后原油组分的占比情况发生变化,w（饱和烃）增加5.28~11.93个百分点,而w（芳香烃）、w（胶质）和w（沥青质）则分别降低了0.10~2.53,2.53~3.80,0.94~3.43个百分点;添加微生物菌剂进行50 d的生物降解后,两种活化剂的最大原油降解率分别达到71.00%和75.70%,比单独微生物降解时提高了5.96~12.08个百分点。     

Use of a novel biomarker,botryococcane, to monitor biodegradation of two lacustrine‐sourced crude oils

Bioremediation is a proven alternative for remediating petroleum‐impacted soils at exploration and production (E&P) sites. Monitoring remediation performance can involve detection and quantification of biodegradation resistant compounds such as C₃₀17α(H),21β(H)‐hopane, which requires the use of gas chromatography with mass spectrometry detection (GC/MS). Due to the remoteness of many E&P sites, this technology is not always available, and alternative methods are needed to provide reliable quantitative measurements of petroleum remediation efficiency. This study provides a detailed chemical characterization of lacustrine‐sourced crude oils and a technical basis for measuring the effectiveness of bioremediation efforts for soil impacted by those crudes. We show that the novel isoprenoid hydrocarbon botryococcane is relatively stable in lacustrine‐sourced crude oils compared with C₃₀17α(H),21β(H)‐hopane under moderate biodegradation conditions generally observed in field samples. We have also demonstrated that, due to the stability and relatively elevated concentration of botryococcane in lacustrine oils, it can be reliably measured using the more cost‐effective and available GC/FID methodology, and thereby be used to monitor the progress of ongoing soil bioremediation activities at remote sites.     

Utilization and treatment of exhausted cooling oil-emulsions

The subject of investigation was exhausted cooling oil-emulsions coming from copper wire drawing. The summary content of the organic substances in emulsions expressed as COD, ranged from 200 to 300 gO₂/dm³. The total amount of copper was about 7 g/dm³. The suggested method of treatment was based on separation of emulsion, thermocatalytic oxidation of the oil phase and electrochemical reduction of copper. The method allows oxidation of 99% organic substances in an autothermic way and over 90% recovery of metallic copper contained in emulsion with energy consumption at 2.2 kWh/kg.     

Laser fluorosensor overflights of the Santa Barbara oil seeps

The Emergencies Science Division of Environment Canada recently participated in a series of remote sensing flights over the naturally occurring oil seeps off Santa Barbara, California. During these flights the laser environmental airborne fluorosensor was operated to test its ability to detect oil in an actual marine environment. This joint project was sponsored by the United States Minerals Management Service and the Emergencies Science Division of Environment Canada. The Santa Barbara area of the California coastline contains numerous gas and petroleum deposits, which are slowly released from faults under the water and rise to the surface in the form of gas, oil and tar. In and around several of these seeps are kelp beds that release biogenic material, which can be mistaken for petroleum oil by certain remote sensors and human observers. This biogenic oil does not fluoresce when irradiated with ultraviolet light since it contains none of the aromatic compounds necessary to absorb the ultraviolet light and return fluorescence. The laser environmental airborne fluorosensor is, therefore, able to discriminate between this non-fluorescing oil and petroleum oils, which fluoresce with characteristic spectral signatures and intensities. High-resolution colour reconnaissance camera images and down-looking video images were collected concurrently with the fluorescence data for documentation purposes. Fluorescence data were collected at 100 Hz and correlated in real-time against reference spectra characteristic of light refined, crude and heavy oils. Maps of oil detection locations were produced in flight and printed in the aircraft. This paper will present details of the overflights and post-flight analysis of the fluorescence data using the Pearson correlation coefficient.