OIL SPILL SCIENCE chapter 15 – oil spill dispersants a technical summary

OIL SPILL SCIENCE chapter 15 – oil spill dispersants a technical summary OIL SPILL SCIENCE chapter 15 – oil spill dispersants a technical summary OIL SPILL SCIENCE chapter 15 – oil spill dispersants a technical summary OIL SPILL SCIENCE chapter 15 – oil spill dispersants a technical summary OIL SPILL SCIENCE chapter 15 – oil spill dispersants a technical summary OIL SPILL SCIENCE chapter 15 – oil spill dispersants a technical summary OIL SPILL SCIENCE chapter 15 – oil spill dispersants a technical summary

Chapter 15 Oil Spill Dispersants: A Technical Summary Merv Fingas Chapter Outline 15.1 Introduction 15.2 The Basic Physics and Chemistry of Dispersants 15.3 The Basic Nature of Dispersions or Oil-inWater Emulsions 15.4 Effectiveness 435 437 440 15.5 Monitoring 15.6 Physical Studies 15.7 Toxicity 15.8 Biodegradation 15.9 Other Information 15.10 Summary and Conclusions 481 500 519 535 539 562 451 15.1 INTRODUCTION The use of dispersants still generates debate four decades after the Torrey Canyon incident Some of the same issues predominate.1 The motivations for using dispersants are the same: reduce the possibility of shoreline impact, lessen the impact on birds and mammals, and promote the biodegradation of oil The issues surrounding dispersants also remain the same: effectiveness, toxicity, the effect of dispersants on biodegradation, and long-term considerations Recently, the National Academy of Sciences released its study of the use of chemical dispersants in the United States.1 This report is particularly instructive and provides some useful assessments of the situation Their assessments and recommendations will be summarized in the applicable sections of this chapter The prime motivation for using dispersants has been stated to be reduction of the impact of oil on shorelines To accomplish this reduction, the dispersant application must be highly successful and effectiveness high As some oil would still come ashore following treatment, there is much discussion on what effectiveness is required to significantly reduce the shoreline impact.2 A major issue that remains is the actual effectiveness during spills so that these values Oil Spill Science and Technology DOI: 10.1016/B978-1-85617-943-0.10015-2 Copyright Ó 2011 Elsevier Inc All rights reserved 435 436 PART | VI Treating Agents can be used in estimates and models in the future A significant physical fact must also be considereddthat is, the lifetime of the dispersion Because not all dispersions are stable and will degrade to surface slick and some residual dispersion, the utility of dispersants in any case should consider this fact The second motivation for using dispersants is to reduce the impact on birds and mammals on the water surface As the National Academy of Sciences (NAS) committee on dispersants states, little or no research on this matter has been carried out anytime since the 1980s In their report (p 274) they note the following: Of additional concern is the effect of dispersed oil and dispersants on the waterproof properties of feathers and their role as thermal insulators One of the recommendations of the NRC (1989) report was that studies be undertaken to “assess the ability of fur and feathers to maintain the water-repellency critical for thermal insulation under dispersed oil exposure conditions comparable to those expected in the field.” This recommendation is reaffirmed because of the importance of this assumption in evaluating the environmental trade-offs associated with the use of oil dispersants in nearshore and estuarine systems because it has not been adequately addressed.1 The third motivation for using dispersants is to “promote the biodegradation of oil in the water column.” The effect of dispersants on biodegradation is still a matter of dispute A number of papers state that dispersants not promote biodegradation, whereas others indicate that dispersants suppress biodegradation The most recent papers, however, confirm that promotion or suppression is a matter of the surfactant in the dispersant itself and the factors of environmental conditions More details of recent findings will appear in the subsequent discussion What is very clear at this time is that the surfactants in some of the current dispersant formulations can either suppress or have no effect on biodegradation Further, there are issues about the biodegradability of the surfactants themselves, and this fact can confound many tests of dispersed oil biodegradation Several questions remain unanswered, however An important issue that never comes up is that it is known that oil-degrading bacteria largely live on the water surface, where they would feed on natural hydrocarbons in the absence of spills Would not putting oil in the water column then remove it from these bacteria? However, in the case of oil seeps or oil-contaminated sediments, there are microbial colonies associated at depth Another serious question is that of timescale Biodegradation takes place over weeks, months, and years Dispersion half-lives are 12 to 24 hours This author prepared a review of dispersants in 2002 and covered the period to 1997.2 Another review covered the period from 2002 to mid-2008.3 The latter review was combined with the earlier review to provide coverage from 1997 to 2008.4 The comprehensive review contained over 450 references Literature not covered in this present summary is covered in the reviews.5 Another bibliographic search was published during this time as well but did not contain a review.6 Previous reviews covered the various oil spill dispersant topics.7 All these are reviews of the literature, and most cover similar topics as this review Chapter | 15 Oil Spill Dispersants: A Technical Summary 437 15.1.1 What Are Dispersants? Many surfactant mixtures for treating oil spills have been promoted in the past four decades to overcome the extensive problems and costs of physical recovery Of particular interest in this section are dispersants; these are formulations containing surfactants as active ingredients Surfactants have varying solubilities in water and varying actions toward oil and water.8 The parameter used to characterize surfactants is the hydrophiliclipophilic balance (HLB) HLB is determined using theoretical equations that relate the length of the water-soluble portion of the surfactant to the oil-soluble portion of the surfactant A surfactant with an HLB between and promotes the formation of water-in-oil emulsions and one with an HLB between 12 and 20 promotes the formation of oil-in-water emulsions A surfactant with an HLB between and 12 may promote either type of emulsion, but generally promotes oil-in-water emulsions Dispersants have an HLB in this range Dispersants are formulated to “disperse” oil slicks into the sea or another water body Surface-washing agents, or beach cleaners as they are sometimes called, are surfactant formulations designed to remove oil from solid surfaces such as beaches Emulsion breakers and inhibitors are intended to break waterin-oil emulsions or to prevent their formation Although many of these treating agents have been promoted, few are still being produced More than 100 dispersants have been tested for toxicity and effectiveness by Environment Canada, but only remain on the department’s list of accepted products.9 The compendium of oil spill treating agents prepared by the American Petroleum Institute in 1972 lists 69 dispersants and 43 surfacewashing agents, most of which are also listed as dispersants.10 Only two of these are commercially available today, each being produced in a different formulation More than 300 surface-washing agents have been sold in the North American market, but only about 36 of these are still commercially available There were 26 surface-washing agents on the U.S National Contingency Plan List in 2010 It is estimated that approximately 600 dispersants have been sold worldwide, of which only about 200 were ever tested in the lab or field, even in a limited way The abundance of products makes it difficult for potential buyers and environmentalists to discriminate between effective products and those that are ineffective or could actually cause more damage than if the oil were left without intervention 15.2 THE BASIC PHYSICS AND CHEMISTRY OF DISPERSANTS 15.2.1 Formulations Dispersants are oil spill treating agents formulated to disperse oil into water in the form of fine droplets Typically, the HLB of dispersants ranges from to 11 Ionic surfactants can be rated using an expanded scale and have HLBs ranging from 25 to 40 Ionic surfactants are strong water-in-oil emulsifiers, very soluble in water, and relatively insoluble in oil, which generally work from the water 438 PART | VI Treating Agents onto any oil present Such products disappear rapidly in the water column and are not effective on oil Because they are readily available at a reasonable price, however, many ionic surfactants are proposed for use as dispersants These agents are better classified as surface-washing agents Some dispersants contain ionic surfactants in small proportions, yielding an average HLB more toward 15 than 10 Studies on the specific effect of this mixing on effectiveness or mode of action have not been done A typical dispersant formulation consists of a pair of nonionic surfactants in proportions to yield an average HLB of 10 and some proportion of ionic surfactants Studies have been done on this mixture, one of which used statistical procedures in an attempt to determine the best mixture of the three ingredients.11 An improvement in performance was claimed by adjusting the three ingredients Several patents are held on dispersants.12-14 The typical ingredients, from patents, are listed in Table 15.1 Some dispersants listed for use in Canada, the United States, and Europe are listed in Table 15.2 15.2.2 Nature of Surfactant Interaction with Oil Surfactants interact with oil and oil droplets to yield a temporary lower-energy statedgiven many conditions and circumstances 15-18 The disperse state is often called an emulsion, and in the oil spill trade it is known as a dispersiondto distinguish these oil-in-water emulsions from water-in-oil emulsions (called emulsions and sometimes mousse) Some surfactants will align along slick and droplet interfaces and thus promote the temporary stabilization of droplets in water This droplet stabilization is enhanced by the presence of surfactants at the interface TABLE 15.1 Contents of Dispersants (patent information) Type Surfactants and Solvents Hydrocarbon-based -1 Sorbitan monooleate Ethoxylated monooleate Na dioctyl sulfosuccinate Solvent - hydrocarbon and butyl cellosolve Hydrocarbon-based-2 Sorbitan monooleate Ethoxylated sorbitan monooleate Ethoxylated sorbitan trioleate Na tridecyl sulfosuccinate Solvent - hydrocarbon and butanols Hydrocarbon-based-3 Mixtures of polyethylene glycol monoleate Solvent- hydrocarbon Aqueous-based-1 Tall oil esters (35%), ethyl dioxitol (47%) Sorbitan monolaurate (7%), water (10%) Calcium Sulfonate (1%) 439 Chapter | 15 Oil Spill Dispersants: A Technical Summary TABLE 15.2 Listed Dispersants in Various Countries (lists may not be complete due to changes with time) Product Manufacturer/Origin United Canada States Corexit 9500 (now EC9500A) Exxon, Houston U U Corexit 9527 (now EC9527A) Exxon, Houston U U Enersperse xx BP, Britain (old stocks) U Biodispers USA, Newport, NH U Dispersit SPC 1000 Polychem, Chestnut Ridge, NY U Finasol OSR 62 Total Fluides, France U JD (109, 2000) Globemark, Houston, TX U Mare Clean (20, 200, 505) Taiho, Japan U NEOS AB-300 Neos, Japan U Nokomis (3-AA, 3-F4) Mar-Len, Hayward, CA U Saf-Ron Gold Sus Env Tech., Mesa, AZ U Sea Brat #4 Alabaster, Pasadena, TX U ZI-400 Studio City, CA U Agma DR 379, OSD 569 Agma, UK U Caflon OSD Univar, UK U Dasic Slickgone LS Dasic, UK U Emulsol LW Arrow Chemicals, UK U Gard Slicksol Larragard, UK U NU CRU Ara Chem, San Diego, CA U OD 4000, OSR 4000 Innospec, UK U OSD/LT Ashland Chem., Boonton, NJ U Britain France U U Radiagreen OSD, OSD-2B Oleon NV, Belgium U Seacare Ecosperse, 52, OSD U Unitor Chemicals, Norway U U U U (Continued ) 440 PART | VI Treating Agents TABLE 15.2 Listed Dispersants in Various Countries (lists may not be complete due to changes with time)dcont’d United Canada States Product Manufacturer/Origin Britain France Super-dispersant 25 Oil Slick Dispersants, UK U Veclean Oil Dispersant Westchem B.V., NL U W-2096 Baker Petrolite, UK U BIOREICO R93 France U Disper 12 M France U Disperep 12 France U Dispolene 36s France U Emulgal C-100 France U Inipol IP 80, IP 90, IPC France U Neutralex C France U Oceania 1000 France U OD 4000 (PE 998) France U 15.3 THE BASIC NATURE OF DISPERSIONS OR OIL-IN-WATER EMULSIONS It is well known that most emulsions are not stable and will break down into their constituent parts This effect is due to a large number of forces, as will be described in this section, but also to the fact that the stabilizers or surfactants act using weak forces It is also known that chemically dispersed oil destabilizes after the initial dispersion There is an extensive body of literature on surfactants and interfacial chemistry, which includes an abundance of experimental data on the topic as well as many theoretical approaches to it This report will summarize both the data and the theory The phenomenon of resurfacing oil is the result of two separate processes: destabilization of an oil-in-water emulsion and desorption of surfactant from the oil-water interface Almost every paper on the topic of the stability of emulsions notes that emulsions are not stable.15-20 There are also many books on the topic.21-24 It is noted that emulsions are not thermodynamically stable, but may be kinetically stable depending on the timescale considered In the case of kinetic stability, emulsions are not stable in terms of years, and the scale of time considered typically relates to consumer products and may be months In terms of oil spill dispersions, half-life may be only a matter of hours The destabilization of Chapter | 15 Oil Spill Dispersants: A Technical Summary 441 oil-in-water emulsions such as chemical oil dispersions is a consequence of the fact that emulsions are not thermodynamically stable Natural forces move the emulsions to a stable state, which consists of separated oil and water What is important is the rate at which this occurs An emulsion that stays sufficiently stable until long past its practical use consideration may be said to be kinetically stable There are several forces and processes that result in the destabilization and resurfacing of oil-in-water emulsions such as chemically dispersed oils These include gravitational forces, surfactant interchange with water and subsequent loss of surfactant to the water column, creaming, coalescence, flocculation, Ostwald ripening, and sedimentation 15.3.1 Forces of Destabilization 15.3.1.1 Droplet Separation The most important force in resurfacing oil droplets from an oil-in-water emulsion is gravitational separation.25 Droplets in an emulsion tend to move upward when their density is lower than that of water This is true for almost all crude oil and petroleum dispersions as they usually have droplets with a density lower than that of the surrounding water Dense or heavy oils are poorly, if at all, dispersible The rate at which oil droplets will rise due to gravitational forces is dependent on the difference in density of the oil droplet and the water, the size of the droplets (Stokes’s Law, as will be described in Section 15.3.2), and the rheological properties of the continuous phase The rise rate is also influenced by the hydrodynamical and colloidal interactions between droplets, the physical state of the droplets, the rheological properties of the dispersed phased, the electrical charge on the droplets, and the nature of the interfacial film Creaming is a process that is simply described by the appearance of the starting dispersed phase at the surface.25 Creaming is the process that might be described in the oil spill world as resurfacing Robins describes creaming at length, noting that it is a very important phenomenon in the food-processing business.19 As much as 40% of the cost of developing a new food emulsion involves the long-term testing related to creaming Examples of this include yogurt, whipped cream, jam, and many other types of food Sedimentation is the reverse of creaming and occurs when the dispersed phase is denser than water Coalescence is the joining of two or more droplets to form a larger droplet Coalescence is an important destabilization process in oil spills Changes in droplet size resulting in coalescence have been monitored as an emulsion destabilizes Ostwald ripening may be an understated mechanism in the destabilization of oil-in-water emulsions.25 Basically, Ostwald ripening is the growth of larger emulsion droplets by absorption of soluble components from the water column The effect is to remove soluble material from the water column and smaller droplets, resulting in an increased growth of the larger droplets The 442 PART | VI Treating Agents phenomenon occurs because the soluble components of the dispersed phase are more soluble in the larger droplets than in the water and the smaller droplets Although the Ostwald ripening phenomenon has not been investigated with oilin-water emulsions to the same extent as other phenomena, it is believed to be quite important Studies of undecane, hexadecane, benzene, and octane-inwater emulsions have shown that Ostwald ripening is an important factor in destabilization.25 Flocculation is another process that occurs when two particles come together to form an agglomerate of particles, but the particles not coalesce 15.3.1.2 Surfactant Separation It is well known that there is an exchange of surfactants between the target droplet and the surrounding water.18 This promotes destabilization of the emulsion When the water is in a large ratio to the droplet concentration, surfactant is largely lost and destabilization is relatively rapid In laboratory tests, a small ratio of oil-to-water then becomes important in simulating the conditions at sea Surfactants will distribute between the bulk phase (water) and the interface to achieve equilibrium between the two phases This equilibrium depends on the watereoil solubility characteristics of the surfactant In a closed system, this equilibrium is achieved rapidly with little loss of surfactant In an open system, however, equilibrium is never achieved, the surfactant leaches into the water, and over a period of hours, little surfactant is left in the oil droplets The Marangoni effect is an important phenomenon in terms of surfactant stability and dynamics.26 This effect is due to the tendency of surfactant concentrations to quickly distribute over an interface If there is a deficit in surfactant concentration on one side of a droplet, the surfactant quickly moves to restore the equilibrium concentration over the droplet The restoration of equilibrium is known as Marangoni stabilization Marangoni instability arises as a result of this surfactant flow because the flow continues and results in areas of greater and lesser surfactant concentration over the droplet interface Some researchers have noted that Marangoni instability was periodic and was about on the order of 1000 seconds for one particular system.27 It was noted that convective instability periodically switched between a slow and a more rapid transport regime During a convective stage, fast absorption of surfactant occurred with rapid inflow of surfactant to the interface During a diffusive stage, desorption occurred and gradients built up until the system became unstable again Several studies have shown, both experimentally and theoretically, that small surfactants will displace larger surfactants or polymers at the interface Although studies have shown that mixed surfactant systems yield more stable emulsions as a rule, the size difference between surfactants is critical to this A mixed surfactant system with large and small surfactants will essentially be more stable than one stabilized by the small surfactants alone, as these small surfactants will displace the larger surfactants at the interface This condition is 443 Chapter | 15 Oil Spill Dispersants: A Technical Summary Marangoni circulation Surface tension Sub-layer viscosity Radius Surfactant concentration Surfactant diffusion Absorption Desorption Surfactant type Surfactant chain length Steric stabilization Surfactant precipitation Ostwald ripening Dissolution Doublet formation Van der Waals force Oscillatory structure Interactions Surface deformation force Electrostatic force Steric forces Brownian movement Bulk diffusivity Micelle formation Film strength Film thinning Film (Gibbs) elasticity Film thickness Film viscosity Capillary force Velocity of approach Legend Force Flux or movement Influence FIGURE 15.1 Capillary wave Thermal fluctuation Pulse Flocculation Depletion flocculation Hydrodynamic forces The forces and influences on two droplets approaching each other predicated on the fact that the concentration of surfactants at the interface is great and there actually is interference between surfactants Several additional forces have been described and are summarized in the literature.25 These are depicted graphically in Figure 15.1 15.3.2 The Science of Stabilization The basis for much of the physics and chemistry surrounding emulsion stability is that emulsions are not thermodynamically stable.15 One view of this is that two immiscible liquids are combined or one immiscible liquid is dispersed into another immiscible liquid Since the interfacial tension between these two 444 PART | VI Treating Agents liquids will always be greater than zero despite the amount or type of surfactants, there is a force or energy leading toward destabilization Furthermore, the interfacial energy is vastly increased by increasing the area between the two liquids through the process of increasing the number of droplets This results in an energy imbalance that will tend to force the two media to separate Kinetic stability is another consideration when describing an emulsion An emulsion is said to be kinetically stable when significant separation, usually considered to be half or 50% of the dispersed phase, occurs outside of the usable time Therefore, if the time of use is one day, an emulsion with a half-life of more than one day may be considered to be usable In food emulsions, this stability would be well past the stated shelf life It should be noted, however, that food emulsions are poor examples for crude oil-in-water emulsions because their stability can be controlled in closed systems by adding enough surfactants and gelling the water media, thereby negating coalescence and suppressing surfactant loss The function of any emulsifying agent or surfactant is to stabilize (somewhat) an otherwise unstable system The emulsifying agent does so by absorption at the liquideliquid interface as an oriented interfacial film This oriented film performs two functions: (1) it reduces the interfacial tension between the two liquids and consequently the thermodynamic instability of the system resulting from the increase in the interfacial area between the two phases, and (2) it decreases the rate of coalescence of the dispersed liquid droplets by forming mechanical, steric, and/or electrical barriers around them The steric and electrical barriers inhibit the close approach of one droplet to another The mechanical barrier increases the resistance of the dispersed particles to mechanical shock and inhibits them from coalescing when they collide When emulsions form, the emulsifying agents or surfactants reduce the amount of work required for formation Stability can be defined as the resistance of the droplets to coalescence.15 Creaming, or standard gravity separation, was not considered to be destabilization in classical terms because it occurs with or without emulsifier stabilization The classic destabilization processes were considered to be coalescence, flocculation, and phase inversion The rate of coalescence was stated to be the only quantitative measure of emulsion stability These factors have now changed to encompass broader areas, as shown in the present review It has been found that the rate at which the droplets of a macroemulsion coalesce from larger droplets depends on a number of factors: the physical nature of the interfacial film, the existence of an electrical or steric barrier on the droplets, the viscosity of the continuous phase, the size distribution of the droplets, the phase volume ratio, and the temperature These factors are dealt with in greater detail in this section The physical nature of the interfacial film is important The droplets of dispersed liquid in an emulsion are in constant motion and frequently collide If the interfacial film surrounding the two colliding droplets in an emulsion ruptures, the droplets will coalesce to form a larger droplet, and eventually the 568 PART | VI Treating Agents 22 Becher PE In: Becher PE, editor Encyclopedia of Emulsion Technology, vol New York: Marcel Dekker; 1988 23 Becher PE In: Becher PE, editor Encyclopedia of Emulsion Technology, vol 265 New York: Marcel Dekker; 1996 24 Sjoăblom J In: Sjoăblom Johan, editor Emulsions and Emulsion Stability, vol 237 New York: Marcel Dekker; 1999 25 Fingas MF, Ka’aihue L Oil Spill Dispersion Stability and Oil Resurfacing AMOP 2006;729 26 Lavabre D, Pradines V, Micheau J-C, Pimiente V Periodic Marangoni Instability in Surfactant (CTAB) Liquid/Liquid Mass Transfer J Phys Chem 2005:7582e6 27 Lee J, Pozrikidis C Effect of Surfactants on the Deformation of Drops and Bubbles in Navier-Stokes Flow Comput Fluids 2006;43 28 Fingas MF, Decola E Oil Spill Dispersant Effectiveness Testing in OHMSETT, 28 Februarye3 March 2006 Anchorage, AK: Prince William Sound Regional Citizens’ Advisory Council (PWSRCAC) Report; 2006 29 Sterling MC, Bonner JS, Ernest ANS, Page CA, Autenreith RL Chemical Dispersant Effectiveness Testing: Influence of Droplet Coalescence Mar Pollut Bull 2004;969 30 Fingas MF, Models of Oil Spill Dispersion Stability In Proceedings of the Thirty-third Arctic and Marine Oil Spill Program Technical Seminar Ottowa, ON: Environment Canada; 2010:555 31 Baca B, Ward GA, Lane CH, Schuler PA Net Environmental Benefit Analysis (NEBA) of Dispersed Oil on Nearshore Tropical Ecosystems Derived from the 20 Year “Tropic” Field Study IOSC 2005;453 32 Fingas MF A White Paper on Oil Dispersant Testing in Large Tanks Anchorage, AK: Prince William Sound Regional Citizens’ Advisory Council (PWSRCAC) http://www.pwsrcac.org/ projects/EnvMonitor/dispers.html; 2002 33 Fingas MF, Ka’aihue L Dispersant Field Testing: A Review of Procedures and Consideration AMOP 2004;1017 34 Fingas MF A White Paper on Oil Dispersant Field Testing Anchorage, AK: Prince William Sound Regional Citizens’ Advisory Council (PWSRCAC) http://www.pwsrcac.org/projects/ EnvMonitor/dispers.html; 2002 35 OSIR Oil Spill Intelligence Report Arlington, MA: Cutter Information Corporation; October 16, 1997 36 Brandvik PJ, Strom-Kristiansen T, Lewis A, Daling PS, Reed M, Rye H, et al The Norwegian Sea Triald1995: Offshore Testing of Two Dispersant Application Systems and Simulation of an Undersea Pipeline Leakage: A Summary Paper AMOP 1996;1395 37 Lunel T, Davies L Dispersant Effectiveness in the Field on Fresh Oils and Emulsions AMOP 1996;1355 38 Lewis A, Daling PS, Strom-Kistiansen T, Brandvik PJ The Behaviour of Sture Blend Crude Oil Spilled at Sea and Treated with a Dispersant AMOP 1995;453 39 Lunel T Field Trials to Determine Quantitative Estimates of Dispersant Efficiency at Sea AMOP 1994;1015 40 Lunel T Dispersion of a Large Experimental Slick by Aerial Application of a Dispersant AMOP 1994;952 41 Lunel T Dispersant Effectiveness at Sea IOSC 1995;147 42 Lunel T, Davies L, Brandvik PJ Field Trials to Determine Dispersant Effectiveness at Sea AMOP 1995;603 Chapter | 15 Oil Spill Dispersants: A Technical Summary 569 43 Lunel T, Lewis A Oil Concentrations Below a Demulsifier-Treated Slick AMOP 1993;955 44 Swiss JJ, Vanderkooy N, Gill SD, Goodman RH, Brown HM Beaufort Sea Oil Spill Dispersant Trial AMOP 1987;307 45 Sørstrøm SE: The 1985 Full Scale Experimental Oil Spill at Haltenbanken, Norway: In: Proceedings of the International Seminar on Chemical and Natural Dispersion of Oil on the Sea Trondheim, Norway: Centre for Industrial Research; 1986 46 Bocard C L’Operation Protecmar VI; Bulletin de Cedre France; 1985;6 47 Bocard C, Castaing G, Dureux J, Gatellier C, Croquette J, Merlin F Protecmar: The French Experience from a Seven-Year Dispersant Offshore Trials Program IOSC 1987;225 48 Lichtenthaler RG, Daling PS Aerial Application of DispersantsdComparison of Slick Behaviour of Chemically Treated Versus Non-Treated Slicks IOSC 1985;471 49 Nichols JA, Parker HD Dispersants: Comparison of Laboratory Tests and Field Trials with Practical Experience at Spills IOSC 1985;421 50 Swiss JJ, Gill SD Planning, Development and Execution of the 1983 East Coast Dispersant Trails AMOP 1984;443 51 Gill SD, Goodman RH, Swiss JJ Halifax, ’83 Sea Trial of Oil Spill Dispersant Concentrates IOSC 1985;479 52 Delvigne GAL Sea Measurements on Natural and Chemical Dispersion of Oil The Netherlands: Report No M1933-1, Delft Hydraulic Laboratory; 1983 53 Bocard C, Ducreaux J, Gatellier C Protecmar IV France: Report IFP 31478, Institut Franc¸ais de Petrole; 1983 54 Cormack D The Use of Aircraft for Dispersant Treatment of Oil Slicks at Sea London, England: Marine Pollution Control Unit, Department of Transport; 1983 55 Lichtenthaler RG, Daling PS: Dispersion of Chemically Treated Crude Oil in Norwegian Offshore Water, in Oil Pollution Control: Research and Development Program, PFO Projects No 1406 and 1470, ISBN 82-7224-198-6, Trondheim, Norway; 1983 56 Gill SD, Ross CW 1981 Dispersant Application Field Trial, St John’s Newfoundland AMOP 1982;255 57 Bocard C, Gatellier C Protecmar III France: Report IFP 30482, Institut Franc¸ais du Petrole; 1982 58 McAuliffe CD, Steelman BL, Leek WR, Fitzgerald DE, Ray RP, Barker CD The 1979 Southern California Dispersant Treated Research Oil Spills IOSC 1981;269 59 Greene DR, Buckley J, Humphrey B: Fate of Chemically Dispersed Oil in the Sea: A Report on Two Field Experiments: Report No EPS 4-EC-82-5 Ottowa, ON: Environment Canada; 1982 60 Smith DD, Holliday GH API/SC-PCO Southern California 1978 Oil Spill Test Program IOSC 1979;475 61 McAuliffe CD, Johnson JC, Greene SH, Canevari GP, Searl TD Dispersion and Weathering of Chemically Treated Crude Oils in the Ocean Environ Sci Tech 1980;1509 62 Cormack D, Nichols JA The Concentration of Oil in Seawater Resulting from Natural and Chemically Induced Dispersion of Oil Slicks IOSC 1977;381 63 Fingas MF Field Measurement of Effectiveness: Historical Review and Examination of Analytical Methods In: Michael Flaherty L, editor Oil Dispersants: New Ecological Approaches, ASTM STP 1018, vol 157 Philadelphia, PA: American Society for Testing and Materials; 1989 64 Fingas MF, Dispersants: A Review of Effectiveness Measures and Studies, Proceedings of a Dispersant Workshop, December 1989, vol 18 Reston, VA, sponsored by National Oceanic and Atmospheric Administration, Washington, DC; 1989 570 PART | VI Treating Agents 65 Brown HM, Goodman RH Dispersants in the Freshwater Environment In: Michael Flaherty L, editor Oil Dispersants: New Ecological Approaches, ASTM STP 1018, vol 31 Philadelphia, PA: American Society for Testing and Materials; 1989 66 ASTM Guide for Ecological Considerations for the Use of Oilspill Dispersants in Freshwater and Other Inland Environments, Lakes and Large Water Bodies, STP F 1210-08 Philadelphia, PA: American Society for Testing and Materials; 2008 67 ASTM Guide for Ecological Considerations for the Use of Oilspill Dispersants in Freshwater and Other Inland Environments, Rivers, and Creeks, STP F 123d08 Philadelphia, PA: American Society for Testing and Materials; 2008 68 ASTM Guide for Ecological Considerations for the Use of Oilspill Dispersants in Freshwater and Other Inland Environments, Ponds, and Sloughs, STP F 1209d08 Philadelphia, PA: American Society for Testing and Materials; 2008 69 Fingas MF A Review of Laboratory Dispersant Testing In: Proceedings of the EPA Workshop on Dispersant Laboratory Testing, vol 46 NJ: Edison; 1991 70 Clayton Jr JR, Payne JR, Tsang S-F, Frank V, Marsden P, Harrington J Chemical Oil Spill Dispersants: Update State-of-the-Art on Mechanism of Action and Laboratory Testing for Performance, EPA/600/S-92/065 Cincinnati, OH: United States Environmental Protection Agency; 1992 71 Clayton Jr JR, Payne JR, Farlow JS Oil Dispersants: Mechanisms of Action and Laboratory Tests Boca Raton, FL: C.K Smoley for CRC Press; 1993 72 Fingas MF, Kyle DA, Wang Z, Ackerman F, Mullin J Testing of Oil Spill Dispersant Effectiveness in the Laboratory AMOP 1994;905 73 Fingas MF, Kyle DA, Wang Z, Handfield D, Ianuzzi D, Ackerman F Laboratory Effectiveness Testing of Oil Spill Dispersants In: Lane Peter, editor The Use of Chemicals in Oil Spill Response, ASTM STP 1252, vol Philadelphia, PA: American Society for Testing and Materials; 1995 74 Becker KW, Coker LG, Walsh MA A Method for Evaluating Oil Spill Dispersants: Exxon Dispersant Effectiveness Test (EXDET), Proceedings of the Oceans 91 Conference Piscataway, NJ: IEEE Service Centre; 1991 75 Nordvik AB, Hudon TJ Interlaboratory Calibration Testing of Dispersant Effectiveness, Phase I, MSRC 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Many surfactant mixtures for treating oil spills... dispersants on a given oil in a given application situation To demonstrate the effectiveness of dispersants and/or application techniques Chapter | 15 Oil Spill Dispersants: A Technical Summary. .. on oil Because they are readily available at a reasonable price, however, many ionic surfactants are proposed for use as dispersants These agents are better classified as surface-washing agents