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29-3 John.Pdf OceTHE OFFICIALa MAGAZINEn ogOF THE OCEANOGRAPHYra SOCIETYphy CITATION John, V., C. Arnosti, J. Field, E. Kujawinski, and A. McCormick. 2016. The role of dispersants in oil spill remediation: Fundamental concepts, rationale for use, fate, and transport issues. Oceanography 29(3):108–117, http://dx.doi.org/10.5670/ oceanog.2016.75. DOI http://dx.doi.org/10.5670/oceanog.2016.75 COPYRIGHT This article has been published in Oceanography, Volume 29, Number 3, a quarterly journal of The Oceanography Society. Copyright 2016 by The Oceanography Society. All rights reserved. USAGE Permission is granted to copy this article for use in teaching and research. Republication, systematic reproduction, or collective redistribution of any portion of this article by photocopy machine, reposting, or other means is permitted only with the approval of The Oceanography Society. Send all correspondence to: [email protected] or The Oceanography Society, PO Box 1931, Rockville, MD 20849-1931, USA. DOWNLOADED FROM HTTP://TOS.ORG/OCEANOGRAPHY GoMRI: DEEPWATER HORIZON OIL SPILL AND ECOSYSTEM SCIENCE The Role of Dispersants in Oil Spill Remediation Fundamental Concepts, Rationale for Use, Fate, and Transport Issues By Vijay John, Carol Arnosti, Jennifer Field, Elizabeth Kujawinski, and Alon McCormick The crew of a Basler BT-67 fixed-wing aircraft releases oil dispersant over the Deepwater Horizon oil spill, offshore Louisiana. US Coast Guard photo by Petty Officer 3rd Class Stephen Lehmann 108 Oceanography | Vol.29, No.3 ABSTRACT. Offering a scientific perspective, this paper provides a rationale for the and their ecological impacts are found use of dispersants in oil spill remediation by discussing their formulations and modes both in earlier research, as summarized of action and connecting their physics and chemistry to a their environmental fates in a National Research Council (2005) and impacts. With the first use of dispersants at the source of the oil release during the report, and in a more recent book sum- Deepwater Horizon incident, there is a new great need for understanding the efficiency marizing dispersant application for the and the environmental impacts of their use. The paper concludes with some cautionary DWH incident (Judson et al., 2010), with recommendations on dispersant research. details on dispersant testing for efficacy and toxicity, especially as designed by the INTRODUCTION AND are typically solutions containing one or US Environmental Protection Agency PHYSICOCHEMICAL ASPECTS more surfactants (amphiphilic molecules (EPA). In addition, recent research spon- OF DISPERSANT ACTION with hydrophilic polar head groups and sored by the Gulf of Mexico Research Oil dispersants have been shown to break hydrophobic hydrocarbon-based tails) Initiative (GoMRI; http://www.gomri. up surface oil slicks when applied under that partition to the oil-water interface. org) has generated a significant body of the appropriate conditions, leading to The surfactants are dissolved in solvent. literature on the ecological and biological reduced oiling of beaches and shorelines The role of the surfactant is to reduce impacts of dispersants. (National Research Council, 2005). The the interfacial tension between oil and The most widely used and bench- DWH spill was unprecedented in that oil water. The interfacial tension is a mea- marked dispersant is the Corexit class of was being released ~1,600 m below the sure of the energy needed to increase dispersants, particularly EC9500A (here- ocean’s surface. Nevertheless, concerns the oil-water interfacial area by one unit, after referred to as Corexit 9500), devel- about surface worker safety and oil on Gulf defined in units of J –2m or N m–1. Thus, oped by ExxonMobil and manufactured of Mexico beaches and marshes led to the the interfacial tension, γ, can be related to by EcoLab. Corexit 9500 was used in decision to apply dispersants at the sur- the energy input (W) through W = γΔA, the DWH incident and represented the face as well as at depth during the DWH where ΔA is the increase in the oil-water first instance of dispersants applied to spill. Over the course of the spill, 2.9 mil- interfacial area. This equation shows that a deep-sea spill at the source of the oil lion liters of dispersant were applied at a reduction in the interfacial tension has release. Other major classes of disper- depth, and 4.1 million liters were applied the effect of increasing the interfacial area sants include the Dasic class (Slickgone) at the surface (Place et al., 2016). Early for a given amount of energy input (wave made by the Dasic Corporation in the in the spill, the dispersant Corexit 9527 action for surface spills and turbulence UK, and the Finasol class of disper- was the primary formulation, but it was associated with deep-sea release). The sants made by Total SA (France). In replaced with Corexit 9500 once suffi- objective of dispersant systems, there- this paper, we focus on Corexit 9500, cient supplies were available (National fore, is to lower interfacial tension suf- which typically contains three surfactant Commission on the BP Deepwater ficiently to create droplets that have a groups, Span 80 (sorbitan monooleate), Horizon Oil Spill and Offshore Drilling, diameter of less than about 70 µm. At this Tween 80 and Tween 85 (polyoxyethylene 2011). At the surface, dispersants were size range, the oil droplets stay suspended (20) sorbitan monooleate), and DOSS (bis applied sporadically in space and time, in the water column (colloidal stability) (2-ethyl hexyl) sodium sulfosuccinate). based on real-time response to oil slicks. and do not rise to the surface. The sig- DOSS (imprecisely expanded as dioctyl At depth, dispersants were applied nificant increase in surface area of dis- sodium sulfosuccinate) is also referred to directly to the damaged wellhead through persed oil compared to the flat interface as AOT or Aerosol OT in the literature a wand inserted into the primary flow of of a surface oil slick is thought to allow on colloidal science, but this is trademark oil and gas. Although the flow of disper- easier access to oil by oil-degrading bac- nomenclature, and we will use the term sants was not constant, the variability in teria, thus enhancing rates of biodegrada- DOSS in this paper. The surfactants are flow rate was not as large as for the appli- tion (Lee et al., 2013; Prince et al., 2013; dissolved in solvents, typically propylene cation rate on the surface, and thus aver- Aeppli et al., 2014; McFarlin et al., 2014; glycol and petroleum distillates. age flow rates could reasonably approxi- Prince and Parkerton, 2014; Prince and Figure 1 shows structures of the mate an input of dispersant to the deep Butler, 2014). However, recent work indi- primary surfactant components of ocean (Kujawinski et al., 2011). cates that dispersants may suppress the Corexit 9500. The Span and the Tweens With these introductory comments, activity of oil-degrading microorganisms are nonionic saccharide-based surfac- we start with the basics of the physics and (Kleindienst et al., 2015a,b). Excellent tants that are considered to be easily bio- chemistry of dispersants. Oil dispersants reviews on dispersants, their effectiveness, degraded due to their easily metabolized Oceanography | September 2016 109 saccharide-containing structures (Place including cosmetics, textiles, paints, and stockpiled at various locations along the et al., 2016). DOSS is an anionic double- medicine, but had not been previously US coastline and is currently considered tailed surfactant that could persist for sig- applied in large volumes to seawater as the dispersant of choice. nificantly longer periods in the marine dispersants. Place et al. (2016) also found In the remediation of surface spills, environment (Kujawinski et al., 2011; that Corexit 9500 contains 0.28% w/w dispersant is sprayed down onto the sur- Place et al., 2016). Span is insoluble in α- and β-ethylhexyl sulfosucccinate face of the oil slick, preferably from an water while DOSS is sparingly soluble, (EHSS); EHSS likely occurs as a syn- airplane (for fast response, and to avoid but both surfactants are fully soluble in thesis impurity in Corexit 9500, but it spreading the slick with boats; see title hydrocarbons. The twin-tailed DOSS eas- is also reported as an abiotic hydroly- page photo). In application, it is import- ily forms reverse micelles, which transi- sis product and biodegradation prod- ant for the dispersant to be injected into tion to water-in-oil microemulsions with uct of DOSS (Hales, 1993; Campo et al., the oil to enhance surfactant attachment the addition of small amounts of water. 2013). The invention of the Corexit class at the oil-water interface. Dispersant Tweens are fully soluble in water. The of dispersants is attributed to Gerard P. application to bulk seawater leads to dilu- roles of the two solvents are not entirely Canevari at Exxon (McAuliffe et al., 1980; tion of the surfactants and a loss of effi- clear, but it is generally accepted that Canevari, 1982; Nedwed et al., 2008) cacy. After delivery to the oil in surface both solvents are used to ensure com- and is a landmark in oil spill remedia- spills, surfactants must be able to assist patibility with the oil-soluble and the tion technologies. Canevari (1973) devel- dispersion into small droplets with only water-soluble surfactants, and are mutu- oped the idea of blending these three wave action for mechanical agitation. ally miscible, leading to a single-phase types of surfactants in an organic sol- Dispersants are only effective in situa- system. Although the exact composi- vent to apply to the surface of an oil slick tions where weather situations are condu- tion of Corexit 9500 was not disclosed on the open sea. This development was cive to wave action. In the DWH incident, by EcoLab (Nedwed et al., 2008), Place stimulated by the need for more effec- dispersant was directly introduced into et al.
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