Dispersion of oil into water using lecithin-Tween 80 blends: The role of spontaneous emulsification.

Lecithin-rich mixtures of the nontoxic surfactants lecithin and Tween 80 are effective marine oil spill dispersants, but produce much higher oil-water interfacial tension than other, comparably effective dispersants. This suggests interfacial phenomena other than interfacial tension influence lecithin-Tween 80 dispersants' effectiveness. The interface between seawater and dispersant-crude oil mixtures was studied using light microscopy, cryogenic scanning electron microscopy, and droplet coalescence tests. Lecithin:Tween 80 ratio was varied from 100:0 to 0:100 and wt% dispersant in the oil was varied from 1.25 to 10wt%. Tween 80-rich dispersants cause oil-into-water spontaneous emulsification, while lecithin-rich dispersants primarily cause water-into-oil spontaneous emulsification. Possible mechanisms for this spontaneous emulsification are discussed, in light of images of spontaneously emulsifying interfaces showing no bursting microstructures, interfacial gel, or phase inversion, and negligible interfacial turbulence. Dispersant loss into seawater due to oil-into-water spontaneous emulsification may explain why Tween 80-rich dispersants are less effective than lecithin-rich dispersants with comparable interfacial tension, although longer droplet coalescence times observed for Tween 80-rich, self-emulsifying dispersant-oil mixtures may mitigate the effects of dispersant leaching. Conversely, surfactant retention in oil via lecithin-rich dispersants' water-into-oil emulsification may explain why lecithin-Tween 80 dispersants are as effective as dispersants containing other surfactant blends which produce lower interfacial tension.

Water-in-Oil Microstructures Formed by Marine Oil Dispersants in a Model Crude Oil.

DOSS (dioctyl sodium sulfosuccinate), Tween 80, and Span 80, surfactants commonly used in marine crude oil spill dispersants, have been mixed into a model oil at a total surfactant concentration of 2 wt %, typical for dispersant-treated oil slicks. These surfactant-oil blends also contained 0.5-1.5 wt % synthetic seawater to enable formation of water-in-oil (W/O) microstructures. Trends in dynamic oil-seawater interfacial tension (IFT) as a function of surfactant blend composition are similar to those observed in prior work for crude oil treated with similar blends of these surfactants. In particular, Span 80-rich surfactant blends exhibit much slower initial dynamic IFT decline than DOSS-rich surfactant blends in both model oil and crude oil, and surfactant blends containing 50 wt % Tween 80 and a DOSS:Span 80 ratio near 1:1 produce ultralow IFT in the model oil (<10(-4) mN/m) just as similar surfactant blends do in crude oil. At all DOSS:Span 80 ratios, surfactant blends containing 50 wt % Tween 80 form clear solutions with seawater in the model oil. Cryo-transmission electron microscopy (cryo-TEM) and dynamic light scattering (DLS) show that these solutions contain spherical W/O microstructures, the size and dispersity of which vary with surfactant blend composition and surfactant:seawater molar ratio. Span 80-rich microstructures exhibit high polydispersity index (PDI > 0.2) and large diameters (≥100 nm), whereas DOSS-rich microstructures exhibit smaller diameters (20-40 nm) and low polydispersity index (PDI < 0.1), indicating a narrow microstructure size distribution. The smaller diameters of DOSS-rich microstructures, as well as the fact that DOSS molecules, being oil-soluble, can diffuse to a bulk oil-water interface as monomers much faster than any of these microstructures, may explain why DOSS-rich blends adsorb to the oil-water interface more quickly than Span 80-rich blends, a phenomenon which has been linked in prior work to the higher effectiveness of DOSS-rich Tween/Span/DOSS-based oil dispersants.

Efficient dispersion of crude oil by blends of food-grade surfactants: Toward greener oil-spill treatments.

Effectiveness of oil spill dispersants containing lecithin/Tween 80 (L/T) blends in ethanol was measured as a function of L:T ratio, surfactant:solvent ratio, solvent composition, and dispersant:oil ratio (DOR) using baffled flask dispersion effectiveness tests. Optimal L:T ratios are between 60:40 and 80:20 (w/w); at higher L:T ratios, effectiveness is limited by high interfacial tension, while at lower L:T ratios, insufficient lecithin is present to form a well-packed monolayer at an oil-water interface. These optimal L:T ratios retain high effectiveness at low DOR: 80:20 (w/w) L:T dispersant is 89% effective at 1:25 DOR (v/v) and 77% effective at 1:100 DOR (v/v). Increasing surfactant:solvent ratio increases dispersant effectiveness even when DOR is proportionally reduced to keep total surfactant concentration dosed into the oil constant. Replacing some of the ethanol with octane or octanol also increases dispersant effectiveness, suggesting that ethanol's hydrophilicity lowers dispersant-oil miscibility, and that more hydrophobic solvents would increase effectiveness.

The role of dispersants' dynamic interfacial tension in effective crude oil spill dispersion.

The dispersion effectiveness of dispersants containing Tween 80, Span 80, and dioctyl sodium sulfosuccinate (DOSS) was characterized using a modified Swirling Flask test, and was correlated with both initial and dynamic interfacial tension produced by those dispersants at an oil-water interface. Compositional trends in effectiveness were shown to be governed by: (1) initial oil-water interfacial tension observed upon dispersant-oil-saltwater contact; (2) rate of increase (or decrease) from the initial interfacial tension as DOSS was rapidly lost to the aqueous phase; and (3) gradually slowing kinetics of dispersant adsorption to the oil-water interface as Span 80 concentration was increased, which ultimately diminished dispersion effectiveness considerably even as dynamic interfacial tension remained <10(-3) mN/m. It is proposed that this third phenomenon results not only from the hydrophobicity of Span 80, but also from the dependence of mixed Tween-Span-DOSS reverse micelles' stability in crude oil on dispersant composition.