Gelation on demand using switchable double emulsions: A potential strategy for the in situ immobilization of organic contaminants

Abstract

Switchable double emulsions (water in oil in water, W/O/W) are proposed for the in situ immobilization of subsurface organic contaminants such as toluene, hexane or benzene. Primary W/O emulsions were prepared by emulsifying 250 mL of 0.36 M CaCl₂ aqueous solutions in 1 L of canola oil (with 12.5 g/L of ethylcellulose, EC, and 2.5 g/L of calcium stearate). In the primary W/O emulsion the water droplets in oil were ≈8 μm, as observed using an optical and a confocal microscope. EC and calcium stearate adsorbed at the oil water interface (as demonstrated by interfacial tension measurements), forming films which stabilized the W/O emulsions (as verified with bottle tests). Experiments conducted using a Langmuir trough suggest that EC and calcium stearate films did not desorb from the oil-water interface upon compression. Crumpling tests and optical microscopy observations indicate that EC and calcium stearate films were skin-like, and buckled when deformed. To obtain double W/O/W emulsions the primary emulsions were emulsified in a 0.75 wt% solution of sodium alginate, with 2 mL/L of Tween 20 and 10 g/L of NaCl. The formation of W/O/W emulsions was verified through optical microscopy and confocal microscopy observations. In the absence of the contaminants the double emulsions were stable, as observed by resting them on the bench over three days and agitating them with a multi-action wrist shaker for 30 min. Also, they had low shear elastic (G' = 2.67 ± 0.58 Pa) and viscous (G″ = 1.69 ± 0.24 Pa) moduli, which should facilitate their transport through geological media (e.g. soil) to polluted areas. Upon mixing with toluene, hexane or benzene at concentrations ranging from 5% to 17%, the double emulsions were destabilized. Emulsion destabilization caused the release of CaCl₂, which crosslinked sodium alginate and formed gels in which the contaminants were incorporated. The gelation rate and the magnitude of the viscoelastic moduli depended on the contaminant type and concentration, and on the mixing time. Gelation occurred fastest with the highest toluene concentrations tested (9% to 17%), but the highest elastic moduli were measured with 9% toluene concentrations for the longest mixing times tested (90 s). Gelation occurred slowest with hexane, likely due to the poor solubility of EC in hexane. Because of their ability to gel exclusively in contaminant proximity, the double emulsions studied offer a potential strategy to control the migration of plumes of contaminants such as toluene, hexane or benzene.

Keywords: Emulsions; Gels; Immobilization; Remediation; Rheology.