Although mixtures of anionic and cationic surfactants can show great synergism, their potential to precipitate and form liquid crystals has limited their use. Previous studies have shown that alcohol addition can prevent liquid crystal formation, thereby allowing formation of middle-phase microemulsions with mixed anionic-cationic systems. This research investigates the role of surfactant selection in designing alcohol-free anionic-cationic microemulsions. Microemulsion phase behavior was studied for three anionic-cationic surfactant systems and three oils of widely varying hydrophobicity [trichloroethylene (TCE), hexane, and n-hexadecane]. Consistent with our hypothesis, using a branched surfactant and surfactants with varying tail length allowed us to form alcohol-free middle-phase microemulsion using mixed anionic-cationic systems (i.e., liquid crystals did not form). The anionic to cationic molar ratio required to form middle-phase microemulsions approached 1:1 for univalent surfactants as oil hydrophobicity increased (i.e., TCE to hexane to n-hexadecane); even for these equimolar systems, liquid crystal formation was avoided. To test the use of these anionic-cationic surfactant mixtures in surfactant-enhanced subsurface remediation, we performed soil column studies: Greater than 95% of the oil was extracted in 2.5 pore volumes using an anionic-rich surfactant system. By contrast, cationic-rich systems performed very poorly (<1% oil removal), reflecting significant losses of the cationic-rich surfactant system in the porous media. The results thus suggest that, when properly designed, anionic-rich mixtures of anionic and cationic surfactants can be efficient for environmental remediation. By corollary, other industrial applications and consumer products should also find these mixtures advantageous.Mixed anionic-cationic surfactant systems. Mixtures of anionic and cationic surfactants often exhibit synergistic effects. The synergism depends on the charge and molecular structure of the individual surfactant components and can be attributed to nonideal mixing effects, which can produce substantially lower critical micelle concentration CMC values and interfacial tensions (IFT) than otherwise possible (1). For anioniccationic surfactant mixtures, the mixed CMC can be two orders of magnitude below that expected if the surfactants have similar structure (2). The use of mixed anionic and cationic surfactants has been evaluated in washing and fabric softening, analytical chemistry, enhanced oil recovery, and pharmaceutical applications (3-5).In this project we are particularly interested in the use of anionic-cationic surfactant mixtures in the formulation of microemulsions. Microemulsions are optically transparent, thermodynamically stable phases containing oil and water stabilized by an interfacial film composed of surfactants and sometimes other molecules (e.g., cosurfactant, alcohols). Microemulsions are important in many applications such as enhanced oil recovery, remediation of oil-impacted aquifer, detergency,...

Environmental contextAmmonium ion, an inorganic pollutant in agricultural land, can induce eutrophication, impacting on water quality. We investigate the adsorption of ammonium ion on surfactant-modified alumina and demonstrate highly efficient removal of ammonium ions by the alumina from two agricultural water samples. Adsorption mechanisms are also proposed based on adsorption isotherms, surface modification and the change in surface charge. AbstractThe adsorptive removal of ammonium ions (NH4+) from aqueous solution using surfactant-modified alumina (SMA) was investigated. The optimum NH4+ adsorption removal conditions on SMA were systematically studied and found to be pH 4, contact time 180min, adsorbent dosage 30mgmL–1 and ionic strength 1mM NaCl. The equilibrium concentration of NH4+ was measured by capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D) and spectrophotometry. Surface modification of α-Al2O3 with the anionic surfactant sodium dodecyl sulfate (SDS) at high salt concentration induced a significant increase of removal efficiency. The change in surface charge and surface modification of α-Al2O3 by pre-adsorption of SDS and subsequent adsorption of NH4+ were evaluated by zeta potential measurements and Fourier-transform infrared spectroscopy. Under optimum adsorption conditions, NH4+ removal from two agricultural water samples achieved very high removal efficiencies of 99.5 and 96.5%. The adsorption of NH4+ onto SMA increases with decreasing NaCl concentration because desorption of SDS from the α-Al2O3 surface is minimised. Experimental results of NH4+–SMA adsorption isotherms at different ionic strengths can be represented well by a two-step adsorption model. Based on adsorption isotherms, surface charge effect and surface modification, we suggest that the adsorption mechanism of NH4+ onto SMA was mainly electrostatic attraction between cationic NH4+ and the negatively charged SMA surface.

Removal of copper ion (Cu2+) by using surfactant modified laterite (SML) was investigated in the present study. Characterizations of laterite were examined by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma mass spectrometry (ICP-MS), and total carbon analysis. The optimum conditions for removal of Cu2+ by adsorption using SML were systematically studied and found as pH 6, contact time 90 min, adsorbent dosage 5 mg/mL, and ionic strength 10 mM NaCl. The equilibrium concentration of copper ions was measured by flame atomic absorption spectrometry (F-AAS). Surface modification of laterite by anionic surfactant sodium dodecyl sulfate (SDS) induced a significant increase of the removal efficiency of Cu2+. The surface modifications of laterite by preadsorption of SDS and sequential adsorption of Cu2+ were also evaluated by XRD and FT-IR. The adsorption of Cu2+ onto SML increases with increasing NaCl concentration from 1 to 10 mM, but at high salt concentration this trend is reversed because desorption of SDS from laterite surface was enhanced by increasing salt concentration. Experimental results of Cu2+/SML adsorption isotherms at different ionic strengths can be represented well by a two-step adsorption model. Based on adsorption isotherms, surface charge effects, and surface modification, we suggest that the adsorption mechanism of Cu2+ onto SML was induced by electrostatic attraction between Cu2+ and the negatively charged SML surface and nonelectrostatic interactions between Cu2+ and organic substances in the laterite.