| Abstract
| - To elucidate interactions of neutral organic contaminants (NOCs) with siloxane surfaces (often referred to hydrophobic nanosites) found between cations in 2:1 phyllosilicates, adsorption of aliphatic and aromatic compounds onto both internal and external siloxane surfaces of tetramethylammonium-intercalated bentonite with a cation exchange capacity (CEC) of 108 cmol/kg (108TMA) and its reduced-charge bentonite (CEC = 65 cmol/kg, 65TMA) were investigated. Reduction of the layer charge and saturation of bentonite interlayers with TMA+ modify the interlayer microenvironments, which dramatically promote adsorption of NOCs. Specific mechanisms (i.e., steric restriction and phenyl-effect) control the adsorption of NOCs onto internal siloxane surfaces of TMA+-bentonites from water. The adsorption sites of 108TMA can not provide sufficient space to accommodate NOCs, hence hindering adsorption. Adsorption mechanism on 65TMA varies with solute-loadings, from polarity-selective at low loadings to aromaticity-preferable at high loadings. Significant contribution of phenyl-effect between adsorbed-solutes to aromatics adsorption on 65TMA is found. Solvent polarity effect on the aggregation of TMA+-bentonites and aniline adsorption demonstrated that the contribution of external siloxane surfaces to favor adsorption in n-hexane are actually exploited but generally omitted. These observations provide significant insights into distinguishing different uptake mechanisms as well as the potential means for the rational design of better organic sorbents.
- The availability of siloxane surfaces in bentonites significantly exploited by reducing layer charge, and subsequently, saturating with TMA+ dominates the nature of adsorption mechanisms.
|
