Sorption of Non-ionic Aromatic Organics to Mineral Micropores: Interactive Effect of Cation Hydration and Mineral Charge Density

Abstract

The influence of K⁺ and Ca²⁺ on the sorption of non-ionic aromatic contaminants (1,4-dinitrobenzene and p-xylene) on a series of microporous zeolite minerals (HZSM-5) with various surface charge densities was investigated. For zeolites with high or low charge density (>1.78 or <0.16 sites/nm²), K⁺ and Ca²⁺ had negligible influence on the sorption of organics, which mainly occurred at the hydrophobic nanosites. For zeolites with charge density in the moderate range (0.16-1.78 sites/nm²), the sorption of organics was strongly dependent upon the cation hydration effect. K⁺ with a lower hydration free energy greatly favored sorption of organics to the micropores compared to Ca²⁺. Differential scanning calorimetry and X-ray photoelectron spectroscopy results indicated that K⁺ can reduce the water affinity and promote specific sorption of organics in the zeolites with moderate charge density. The above mechanisms were successfully applied to explain the retention of 1,4-dinitrobenzene and p-xylene on four natural minerals (smectite, illite, kaolinite, and mordenite). This study shed new insights on how cation hydration influences sorption interactions of non-ionic aromatic contaminants at mineral-water interfaces as a function of the mineral charge density.