The Influence of Humic Substances on the Sorption of Three Organic Contaminants with Different Structure and Polarity to Clay Minerals

The sorption of three organic contaminants with different structure and polarity including non-polar phenanthrene (PHEN), 1,2,4,5-tetrachlorobenzene (TeCB), and polar 1,2-dichlorobenzene (DCB) onto original kaolinite, smectite, vermiculite, and fulvic acid (FA)/humic acid (HA)–clay complexes were investigated, and possible sorption mechanisms were inferred from sorption isotherms and characteristics of humic substances (HS) and HS–mineral complexes. Results showed smectite and vermiculite had stronger sorption ability than kaolinite, and the adsorbed amount of DCB was much higher than that of PHEN and TeCB on each clay. Due to FA/HA-facilitated hydrophobic interaction, FA/HA–clay complexes except FA–vermiculite complex showed a stronger affinity for PHEN and TeCB than the original clays, particularly for HA–clay complexes. The non-linearity parameter values of n for all the Freundlich sorption isotherms of DCB were greater than 1, indicating that clays possessed some unique sites with strong affinity and capacity to sorb DCB from aqueous solutions. FA/HA did not significantly affect the sorption of polar DCB on clays, implying sorption of DCB on clays was probably due to polar interactions between the polar group of DCB and clays. Cation-π bonding between PHEN and iron cation was directly evidenced by X-ray photoelectron spectroscopy, and FA impeded the sorption of PHEN on vermiculite by occupation of iron cation sites. This study will benefit understanding behaviors of contaminants in the soil environments.