Environmental Factors Influencing Sorption of Heterocyclic Aromatic Compounds to Soil

摘要

Heterocyclic organic compounds containing nitrogen, sulfur, or oxygen (NSOs) are an important class of groundwater contaminants related to the production and use of manufactured gas, heavy oils, and coal tar. Surprisingly little is known about the processes that control sorption and transport of NSOs in the subsurface. In this study, the effects of various environmental factors including temperature, ionic strength, and dissolved/sorbed ion composition on the sorption of NSOs have been investigated by means of a soil column chromatography approach. For the investigated compounds, increased temperature normally decreases their sorption to soil. The enthalpy change of the sorption process corroborates earlier findings that van der Waals forces dominate the sorption of S- and O-heterocyclic compounds such as thiophene, benzothiophene, benzofuran, and 2-methylbenzofuran. Ionic strength and ion composition (Ca~(2+) vs K~+ at given ionic strength) of the aqueous phase show no significant effects on the sorption of these compounds. Previous studies demonstrated that for N-heterocyclic compounds, cation exchange and surface complex formation rather than partitioning into soil organic matter control their overall sorption. In contrast to S- and O-heterocyclic compounds, increasing ionic strength reduced the sorption of ionizable N-heterocyclic compounds (pyridine, 2-methylpyridine, quinoline, 2-methylquinoline, and isoquinoline), due to increased electrostatic competition by cations. At given ionic strength, an increase of the K~+/Ca~(2+) ratio in the mobile phase enhanced the sorption of N-heterocyclic compounds, consistent with cation exchange of the protonated organic species as the dominating sorption process. Among the investigated N-heterocyclic compounds sorption of benzotriazole showed a peculiar feature in that ternary surface complexation with Ca~(2+) appears to be the dominant sorption mechanism.