Gaseous transport of volatile organic chemicals in unsaturated porous media: effect of water-partitioning and air-water interfacial adsorption.

Laboratory experiments were conducted employing gas chromatographic techniques to evaluate the gaseous transport of volatile organic chemicals (VOCs) in water-unsaturated soil columns as influenced by interfacial (air-water) adsorption and water partitioning. VOCs [methylene chloride, tetrachloroethene (PCE), 1,1,1-trichloroethane (TCA), ethyl-benzene, p-xylene, chlorobenzene] with different water-partitioning and interfacial adsorption coefficients (air-water) were used to evaluate the theoretical basis of using these coefficients to predict the retardation factors (Rt) observed during gaseous transport. A loamy sand from Dover Air Force Base, DE, and a commercial sand were used as the column packing material to assess the effect of grain size on the air-water interfacial area (ai) and retardation at different water saturations (Sw). The ai were measured using n-alkanes. At low Sw, interfacial adsorption contributed most to the retardation for all VOCs during gaseous transport in the Dover soil which has little sorption capacity for the VOCs. As Sw increased, the fraction of Rt attributed to interfacial adsorption decreased, while that due to water partitioning increased for all of the VOCs used for this study. For the sand, with a more uniform grain-size distribution than the Dover soil, the contribution of air-water interfacial adsorption to the Rt of a VOC (p-xylene) was not as significant as that for the Dover soil due to small ai. The fractions of Rt attributed to interfacial adsorption and water partitioning were quantified. The observed Rt for the VOCs agreed well with those predicted based on the sorption coefficients and the quantities of sorption domains (Sw, ai).