Abstract

AbstractThe fate of volatile organic compounds (VOCs) moving as vapors in the subsurface is dependent on their interaction with the soil. Adsorption of VOC vapors is greatly influenced by soil texture and soil‐water content. The effects of differences in texture and soil‐water content on vapor partition coefficients for trichloroethylene (TCE) were examined. Batch experiments were conducted for a variety of soils and at different soil‐water contents, w, to determine the relationship between the vapor/solid partition coefficient, KD′, and w. In dry soils, KD′ was nonlinearly related to soil‐water content because, in that range, water molecules compete with VOC molecules for adsorption sites on the soil surface. Under wet conditions, KD′ became linearly related to water content according to Henry's law, indicating that adsorbed water molecules were acting as a solvent for VOC molecules. In general, KD′ under oven‐dry conditions did not relate well to total specific surface area of soils, most likely because VOC molecules adsorb only on the outside surfaces of soil particles (due to their nonpolarity), rather than the total surface area present. In the dry range, adsorption was dominated by soils with high specific areas (i.e., high clay content), while soils with higher organic carbon content manifested higher adsorption amounts in the wet moisture range. A one‐parameter, exponential model well described the log KD′‐w curve in the nonlinear region. The model parameter, a, was found to be highly dependent on the specific surface area of the soil. The proposed KD′‐(w) model incorporated in conventional VOC transport models seems promising for analyzing the effects of VOC vapor adsorption on VOC subsurface transport.

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