Three models for sorption/desorption of polycyclic aromatic hydrocarbon (PAH) contaminants from soil were compared for their ability to predict the transport of PAH in soil: a "gamma" model, a "two-site/two-region" nonequilibrium model, and a"hybrid" model. In the "hybrid" model, soil organic matter was conceptually divided into two compartments; a fraction with rapid sorption/desorption kinetics and a compartment with mass-transfer-limited kinetics. Contaminant sorbed in the rapidcompartment was assumed to be in instantaneous equilibrium with the aqueous phase, while the release of contaminant from the slow fraction was assumed to be governed by a gamma distribution of rate coefficients. The "hybrid" model successfully describedthe initial rapid release of a model PAH contaminant, naphthalene, from a sieved soil sample of moderate organic content (≈2.3) as well as the following slow release observed over 25 days in batch desorption experiments. Other necessary modelparameters, such as the hydrodynamic dispersion coefficient of naphthalene and the macropore porosity, were evaluated in separate experiments. A transport model incorporating the "hybrid" model for naphthalene sorption/desorption successfully predictedthe elution profile of naphthalene in independent soil-column experiments with no adjustable parameters. The success of the hybrid model suggests that a wide array of rate controls govern PAH desorption. This conclusion is consistent with the view ofsoils as consisting of a mix of different sorptive constituents and heterogeneous physical constraints on PAH release.
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