Comparing Linear Free Energy Relationships for Organic Chemicals in Soils: Effects of Soil and Solute Properties

Abstract

Sorption isotherm data were determined for a set of 8 aromatic organic compounds with varying physical chemical properties in three soils with organic matter of differing quantity and composition. The primary goals of this study were to test single and multiparameter linear free energy relationships on their ability to predict the observed sorption behavior on different types of natural sorbents across a range of solutes and concentrations and to relate the accuracy of the predictions to sorbent and solute structural descriptors. Organic carbon normalized sorption coefficients (K(OC)) predicted using both single and multiparameter LFERs were in good agreement with experimental data obtained at the highest tested aqueous concentrations (average deviation less than 0.1 log units over all solutes and sorbents), but deviations were more substantial (0.59-0.65 log units) at the lowest tested concentrations. For chlorinated benzenes there was a significant correlation between experiment-prediction discrepancies and the aromatic content of the soil organic matter measured by (13)C NMR, and the magnitude of the effect was similar to that observed previously for dissolved organic matter.