Predicting soil-water partitioning of polycyclic aromatic hydrocarbons and polychlorinated biphenyls by desorption with methanol-water mixtures at different temperatures.

We evaluated a method to determine organic carbon-normalized soil-water partition coefficients (Koc) of 20 PAHs and 12 PCBs by desorption in the presence of a cosolvent (methanol fractions of 0.1-0.9) and at different temperatures (20-80 degrees C). The Koc values, the deviation factor from ideal sorption alpha, and the desorption enthalpies delta Hdes were estimated by nonlinear regression of log Koc on the methanol fractions and on T. The Koc values of individual compounds varied up to a factor of 100 among the studied 11 urban soils. The calculated alpha and delta Hdes of individual compounds varied considerably among the soils (coefficients of variation 5-20% and 20-30%, respectively), alpha increased with increasing hydrophobicity of the compounds. A sequential extraction with four temperature/methanol fraction combinations followed by a nonlinear regression allowed for the direct determination of the Koc, alpha, and delta Hdes. The use of less temperature/methanol fraction combinations requires a suitable estimation of alpha and delta Hdes, as their choice may change the obtained Koc values by up to a factor of 10. The proposed method is suitable for a routine determination of Koc values of PAHs and PCBs for small soil samples (2-6 g) and low concentrations (down to 0.3 mg kg-1 of sigma 20 PAHs and 1.2 micrograms kg-1 of sigma 12 PCBs).