How good are the predictions of mobility of aged polychlorinated biphenyls (PCBs) in soil? Insights from a soil column experiment

A column leaching experiment was performed to evaluate the influence of some relevant environmental factors (soil/water contact time, temperature, saturation) on mobility of aged polychlorinated biphenyls (PCBs) in soil together with transport mediated by dissolved organic carbon (DOC) and mobile organic carbon (OC) coated fine particles/colloids. Consecutive fractions of leachates were collected after a variable pre-equilibration time (2, 5, 7, 48 days), using leaching solutions with different DOC content (tap water vs. Aldrich humic acid), in saturated vs. field capacity conditions and at different temperatures (25 °C vs. 15 °C). The data obtained were compared to the predicted values using a multimedia model (SoilPlusVeg) to evaluate model behaviour. Contact time and temperature determined a relevant effect on DOC and particle/colloid availability, with significant variations in leachate concentrations (up to 1 order of magnitude), typically overlooked by most environmental fate models. Results obtained at different temperatures show a modulation of the DOC/particles production with temperature and therefore the role of temperature changes in the environmental scenarios (e.g. seasonal variations). Transport of PCBs enhanced by Aldrich DOC was not linearly correlated to chemical hydrophobicity but revealed a threshold to ~Log KOW 6.5, likely because of the slow sorption kinetics of more hydrophobic chemicals. Additionally, variation of the saturation conditions (e.g. drying-wetting cycles) can determine contamination peaks at the beginning of an irrigation/rainfall event because of the soil/water equilibration. Model simulations, even when including DOC in the water phase, but not accounting for the particle/colloidal transport and sorption/desorption kinetics, mismatched the ratio of dissolved vs. DOC-associated and particle-associated PCBs and substantially underpredicted concentrations, especially for the high chlorinated congeners. The results indicated that some of the common assumptions and paradigms in fate modelling of such hydrophobic compounds should be revisited and models updated.