Effects of Microbially Mediated Redox Conditions on PAH−Soil Interactions

The impacts of microbially mediated redox conditions on the bioavailability of persistent polycyclic aromatic hydrocarbons (PAHs) in soils and sediments have received little study, despite the fact that most water-saturated soils and sediments spend a significant portion of the time under reduced conditions. To address this need an uncontaminated surface soil was incubated under various redox conditions (aerobic, nitrate-reducing, sulfate-reducing, and methanogenic). Depending on redox conditions, different quantities of fulvic and humic acids were liberated as dissolved organic matter (DOM) from the soil during incubation. The DOM released under highly reduced conditions was more nonpolar, aromatic, and polydisperse, of higher molecular weight, and had a higher sorption capacity for pyrene compared to that obtained from relatively oxic incubations. The soil-phase organic matter incubated under reduced conditions also became relatively more aromatic, containing nonpolar organic molecules of lower oxygen contents and exhibiting higher capacity and more nonlinear and hysteric sorption/desorption behavior for pyrene. These observations support the hypothesis that reduced environments established by indigenous soil microbes alter soil organic matter in a matter similar to diagenetic processes. Such humification-like alteration occurred principally in relatively more labile fractions of soil organic matter. These findings are important for assessing the ultimate fate and exposure risk of hydrophobic organic contaminants in soils and sediments where living microorganisms play a significant role in formation and evolution of soil/sediment organic matter.