The distribution and potential bioavailability of polycyclic aromatic hydrocarbons (PAHs) in soil from a former manufactured-gas plant (MGP) site were examined before and after long-term biostimulation under simulated in situ conditions. Treated soil was collected from the oxygenated zones of two continuous-flow columns, one subjected to biostimulation and the other serving as a control, and separated into low- and high-density fractions. In the original soil, over 50% of the total PAH mass was associated with lower density particles, which made up <2% of the total soil mass. However, desorbable fractions of PAHs were much lower in the low-density material than in the high-density material. After more than 500 d of biostimulation, significant removal of total PAHs occurred in both the high- and low-density materials (77 and 53%, respectively), with three- and four-ring PAHs accounting for the majority of the observed mass loss. Total PAHs that desorbed over a 28-d period were substantially lower in treated soil from the biostimulated column than in the original soil for both the high-density material (23 vs. 63%) and the low-density material (5 vs. 20%). The fast-desorbing fractions quantified by a two-site desorption model ranged from 0.1 to 0.5 for most PAHs in the original soil but were essentially zero in the biostimulated soil. The fast-desorbing fractions in the original soil underestimated the extent of PAH biodegradation observed in the biostimulated column and thus was not a good predictor of PAH bioavailability after long-term, simulated in situ biostimulation.
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