We examined the adsorption of the allelopathic aromatic acids (AA), cinnamic and coumaric, to different charcoals (biochars) as part of a study on bioavailability of natural signaling chemicals in soil. Sorption isotherms in pH 7 buffer, where the AAs are >99% dissociated, are highly nonlinear, give distribution ratios as high as 10(4.8) L/kg, and are insensitive to Ca(2+) or Mg(2+). In unbuffered media, sorption becomes progressively suppressed with loading and is accompanied by release of OH(-) with a stoichiometry approaching 1 at low concentrations, declining to about 0.4-0.5 as the pH rises. Sorption of cinnamate on graphite as a model for charcoal was roughly comparable on a surface area basis, but released negligible OH(-). A novel scheme is proposed that explains the pH dependence of adsorption and OH(-) stoichiometry and the graphite results. In a key step, AA(-) undergoes proton exchange with water. To overcome the unfavorable proton exchange free energy, we suggest AA engages in a type of hydrogen bond recognized to be of unusual strength with a surface carboxylate or phenolate group having a comparable pK(a). This bond is depicted as [RCO(2)···H···O-surf](-). The same is possible for AA(-), but results in increased surface charge. The proton exchange pathway appears open to other weak acid adsorbates, including humic substances, on carbonaceous materials.

Microcosms were set up with a PAHs-contaminated soil using biostimulation (addition of ground corn cob) and bioaugmentation (inoculated with Monilinia sp. W5-2). Degradation of polycyclic aromatic hydrocarbons and microbial community were examined at the end of incubation period. After 30 days, bioaugmented microcosms showed a 35+/-0% decrease in total PAHs, while biostimulated and control microcosms showed 16+/-9% and 3+/-0% decrease in total PAHs, respectively. Bioaugmented microcosms also revealed 70+/-8% and 72+/-2% decreases in benzo[a]pyrene and anthracene, respectively, while the values for biostimulated and control microcosms were much lower. Detoxification of soils in bioaugmented microcosms was confirmed by genetic toxicity assay, suggesting important role of fungal remediation. Molecular fingerprint profiles and selective enumeration showed biostimulation with ground corn cob increased both number and abundance of indigenous aromatic hydrocarbons degraders and changed microbial community composition in soil, which is beneficial to natural attenuation of PAHs. At the same time, bioaugmentation with Monilinia strain W5-2 imposed negligible effect on indigenous microbial community. This study suggests that fungal remediation is promising in eliminating PAHs, especially the part of recalcitrant and highly toxic benzo[a]pyrene, in contaminated soil. It is also the first description of soil bioremediation with Monilinia sp.

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