Adsorption of aromatic carboxylate ions to black carbon (biochar) is accompanied by proton exchange with water

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.