Adsorption of organic matter at mineral/water interfaces. IV. Adsorption of humic substances at boehmite/water interfaces and impact on boehmite dissolution

The adsorption of Suwannee River fulvic acid (SRFA) and Pahokee peat humic acid (PPHA) at the boehmite (gamma-AlOOH)/water interface and the impact of SRFA on boehmite dissolution have been examined over a wide range of solution pH conditions (pH 2-12), SRFA surface coverages (Gamma(SRFA), total SRFA binding site concentration normalized by the boehmite surface area) of 0.0-5.33 micromol m(-2), and PPHA surface coverages (Gamma(PPHA), PPHA binding site concentration normalized by boehmite surface area) of 0.0-4.0 micromol m(-2), using macroscopic adsorption and in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. At relatively high SRFA surface coverages (Gamma(SRFA) = 5.33 micromol m(-2)), in situ ATR-FTIR spectral features of adsorbed SRFA are very similar to those measured for SRFA in solution at approximately 1-3 pH units higher. At sub-monolayer surface coverages (Gamma(SRFA) = 1.20 and 2.20 micromol m(-2)), several new peaks and enhancements of the intensities of a number of existing peaks are observed. The latter spectral changes arise from several nonorganic extrinsic species (i.e., adsorbed carbonate and water, for alkaline solution conditions), partially protonated SRFA carboxyl functional groups (near-neutral pH conditions), and small quantities of inner-spherically adsorbed SRFA carboxyl groups and/or Al(III)-SRFA complexes (for acidic conditions). The spectra of PPHA adsorbed at boehmite/water interfaces also showed changes generally consistent with our observations for SRFA sorbed on boehmite. These observations confirm that SRFA and PPHA are predominantly adsorbed at the boehmite/water interface in an outer-sphere fashion, with minor inner-sphere adsorption complexes being formed only under quite acidic conditions. They also suggest that the positively charged boehmite/water interface stabilizes SRFA and PPHA carboxyl functional groups against protonation at lower pH. Measurements of the concentration of dissolved Al(III) ions in the absence and presence of SRFA showed that the boehmite dissolution process is clearly inhibited by the adsorption of SRFA, which is consistent with previous observations that outer-spherically adsorbed organic anions inhibit Al-(oxyhydr)oxide dissolution.