Phosphate sorption on Fe- and Al-oxide minerals helps regulate the solubility and mobility of P in the environment. The objective of this study was to characterize phosphate adsorption and precipitation in single and binary systems of Fe- and Al-oxide minerals. Varying concentrations of phosphate were reacted for 42 h in aqueous suspensions containing goethite, ferrihydrite, boehmite, or noncrystalline (non-xl) Al-hydroxide, and in 1:1 (by mass) mixed-mineral suspensions of goethite/boehmite and ferrihydrite/ non-xl Al-hydroxide at pH 6 and 22 degrees C. X-ray absorption near edge structure (XANES) spectroscopy was used to detect precipitated phosphate and distinguish PO4 associated with Fe(III) versus Al(III) in mixed-mineral systems. Changes in the full width at half-maximum height (fwhm) in the white-line peak in P K-XANES spectra provided evidence for precipitation in Al-oxide single-mineral systems, but not in goethite or ferrihydrite systems. Similarly, adsorption isotherms and XANES data showed evidence for precipitation in goethite/boehmite mixtures, suggesting that mineral interactive effects on PO4 sorption were minimal. However, sorption in ferrihydrite/non-xl Al-hydroxide systems and a lack of XANES evidence for precipitation indicated that mineral interactions inhibited precipitation in these binary mixtures.

Iron‐ and Al‐(hydr)oxide minerals are important sorbents for retaining PO4 in soils. Our objective was to determine the distribution of adsorbed PO4 between ferrihydrite and boehmite in aqueous mixtures of these minerals. Phosphate was adsorbed in aqueous suspensions up to maximum concentrations of 1860, 850, and 1420 mmol kg−1 for ferrihydrite, boehmite, and 1:1 (by mass) mixtures of these minerals at pH 6. The solids were analyzed as moist pastes using P K‐XANES (X‐ray absorption near edge structure) spectroscopy. The adsorption isotherm for the mixed‐mineral suspensions could essentially be described as a linear combination of Freundlich isotherm models for each single‐mineral system, indicating negligible mineral interactive effects on PO4 adsorption in the mixtures. X‐ray absorption near edge structure spectra for PO4 adsorbed on ferrihydrite or in ferrihydrite/boehmite mixtures showed a pre‐edge feature at approximately 2146 eV that was absent in boehmite systems. Linear combination fitting of the pre‐edge region of XANES spectra for mixtures with average spectra for PO4 adsorbed on boehmite or ferrihydrite alone, indicated that 59 to 97% of the PO4 was adsorbed on ferrihydrite in the mixtures. With increasing concentration of adsorbed PO4 in the mineral mixtures, the concentration adsorbed on the ferrihydrite component increased linearly. Phosphate distribution trends in the mixtures suggested an affinity preference for ferrihydrite at the lowest adsorbed PO4 concentration (100 mmol kg−1 minerals), no affinity preference for either mineral at intermediate concentrations (200 to 600 mmol PO4 kg−1), and the possibility of a surface precipitate involving Al at the highest concentration (1300 mmol PO4 kg−1).

Bacterial metal reduction is an important biogeochemical process in anaerobic environments. An understanding of electron transfer pathways from dissimilatory metal-reducing bacteria (DMRB) to solid phase metal (hydr)oxides is important for understanding metal redox cycling in soils and sediments, for utilizing DMRB in bioremedation, and for developing technologies such as microbial fuel cells. Here we hypothesize that the outer membrane cytochromes OmcA and MtrC from Shewanella oneidensis MR-1 are the only terminal reductases capable of direct electron transfer to a hematite working electrode. Cyclic voltammetry (CV) was used to study electron transfer between hematite electrodes and protein films, S. oneidensis MR-1 wild-type cell suspensions, and cytochrome deletion mutants. After controlling for hematite electrode dissolution at negative potential, the midpoint potentials of adsorbed OmcA and MtrC were measured (À201 mV and À163 mV vs. Ag/ AgCl, respectively). Cell suspensions of wild-type MR-1, deletion mutants deficient in OmcA (DomcA), MtrC (DmtrC), and both OmcA and MtrC (DmtrC-DomcA) were also studied; voltammograms for DmtrC-DomcA were indistinguishable from the control. When the control was subtracted from the single deletion mutant voltammograms, redox peaks were consistent with the present cytochrome (i.e., DomcA consistent with MtrC and DmtrC consistent with OmcA). The results indicate that OmcA and MtrC are capable of direct electron exchange with hematite electrodes, consistent with a role as terminal reductases in the S. oneidensis MR-1 anaerobic respiratory pathway involving ferric minerals. There was no evidence for other terminal reductases operating under the conditions investigated. A Marcus-based approach to electron transfer kinetics indicated that the rate constant for electron transfer k et varies from 0.025 s À1 in the absence of a barrier to 63.5 s À1 with a 0.2 eV barrier.

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