Biologically catalyzed Mn(II) oxidation produces biogenic Mn-oxides (BioMnO(x)) and may serve as one of the major formation pathways for layered Mn-oxides in soils and sediments. The structure of Mn octahedral layers in layered Mn-oxides controls its metal sequestration properties, photochemistry, oxidizing ability, and topotactic transformation to tunneled structures. This study investigates the impacts of cations (H(+), Ni(II), Na(+), and Ca(2+)) during biotic Mn(II) oxidation on the structure of Mn octahedral layers of BioMnO(x) using solution chemistry and synchrotron X-ray techniques. Results demonstrate that Mn octahedral layer symmetry and composition are sensitive to previous cations during BioMnO(x) formation. Specifically, H(+) and Ni(II) enhance vacant site formation, whereas Na(+) and Ca(2+) favor formation of Mn(III) and its ordered distribution in Mn octahedral layers. This study emphasizes the importance of the abiotic reaction between Mn(II) and BioMnO(x) and dependence of the crystal structure of BioMnO(x) on solution chemistry.

The influence of crystallite size on the adsorption reactivity of phosphate on 2-line to 6-line ferrihydrites was investigated by combining adsorption experiments, structure and surface analysis, and spectroscopic analysis. X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that the ferrihydrite samples possessed a similar fundamental structure with a crystallite size varying from 1.6 to 4.4 nm. N2 adsorption on freeze-dried samples revealed that the specific surface area (SSABET) decreased from 427 to 234 m(2) g(-1) with increasing crystallite size and micropore volume (Vmicro) from 0.137 to 0.079 cm(3) g(-1). Proton adsorption (QH) at pH 4.5 and 0.01 M KCl ranged from 0.73 to 0.55 mmol g(-1). Phosphate adsorption capacity at pH 4.5 and 0.01 M KCl for the ferrihydrites decreased from 1690 to 980 μmol g(-1) as crystallite size increased, while the adsorption density normalized to SSABET was similar. Phosphate adsorption on the ferrihydrites exhibited similar behavior with respect to both kinetics and the adsorption mechanism. The kinetics could be divided into three successive first-order stages: relatively fast adsorption, slow adsorption, and a very slow stage. With decreasing crystallite size, ferrihydrites exhibited increasing rate constants per mass for all stages. Analysis of OH(-) release and attenuated total reflectance infrared spectroscopy (ATR-IR) and differential pair distribution function (d-PDF) results indicated that initially phosphate preferentially bound to two Fe-OH2(1/2+) groups to form a binuclear bidentate surface complex without OH(-) release, with smaller size ferrihydrites exchanging more Fe-OH2(1/2+) per mass. Subsequently, phosphate exchanged with both Fe-OH2(1/2+) and Fe-OH(1/2-) with a constant amount of OH(-) released per phosphate adsorbed. Also in this stage binuclear bidentate surface complexes were formed with a P-Fe atomic pair distance of ~3.25 Å.

Birnessite, a phyllomanganate and the most common type of Mn oxide, affects the fate and transport of numerous contaminants and nutrients in nature. Birnessite exhibits hexagonal (HexLayBir) or orthogonal (OrthLayBir) layer symmetry. The two types of birnessite contain contrasting content of layer vacancies and Mn­(III), and accordingly have different sorption and oxidation abilities. OrthLayBir can transform to HexLayBir, but it is still vaguely understood if and how the reverse transformation occurs. Here, we show that HexLayBir (e.g., δ-MnO2 and acid birnessite) transforms to OrthLayBir after reaction with aqueous Mn­(II) at low Mn­(II)/Mn (in HexLayBir) molar ratios (5–24%) and pH ≥ 8. The transformation is promoted by higher pH values, as well as smaller particle size, and/or greater stacking disorder of HexLayBir. The transformation is ascribed to Mn­(III) formation via the comproportionation reaction between Mn­(II) adsorbed on vacant sites and the surrounding layer Mn­(IV), and the subsequent migration of the Mn­(III) into the vacancies with an ordered distribution in the birnessite layers. This study indicates that aqueous Mn­(II) and pH are critical environmental factors controlling birnessite layer structure and reactivity in the environment.

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Inositol hexakisphosphates are the most abundant organic phosphates (OPs) in most soils and sediments. Adsorption, desorption, and precipitation reactions at environmental interfaces govern the reactivity, speciation, mobility, and bioavailability of inositol hexakisphosphates in terrestrial and aquatic environments. However, surface complexation and precipitation reactions of inositol hexakisphosphates on soil minerals have not been well understood. Here we investigate the surface complexation-precipitation process and mechanism of myo-inositol hexakisphosphate (IHP, phytate) on amorphous aluminum hydroxide (AAH) using macroscopic sorption experiments and multiple spectroscopic tools. The AAH (16.01 μmol m(-2)) exhibits much higher sorption density than boehmite (0.73 μmol m(-2)) and α-Al2O3 (1.13 μmol m(-2)). Kinetics of IHP sorption and accompanying OH(-) release, as well as zeta potential measurements, indicate that IHP is initially adsorbed on AAH through inner-sphere complexation via ligand exchange, followed by AAH dissolution and ternary complex formation; last, the ternary complexes rapidly transform to surface precipitates and bulk phase analogous to aluminum phytate (Al-IHP). The pH level, reaction time, and initial IHP loading evidently affect the interaction of IHP on AAH. In situ ATR-FTIR and solid-state NMR spectra further demonstrate that IHP sorbs on AAH and transforms to surface precipitates analogous to Al-IHP, consistent with the results of XRD analysis. This study indicates that active metal oxides such as AAH strongly mediate the speciation and behavior of IHP via rapid surface complexation-precipitation reactions, thus controlling the mobility and bioavailability of inositol phosphates in the environment.

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