A lack of understanding about the selenite adsorption behavior on hydroxyaluminum (HyA)‐ and hydroxyaluminosilicate (HAS)‐interlayered phyllosilicates led us to conduct the present study. The kinetics of selenite adsorption on montmorillonite (Mt), HyA(OH/Al = 2.0)‐Mt, HAS1(OH/Al = 2.0; Si/Al = 0.24)‐Mt, and HAS2(OH/Al = 2.0; Si/Al = 0.48)‐Mt were studied at pH 4.5, with an initial selenite concentration of 0.025 mM, a clay concentration of 0.5 g L−1, temperatures of 288, 298, 308, and 318 K, and background electrolyte concentration of 10−2 M NaNO3 Of the six different kinetic models tested, the second‐order rate equation best described the kinetic data obtained for the initial fast reaction (5–30 min) followed by a slow reaction (30–180 min) in the adsorption systems. Elevated temperatures brought about a substantial increase in the rate constants. Compared with Mt, different HyA/HAS‐Mts had 2 to 21 times higher rate constants for the fast reaction and up to five times higher rate constants for the slow reaction. Silication of HyA‐Mt to form HAS1‐Mt and HAS2‐Mt substantially lowered the rate constants for both the fast and slow reactions. For the fast reaction, Mt had the highest activation energy and HyA‐Mt had the lowest activation energy (around four times lower than Mt); silication increased the activation energy of selenite adsorption on the HAS‐Mts. The pre‐exponential factor, an index of the frequency of selenite collision with the clay surface, was remarkably lower for the HyA/HAS‐Mts in comparison with Mt. The data obtained in the present study are of fundamental significance in understanding the role of Al interlayering and coating and silication of Al polymers on expansible phyllosilicates in influencing the dynamics of Se in soil and related environments.
Surface geometry of minerals greatly influences the physical, chemical, and biological processes occurring on the surface. However, a quantitative or even a qualitative description of the surface geometry of minerals has proven to be extremely difficult. In our study, the fine‐scale morphology (1 by 1 µm scale) and surface geometry described by mean surface roughness and surface fractal dimension of Fe oxides formed at various concentrations of citrate, which is common in terrestrial and aquatic environments, were investigated by atomic force microscopy (AFM). Specific surface area and Point of Zero Salt Effect (PZSE) of the Fe oxides, as well as P adsorption, were also studied. Citrate present during the formation of Fe oxides significantly altered the fine‐scale morphology, surface geometry, and other surface characteristics of the products. The mean surface roughness and surface fractal dimension determined by AFM measured the degree of the disorder of surface structure of Fe oxides. The modification of the surface characteristics of the Fe oxides by coprecipitated citrate through fundamental structural changes and the blocking of P‐adsorption sites by citrate affected the P adsorption. Due to the hindrance of the crystallization process, P adsorption per unit weight of the Fe oxides formed at 10‐3 M citrate was very significantly enhanced. The fine‐scale morphology, surface geometry, and related surface characteristics of Fe oxides formed under the influence of organic acids merit close attention as we advance our understanding of their surface chemistry pertaining to dynamics and transformations of nutrients and pollutants in terrestrial and aquatic environments.
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