Factors Affecting Cr(Ⅲ) Oxidation by Manganese Oxides

The high oxidation ability of manganese oxides or soils was used to study effects of pH and coatingon Cr(Ⅲ) oxidation. The results indicated that Cr(Ⅲ) oxidation peaked in pH 4.0-6.5. The amount andrate of Cr(Ⅲ) being oxidized by uncoated δ-MnO2 were larger than those by Fe oxide- or CaCO3-coatedone. Inorganic Cr(Ⅲ) was more easi1y oxidized by MnO2 than organic complex Cr(Ⅲ) due to differentsurface affinities. Precipitated Cr(Ⅲ) and adsorbed Cr(Ⅲ) might be transferred onto MnO2 surface andthen oxidized to Cr(VI).

Equilibrium and kinetic Si isotope fractionation factors and their implications for Si isotope distributions in the Earth's surface environments

Several important equilibrium Si isotope fractionation factors among minerals,organic molecules and the H_4SiO_4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth's surface environments.The results reveal that,in comparison to aqueous H_4SiO_4,heavy Si isotopes will be significantly enriched in secondary silicate minerals.On the contrary,quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution.The extent of ^(28)Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest.In addition,the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated,and the results support the previous statement that highly ^(28)Sienrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations.With the equilibrium Si isotope fractionation factors provided here,Si isotope distributions in many of Earth's surface systems can be explained.For example,the change of bulk soil δ^(30)Si can be predicted as a concave pattern with respect to the weathering degree,with the minimum value where allophane completely dissolves and the total amount of sesquioxides and poorly crystalline minerals reaches their maximum.When,under equilibrium conditions,the well-crystallized clays start to precipitate from the pore solutions,the bulk soil δ^(30)Si will increase again and reach a constant value.Similarly,the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ^(30)Si variations in the ground water profile.The equilibrium Si isotope fractionations among the quadracoordinated organosilicon complexes and the H_4SiO_4solution may also shed light on the Si isotope distributions in the Si-accumulating plants.