Manganese oxides hydrous

Manceau, A., Gorshkov, A. 1., and Drits, V. A., 1992a, Structural chemistry of Mn, Fe, Co, and Ni in manganese hydrous oxides Part 1. Information from XANES spectroscopy American Mineralogist, v. 77, p. 1133-1143. 

Sequential extraction procedures developed by Tessier etal. (1979) were applied to house dust and street dust by Fergusson and Kim (1991). Results indicated that most of the Pb (65-85%), Zn (70-95%), and Cd (60 -80%) was associated with the carbonate phase and the amorphous iron/ manganese hydrous oxide phases, but it was noted that the distribution of metals amongst different matrix components varied with proximity to different industrial sources. In another study, Zn was associated with the calcium-rich matrix, whereas Cd and Pb were associated with the silicon-rich matrix (Johnson et al., 1982). 

The Mn ion is so unstable that it scarcely exists in aqueous solution. In acidic aqueous solution, manganic compounds readily disproportionate to form Mn ions and hydrated manganese(IV) oxide, Mn02 2H20 in basic solution these compounds hydroly2e to hydrous manganese(III) oxide, MnO(OH). Sulfuric acid concentrations of about 400 450 g/L are required to stabilize the noncomplexed Mn ion in aqueous solutions. 

In Skirmer, H.G.W. Fitzpatrick, R.W. (eds.) Biomineralization processes of iron and manganese. Catena Verlag, Cremhngen-Destedt, Catena Suppl. 21 75—99 Ghoneimy, H.F. Morcos.T.N. Misak, N.Z. (1997) Adsorption of Co and Zn ions on hydrous Fe(lll), Sn(lV) and mixed Fe(lll)/ Sn(IV) oxides. Part 1. Characteristics of the hydrous oxides, apparent capacity and some equilibria measurements. Colloids Surfaces A. 122 13-26... 

Samples of the red clay having uniform physical and chemical characteristics were provided by G. R. Heath of the University of Rhode Island. The samples were obtained from core LLUU-GPC-2, collected on October 11, 1976, at 30° 20.9 n, 157° 50.85 w, water depth 5821 meters, and are representative of the smectite-rich region of the red clays which occurs in the sediment at depths below about ten meters. In this region, the sediment appears to contain about five to six percent by weight leachable iron and manganese in the form of hydrous oxides. The remaining material appears to be dominated by iron-rich smectite and lesser, varying amounts of phillipsite (2). The results of a semi-quantitative (precision in data is within a factor of 2) elemental analysis... 

Arsenic is most prone to form surface complexes by adsorption on metal (mostly iron and manganese) (oxy)(hydr)oxides, followed by clays and feldspars (Lin and Puls, 2003). As discussed in Chapters 3 and 7, iron (oxy)(hydr)oxides are groups of Fe(III) Fe(II) (hydrous) oxides, (hydrous) hydroxides, and (hydrous) oxyhydroxides. Individual compounds, such as ferrihydrite, often have highly variable and... 

Literally hundreds of complex equilibria like this can be combined to model what happens to metals in aqueous systems. Numerous speciation models exist for this application that include all of the necessary equilibrium constants. Several of these models include surface complexation reactions that take place at the particle-water interface. Unlike the partitioning of hydrophobic organic contaminants into organic carbon, metals actually form ionic and covalent bonds with surface ligands such as sulfhydryl groups on metal sulfides and oxide groups on the hydrous oxides of manganese and iron. Metals also can be biotransformed to more toxic species (e.g., conversion of elemental mercury to methyl-mercury by anaerobic bacteria), less toxic species (oxidation of tributyl tin to elemental tin), or temporarily immobilized (e.g., via microbial reduction of sulfate to sulfide, which then precipitates as an insoluble metal sulfide mineral). 

Bound to hydrous oxides of iron and manganese (HOx/NH4Ox)... 

In addition to the soluble chemical species and possible solid phase species described in the previous sections no discussion on speciation can be complete without the consideration of surface species. These include the inorganic and organic ions adsorbed on the surface of particles. Natural systems such as soils, sediments and waters abound with colloids such as the hydrous oxides of iron, aluminium, manganese and silicon which have the potential to form surface complexes with the various cationic and anionic dissolved species (Evans, 1989). 

Figure 1-4 shows an exchange between the soil solution and precipitates . Both soluble iron and manganese will precipitate out from the soil solution as hydrous oxides, as pH or redox potential change, for iron, the changes can be represented very simply as ... 

CNTs were also demonstrated to be a perfect support for cheap transition metal oxides of poor electrical conductivity, such as amorphous manganese oxide (a-Mn02 H20) [5,96], The pseudocapacitance properties of hydrous oxides are attributed to the redox exchange of protons and/or cations with the electrolyte as in Equation 8.13 for a-Mn02 H20 [97] ... 

Surface Complex Formation. Metal ions form both outer and inner sphere complexes with solid surfaces, e.g. hydrous oxides of iron, manganese, and aluminium. In addition, metal ions, attracted to charged surfaces, may be held in a diffuse layer, which, depending upon ionic strength, extends several nanometres from the surface into solution. 

Hydrous Oxides. This term is generally taken to include the oxides, hydroxides, and oxyhydroxides of aluminium, iron and manganese, which form in soil when these elements are released from primary minerals by weathering. They exist mainly as small particles in the claysized fraction of a soil (<2 pm), and also as coatings on other soil minerals or as components of larger aggregates. 

Manganese is relatively abundant, constituting about 0.085% of the earth s crust. Among the heavy metals, only Fe is more abundant. Although widely distributed, it occurs in a number of substantial deposits, mainly oxides, hydrous oxides, or carbonate. It also occurs in nodules on the Pacific seabed together with Ni, Cu, and Co. 

Phosphorus extracted from sediment by NaOH has been related to non-occluded, surface-exchangeable, bioavailable forms (22). Hydrochloric acid extraction yields occluded phosphorus incorporated in hydrous metal oxides, carbonate and phosphate minerals of sediment. Hydroxylamine reagent specifically removes hydrous manganese oxides, while amorphous hydrous oxides of iron and aluminijm are removed by the oxalate reagent. Total available sediment phosphorus analyses includes sediment organic phosphorus components in addition to the inorganic portion determined by the selective extraction procedures. 

Inorganic phosphorus Incorporated with easily reducible hydrous manganese oxides is typically less than that found for the hydrous oxides of iron and aluminum. 

Finally, finely divided hydrous oxides of iron, aluminum, manganese, and silicon are the dominant sorbents in nature because they are common in soils and rivers, where they tend to coat other particles. This is the reason why numerous laboratory researchers have been studying the uptake of trace elements by adsorption on hydrous oxides (Dzomback and Morel, 1990). Partition coefficients (concentration in solid/concentration in the solution) for a number of trace elements and a great variety of surfaces have been determined. The comparison of these experimental with natural values should give information on the nature of the material on which trace elements adsorb in namral systems and allow quantitative modeling. 

Many of the important chemical reactions controlling arsenic partitioning between solid and liquid phases in aquifers occur at particle-water interfaces. Several spectroscopic methods exist to monitor the electronic, vibrational, and other properties of atoms or molecules localized in the interfacial region. These methods provide information on valence, local coordination, protonation, and other properties that is difficult to obtain by other means. This chapter synthesizes recent infrared, x-ray photoelectron, and x-ray absorption spectroscopic studies of arsenic speciation in natural and synthetic solid phases. The local coordination of arsenic in sulfide minerals, in arsenate and arsenite precipitates, in secondary sulfates and carbonates, adsorbed on iron, manganese, and aluminium hydrous oxides, and adsorbed on aluminosilicate clay minerals is summarized. The chapter concludes with a discussion of the implications of these studies (conducted primarily in model systems) for arsenic speciation in aquifer sediments. 

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