Reduction, state organic matter

Reductants C N A range of oxidation states Organic matter Marine production and anthropogenic... 

There are several environmentally significant mercury species. In the lithosphere, mercury is present primarily in the +II oxidation state as the very insoluble mineral cirmabar (HgS), as a minor constituent in other sulfide ores, bound to the surfaces of other minerals such as oxides, or bound to organic matter. In soil, biological reduction apparently is primarily responsible for the formation of mercury metal, which can then be volatilized. Metallic mercury is also thought to be the primary form emitted in high-temperature industrial processes. The insolubility of cinnabar probably limits the direct mobilization of mercury where this mineral occurs, but oxidation of the sulfide in oxygenated water can allow mercury to become available and participate in other reactions, including bacterial transformations. 

There are various possible explanations for the decrease in oxidation state of the SOM carbon in most of the soils. One is that the SOM comprises different pools of organic matter with carbon in different oxidation states, and Z decreases as a result of preferential oxidation of more-oxidized pools of SOM, leaving a greater proportion of the more-reduced forms in the residue. The more oxidized SOM would include compounds in the original SOM and also compounds generated in the course of reduction, for example as a result of chemical oxidation by Fe(III) and other metal oxides. Alternatively, part of the organic matter could... 

Iodine is present in the environment predominantly in the oxidation states —1 (1, iodide) and - -5 (lOs", iodate). Reduction of lOs" to 1 occurs at pe = 13.3 at pH 5 and pe° = 11.3 at pH 7. Hence 1 is expected to predominate in the soil solution except in oxic alkaline soils (Whitehead, 1984). However Yuita (1992) found predominantly IO3 in acid Japanese soils contaminated with iodine the concentrations in solution were some 20 times those of 1 and I2. On flooding the soils, the total concentration of 1 in solution increased 10- to 50-fold, predominantly as I. The concentrations of sorbed 1 were not measured, but both lOs and 1 are expected to be bound to organic matter and oxides and hence their concentrations in solution are expected to increase with reductive dissolution reactions. Further, for a given concentration in solution, 1 is more rapidly absorbed by plants than IO3 (Mackowiak and Grossl, 1999). Hence flooding is expected to increase accumulation in plants both through increased solubility and increased absorption. 

Figure 24-1 The nitrogen cycle. Conversion of N2 (oxidation state 0) to NH4+ by nitrogen-fixing bacteria, assimilation of NH4+ by other organisms, decay of organic matter, oxidation of NH4+ by the nitrifying bacteria Nitrosomas and Nitro-bacter, reduction of N03 and N02 back to NH4+, and release of nitrogen as N2 by denitrifying bacteria are all part of this complex cycle.1...

The kinetics of the oxidation of Cr(III) and Cu(I) have been discussed before. Cr(VI) is reduced by dissolved organic matter, the slow re-oxidation resulting in a large enough ti for an existence of Cr(III). Also the existence of Cu(I) in seawater is a steady state between the reduction- and back-oxidation reactions. The lifetime is dependent on pH, PC>2, complexing ligands and redox intermediates such as H2O2 (Moffet and Zika, 1983). 

Among the four elemental components, carbon, nitrogen, and sulfur represent natural chemical redox couples, because each element occurs both in an oxidized and a reduced state. The process of formation of organic matter by photosynthesis constitutes chemical reduction of C, N, and S from their inorganic... 

Equilibria involving reductive dissolution reactions add to the complexity of mineral solubility phenomena in just the way that pE-pH diagrams are more complicated than ordinary predominance diagrams, like that in Fig. 3.7. The electron activity or pE value becomes one of the master variables whose influence on dissolution reactions must be evaluated in tandem with other intensive master variables, like pH or p(H4Si04). Moreover, the status of microbial catalysis under the suboxic conditions that facilitate changes in the oxidation states of transition metals has to be considered in formulating a thermodynamic description of reductive dissolution. This consideration is connected closely to the existence of labile organic matter and, in some cases, to the availability of photons.26... 

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