Biotically mediated oxidation

DOM can also act as an electron acceptor for biotically mediated oxidation reactions. Many active microorganisms, particularly phototrophs, produce reductants in excess of metabolic needs that must be regenerated by transfering electrons to acceptors in the environment via membrane-spanning reductases (Price and Morel, 1990). It has been discovered that some iron-reducing bacteria use humic and fulvic acids as terminal electron acceptors for their respiratory transport systems (Coates et al., 1998). 

Figure 4. Multiscale aspects of oxide surfaces in aqueous environments, (b) represents a single trace across a hematite (001) surface undergoing biotically mediated reductive dissolution (a). Relatively clean steps 2.6 nm in size on the left of the figure give way to a complex surface morphology on the right side of the image where biotic dissolution was pervasive. The wavelet transform, to /2 levels, is shown in (c). (b) provided by Kevin Rosso, Pacific Northwest National Laboratory.

Many of the chemical reactions that occur in sediments during diagenesis are mediated by marine organisms or are a consequence of biotic activities. Most are energy-yielding redox reactions driven by the oxidation of organic matter and, hence, represent a critical metabolic resource to benthic organisms. 

A third mechanism by which the structural bonds between Fe atoms in iron oxides may be weakened involves reduction of structural Fe to Fe". In natural environments, reductive dissolution is by far the most important dissolution mechanism. It is mediated both biotically and abiotically. The most important electron donors, particularly in near surface ecosystems result from metabolic oxidation of organic compounds under O2 deficient conditions. In anaerobic systems, therefore, the availability of Fe oxides i. e. the electron sink, may control the degradation of dead biomass and organic pollutants in the ground water zone (see chap. 21). Reductive dissolution is also often applied to the removal of corrosion products from piping in industrial equipment and the bleaching of kaolin. 

The need for biological mediation of most redox processes encountered in natural waters means that approaches to equilibrium depend strongly on the activities of the biota. Moreover, quite different oxidation-reduction levels may be established within biotic microenvironments than those prevalent in the over-all environment diffusion or dispersion of products from the microenvironment into the macroenvironment may give an erroneous view of redox conditions in the latter. Also, because many redox processes do not couple with one another readily, it is possible to have several different apparent oxidation-reduction levels in the same locale, depending upon the system that is being used as reference. 

Thus, the reduced form of cytochrome P-450 functions as the oxygenactivating biocatalyst of a wide variety of mixed-function oxidations by vertebrate tissues effecting biosynthesis and catabolism of steroid hormones, bile acid formation, and the metabolism of drugs and other xeno-biotics (16). Since reduced pyridine nucleotides do not react directly with hemoproteins, the hydroxylase systems must include components that mediate the electron transport from TPNH to cytochrome P-450. There also must be distinctive diflFerences in composition causing the substrate specificity of the oxygenations. 

Wetlands exhibit distinct redox gradients between the soil and overlying water column and in the root zone (Chapter 4), resulting in aerobic interfaces. For example, the aerobic layer at the soil-floodwater interface is created by a slow diffusion of oxygen and the rapid consumption at the interface. The thin aerobic layer at the soil-floodwater interface and around roots functions as an effective zone for aerobic oxidation of Fe(ll) and Mn(II). Below this aerobic layer there exists the zone of anaerobic oxidation of Fe(ll) and Mn(ll) and reduction of Fe(III) and Mn(IV). The juxtaposition of aerobic and anaerobic zones creates conditions of intense cycling of iron and manganese mediated by both biotic and abiotic reactions. 

Several researchers have also suggested that bacteria mediate mercury reduction [54,55]. SicUiano et al. [56] recently examined the role of microbial reduction and oxidation processes in regulating DGM diel (over a 24h period) patterns in freshwater lakes. The authors demonstrate that photochemi-cally produced hydrogen peroxide regulates microbial oxidation processes and may account for the diel patterns observed in DGM data. Overall, the mechanisms responsible for mercury reduction and the relative contributions of biotic and abiotic processes are still unclear but solar radiation appears to be a common instigator of photo-reduction. 

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