Microbial Redox Reactions

Cr(VI).Other remediation processes for Cr(VI) contaminated soils include H2S injection, aqueous Fe(II) injection, and the use of reduced Fe solids. Aqueous-phase Cr(VI)-Fe(II) redox reactions may be significant if Fe2+ concentrations are in equilibrium with relatively soluble, ferric hydroxide-like phases (Tokunaga et al., 2003). The overall interactions involving microbial activity, organic carbon degradation, Fe2+, and mineral surfaces control the net rates of Cr(VI) reactions in soils. 

Field JA, Cervantes FJ (2005) Microbial redox reactions mediated by humus and structurally related quinones. In Perminova IV, Hatfield K, Hertkom N (eds) Use of humic substances to remediate polluted environments from theory to practice, vol 52. Springer, Dordrecht, pp 343-352... 

As discussed already in Chapter 7, redox reactions constitute a second class of geochemical reactions that in many cases proceed too slowly in the natural environment to attain equilibrium. The kinetics of redox reactions, both homogeneous and those catalyzed on a mineral surface are considered in detail in the next chapter, Chapter 17, and the role microbial life plays in catalyzing redox reactions is discussed in Chapter 18. 

The first class, discussed in detail in Chapter 6, was reaction between a fluid and the minerals it contacts. The kinetics of the reactions by which minerals dissolve and precipitate was the subject of the preceding chapter (Chapter 16). The second class of reactions commonly observed to be in disequilibrium in natural waters, as discussed in Chapter 7, is redox reactions. The subject of this chapter is modeling the rates at which redox reactions proceed within the aqueous solution, or when catalyzed on a mineral surface or by the action of an enzyme. In the following chapter (Chapter 18), we consider the related question of how rapidly redox reactions proceed when catalyzed in the geosphere by the action of microbial life. 

Redox reactions in the geochemical environment, as discussed in previous chapters (Chapters 7 and 17), are commonly in disequilibrium at low temperature, their progress described by kinetic rate laws. The reactions may proceed in solution homogeneously or be catalyzed on the surface of minerals or organic matter. In a great many cases, however, they are promoted by the enzymes of the ambient microbial community. 

In considering the energetics of a microbially catalyzed reaction, it is important to recall that progress of the redox reaction (e.g., Reaction 18.7) is coupled to synthesis of ATP within the cell, so the overall reaction is the redox reaction combined with ATP synthesis. The free energy liberated by the overall reaction is the energy liberated by the redox reaction, less that consumed to make ATP. The overall reaction s equilibrium point is where this difference vanishes at this point,... 

The reaction rate Rj in these equations is a catch-all for the many types of reactions by which a component can be added to or removed from solution in a geochemical model. It is the sum of the effects of equilibrium reactions, such as dissolution and precipitation of buffer minerals and the sorption and desorption of species on mineral surfaces, as well as the kinetics of mineral dissolution and precipitation reactions, redox reactions, and microbial activity. 

Fig. 22.6. Redox potentials (mV) of various half-cell reactions during mixing of fluid from a subsea hydrothermal vent with seawater, as a function of the temperature of the mixture. Since the model is calculated assuming 02(aq) and H2(aq) remain in equilibrium, the potential for electron acceptance by dioxygen is the same as that for donation by dihydrogen. Dotted line shows currently recognized upper temperature limit (121 °C) for microbial life in hydrothermal systems. A redox reaction is favored thermodynamically when the redox potential for the electron-donating half-cell reaction falls below that of the accepting half-reaction.

We take two cases in which mineral surfaces catalyze oxidation or reduction, and one in which a consortium of microbes, modeled as if it were a simple enzyme, promotes a redox reaction. In Chapter 33, we treat the question of modeling the interaction of microbial populations with geochemical systems in a more general way. 

The following exemplifies how the total balance of a redox reaction is completed taking an electron donor and an electron acceptor (cf. the outline of the total redox reaction in Figure 2.3). Example 2.2 is, in this respect, used as an example of an (microbial) oxidation of an electron donor (organic matter) under anoxic conditions, i.e., with reduction of NO3 as electron acceptor (cf. Example 2.4). 

Biological action is very important in Se redox transformations. Rates of abiotic selenium redox reactions tend to be slow, and in soils and sediments, Se(VI), Se(IV), Se(0) and organically bormd Se often coexist (Tokrmaga et al. 1991 Zhang and Moore 1996 Zawislanski and McGratii 1998). Bacteria use Se(VI) and Se(IV) as eleclron acceptors (Blum et al. 1998 Dungan and Frankenberger 1998 Oremland et al. 1989), or oxidize elemental Se (Dowdle and Oremland 1998), and it is likely that most of the important redox transformations are microbially mediated. 

These redox reactions are abiogenic, whereas the methane sinks are thought to be biogenic, such as the anaerobic oxidation of methane by archaea as observed at the Lost City vent fields (Figure 19.20). Microbial production of methane has also been observed at this site. 

Most redox reactions in vitro reach equilibrium only extremely slowly with half times of the order of months or years, even though they may be highly favoured thermodynamically. This is illustrated by the persistence of N2 in oxic systems even though its oxidation to NOs is strongly favoured (Table 4.1). However, microbes in soil and water are capable of catalysing particular reactions from which they obtain energy for metabolism. The half times of such microbially catalysed reactions are of the order of hours or days. 

Before we proceed to evaluate the thermodynamics of redox reactions at environmental conditions, we need to make a few remarks on microbial processes that determine the redox conditions in the environment. 

What is apparent in the examination of microbial metal redox reactions is that the metal one microorganism can immobilize, another is capable of solubilizing. This can lead to inadequate metal detoxification and complexation in systems where metal removal is not performed. 

Like the various forms of iron, NOM apparently serves as both bulk reductant and mediator of reduction as well as bulk reductant (recall section 2.2.2). NOM also can act as an electron acceptor for microbial respiration by iron reducing bacteria (26), thereby facilitating the catabolism of aromatic hydrocarbons under anaerobic conditions (103). In general, it appears that NOM can mediate electron transfer between a wide range of donors and acceptors in environmental systems (104,105). In this way, NOM probably facilitates many redox reactions that are favorable in a thermodynamic sense but do not occur by direct interaction between donor and acceptor due to unfavorable kinetics. 

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