Redox reactions, microbially catalyzed

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,... 

In the next chapter (Chapter 27) we show calculations of this type can be integrated into mass transport models to produce models of weathering in soils and sediments open to groundwater flow. In later chapters, we consider redox kinetics in geochemical systems in which a mineral surface or enzyme acts as a catalyst (Chapter 28), and those in which the reactions are catalyzed by microbial populations (Chapter 33). 

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. 

Lovley, D.R., F.H. Chapelle, and J.C. Woodward. 1994. Use of dissolved H2 concentrations to determine distribution of microbially catalyzed redox reactions in anoxic groundwater. Environ. Sci. Technol. 28, 1205-1210. 

Fig. 20 Microbially catalyzed redox reactions in dependence on pE/EH value (after Stumm and Morgan 1996)...

Figure 11.16 Schematic cross-sections of groundwater systems contaminated by organic-rich Wastes, (a) Development of redox zones down gradient from a landfill in the ground-water flow direction (Baedecker and Back 1979). (b) Possible sequence of redox zones encountered in the groundwater flow direction from a source of organic contamination. After D. R. Lovley, F. H. Chapelle, and J. C. Woodward, Use of dissolved H2 concentrations to determine distribution of microbially catalyzed redox reactions in anoxic groundwater.

Microbial biofuel cells were the earliest biofuel cell technology to be developed, as an alternative to conventional fuel cell technology. The concept and performance of several microbial biofuel cells have been summarized in recent review chapters." The most fuel-efficient way of utilizing complex fuels, such as carbohydrates, is by using microbial biofuel cells where the oxidation process involves a cascade of enzyme-catalyzed reactions. The two classical methods of operating the microbial fuel cells are (1) utilization of the electroactive metabolite produced by the fermentation of the fuel substrate " and (2) use of redox mediators to shuttle electrons from the metabolic pathway of the microorganism to the electrodes. ... 

Some solids dissolve and others precipitate. Many reactions are driven by redox processes associated with the oxidation of organic matter, largely catalyzed by microbial activities as they extract metabolic energy. Some of these are illustrated in... 

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