Oxidation, aerobic, site

Aerobic sites. Under aerobic conditions, oxygen reduction is the dominant cathodic reaction. Corrosion rates thus depend on the mass transport of oxygen to the steel surface. Under stagnant conditions, oxygen diffusion into the solution under the shielded disbondment is the rate-limiting step. The formation of surface oxides is also important for corrosion kinetics. The main corrosion products expected under aerobic conditions are iron (III) oxides/hydroxides. 

The transformation from anaerobic sites to aerobic sites is a drastic one, with high CP current demand and extremely high corrosion rates. Iron (II) sulfides are oxidized to iron (III) oxides and sulfur species. In turn, sulfur is ultimately oxidized to sulfate. 

The change of aerobic sites to anaerobic sites with SRB leads to reduction of Fe (III) oxides to iron sulfide species. The conversion kinetics are pH dependent. Increasingly corrosive conditions should be anticipated with the formation of sulfide species. 

In the thermodynamically redox-stable resting state, CcOs all Cu ions are in the Cu state and all hemes are Fe . From this state, CcOs can be reduced by one to four electrons. One-electron reduced CcOs are aerobically stable with the electron delocalized over the Cua and heme a sites. The more reduced forms—mixed-valence (two-electron reduced), three-electron reduced, and fully (four-electron) reduced—bind O2 rapidly and reduce it to the redox level of oxide (—2 oxidation state) within <200 p-s [Wikstrom, 2004 Michel, 1999]. This rate is up to 100 times faster than the average rate of electron transfer through the mammalian respiratory chain under normal... 

This process of creating ATP, known as electron transport phosphorylation, then, involves two half-cell reactions, one at the electron donation site and the other where the electrons are accepted from the transport chain. Taking aerobic sulfide oxidation as an example, the donating species H2S(aq) gives up electrons, two at a time, to a series of redox complexes. With the loss of each pair of electrons, the sulfide oxidizes first to S°, then thiosulfate, sulfite, and finally sulfate. 

TCE is the other major contaminant at the site and is a common groundwater contaminant in aquifers throughout the United States [425]. Since TCE is a suspected carcinogen, the fate and transport of TCE in the environment and its microbial degradation have been extensively studied [25,63, 95,268,426,427]. Reductive dechlorination under anaerobic conditions and aerobic co-metabolic processes are the predominant pathways for TCE transformation. In aerobic co-metabolic processes, oxidation of TCE is catalyzed by the enzymes induced and expressed for the initial oxidation of the growth substrates [25, 63, 268, 426]. Several growth substrates such as methane, propane, butane, phenol, and toluene have been shown to induce oxygenase enzymes which co-metabolize TCE [428]. 

Anaerobic conditions often develop in hydrocarbon-contaminated subsurface sites due to rapid aerobic biodegradation rates and limited supply of oxygen. In the absence of O, oxidized forms or natural organic materials, such as humic substances, are used by microorganisms as electron acceptors. Because many sites polluted by petroleum hydrocarbons are depleted of oxygen, alternative degradation pathways under anaerobic conditions tend to develop. Cervantes et al. (2001) tested the possibility of microbially mediated mineralization of toluene by quinones and humus as terminal electron acceptors. Anaerobic microbial oxidation of toluene to CO, coupled to humus respiration, was demonstrated by use of enriched anaerobic sediments (e.g., from the Amsterdam petroleum harbor). Natural humic acids and... 

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