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The Chemistry of Soils$
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Garrison Sposito

Print publication date: 2016

Print ISBN-13: 9780190630881

Published to Oxford Scholarship Online: November 2020

DOI: 10.1093/oso/9780190630881.001.0001

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Oxidation– Reduction Reactions

Oxidation– Reduction Reactions

6 Oxidation– Reduction Reactions
The Chemistry of Soils

Garrison Sposito

Oxford University Press

Soils become flooded occasionally by intense rainfall or by runoff, and a significant portion of soils globally underlies highly productive wetlands ecosystems that are inundated intermittently or permanently. Peat-producing wetlands (bogs and fens) account for about half the inundated soils, with swamps and rice fields each accounting for about one-sixth. Wetlands soils hold about one-third of the total nonfossil fuel organic C stored below the land surface, which is about the same amount of C as found in the atmosphere or in the terrestrial biosphere. This C storage is all the more impressive given that wetlands cover less than 6% of the global land area. On the other hand, wetlands ecosystems are also significant locales for greenhouse gas production. They constitute the largest single source of CH4 entering the atmosphere, emitting about one-third the global total, with half this amount plus more than half the global N2O emissions coming from just three rice-producing countries. A soil inundated by water cannot exchange O2 readily with the atmosphere. Therefore, consumption of O2 and the accumulation of CO2 ensue as a result of soil respiration. If sufficient humus metabolized readily by the soil microbiome (“labile humus”) is available, O2 disappearance after inundation is followed by a characteristic sequence of additional chemical transformations. This sequence is illustrated in Fig. 6.1 for two agricultural soils: a German Inceptisol under cereal cultivation and a Philippines Vertisol under paddy rice cultivation. In the German soil, which was always well aerated prior to its sudden inundation, NO3- is observed to disappear from the soil solution, after which soluble Mn(II) and Fe(II) begin to appear, whereas soluble SO42- is depleted (left side of Fig. 6.1). The appearance of the two soluble metals results from the dissolution of oxyhydroxide minerals (Section 2.4). Despite no previous history of inundation, CH4 accumulation in the soil occurs and increases rapidly after SO42- becomes undetectable and soluble Mn(II) and Fe(II) levels have become stabilized. During the incubation time of about 40 days, the pH value in the soil solution increased from 6.3 to 7.5, whereas acetic acid (Section 3.1) as well as H2 gas were produced.

Keywords:   Faraday constant, anoxic soil, carbon corrosion, dissimilatory, electrode potential, flooded soils, iron reduction, microbial catalysis, oxic soil, reductant

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