Summary: | Rice fields are a major source of the greenhouse gases methane (CH<sub>4</sub>) and nitrous oxide (N<sub>2</sub>O) and contribute to nitrate (NO<sub>3</sub><sup>-</sup>) pollution in waters. Ferric iron (Fe<sup>3+</sup>) and manganic manganese (Mn<sup>4+</sup>) are two intermediate alternative electron acceptors (AEAs) capable of regeneration in freshwater soils. In this investigation, the influences of iron-centered intermediate redox processes on NO<sub>3</sub><sup>-</sup> reduction and CH<sub>4</sub> formation in rice soils were studied using soil slurries, soil columns, and potted rice.
Reduction of Fe<sup>3+</sup>-centered intermediate AEAs was mainly mediated by obligate anaerobes relying on fermentation products. Ferric iron reducers are bioelectrochemically active, supporting bioelectricity generation through a fuel cell process from the flooded soil coupled to the reduction of O<sub>2</sub> or NO<sub>3</sub><sup>-</sup> in the overlying water. As a major electron accepting process in anaerobic carbon decomposition, Fe<sup>3+</sup> reduction stimulated N<sub>2</sub>O production but had little influence on overall NO<sub>3</sub><sup>-</sup> reduction in the homogenized soil slurries under near-neutral pH conditions. In the flooded soil column and pot experiments, intensification of iron-centered intermediate redox processes under amendments of iron and/or manganese oxides changed the fate of NO<sub>3</sub><sup>-</sup> in the overlying water, decreasing heterotrophic denitrification and increasing NO<sub>3</sub><sup>-</sup> percolation and N<sub>2</sub>O emission. Ferric iron reduction competitively suppressed methanogenic activity in the homogenized soil slurries. The diffusion of the stronger oxidants O<sub>2</sub> and NO<sub>3</sub><sup>-</sup> controlled temporal and vertical variations of iron-centered intermediate redox processes, which subsequently controlled temporal and vertical variations of methanogenic activity in the flooded soil columns. In the pot experiment, Fe<sup>3+</sup> reduction had small effect on CH<sub>4</sub> emission in the early season when CH<sub>4</sub> emission was low but effectively reduced CH<sub>4</sub> emission after midseason drainage intervals through Fe<sup>3+</sup> regeneration. The roles of iron-centered intermediate redox processes need to be considered in the evaluation and predication of NO<sub>3</sub><sup>-</sup> reduction and CH<sub>4</sub> formation in rice fields.
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