Electron transfer (redox) reactions, mediated by soil microbiota, modulate elemental cycling and, in part, establish the redox poise of soil systems. Understanding soil redox processes significantly improves our ability to characterize coupled biogeochemical cycling in soils and aids in soil health management. Redox-sensitive species exhibit different reactivity, mobility, and toxicity subjected to their redox state. Thus, it is crucial to quantify the redox potential (Eh) in soils and to characterize the dominant redox couples therein. Several, often coupled, external drivers, can influence Eh. Among these factors, soil hydrology dominates. It controls soil physical properties that in turn further regulates Eh. Soil spatial heterogeneity and temporally dynamic hydrologic regimes yield complex distributions of Eh. Soil redox processes have been studied under various environmental conditions, including relatively static and dynamic hydrologic regimes. Our focus here is on dynamic, variably water-saturated environments. Herein, we review previous studies on soil redox dynamics, with a specific focus on dynamic hydrologic regimes, provide recommendations on knowledge gaps, and targeted future research needs and directions. We review (1) the role of soil redox conditions on the soil chemical-species cycling of organic carbon, nitrogen, phosphorus, redox-active metals, and organic contaminants; (2) interactions between microbial activity and redox state in the near-surface and deep subsurface soil, and biomolecular methods to reveal the role of microbes in the redox processes; (3) the effects of dynamic hydrologic regimes on chemical-species cycling and microbial dynamics; (4) the experimental setups for mimicking different hydrologic regimes at both laboratory and field scales. Finally, we identify the current knowledge gaps related to the study of soil redox dynamics under different hydrologic regimes: (1) fluctuating conditions in the deep subsurface; (2) the use of biomolecular tools to understand soil biogeochemical processes beyond nitrogen; (3) limited current field measurements and potential alternative experimental setups.

Vanadium (V), although serving as an important component of industrial activities, has bioinorganic implications to pose highly toxic hazards to humans and animals. Soils and sediments throughout the world exhibit wide ranges of vanadium concentrations. Although vanadium toxicity varies between different species, it is mainly controlled by soil redox potential (EH). Nonetheless, knowledge of the redox geochemistry of vanadium lags in comparison to what is known about other potentially toxic elements (PTEs). In particular, the redox-induced speciation and mobilization of vanadium in soils and sediments and the associated risks to the environment have not been reviewed to date. Therefore, this review aims to address 1) the content and geochemical fate of vanadium in soils and sediments, 2) its redox-induced release dynamics, 3) redox-mediated chemical reactions between vanadium and soil organic and inorganic colloidal materials in soil solution, 4) its speciation in soil solution and soil-sediments, and 5) the use of advanced geochemical and spectroscopic techniques to investigate these complex systems. Vanadium (+5) is the most mobile and toxic form of its species while being the thermodynamically stable valence state in oxic environments, while vanadium (+3) might be expected to be predominant under euxinic (anoxic and sulfidic) conditions. Vanadium can react variably in response to changing soil EH: under anoxic conditions, the mobilization of vanadium can decrease because vanadium (+5) can be reduced to relatively less soluble vanadium (+4) via inorganic reactions such as with H2S and organic matter and by metal-reducing microorganisms. On the other hand, dissolved concentrations of vanadium can increase at low EH in many soils to reveal a similar pattern to that of Fe, which may be due to the reductive dissolution of Fe(hydr)oxides and the release of the associated vanadium. Those differences in vanadium release dynamics might occur as a result of the direct impact of EH on vanadium speciation in soil solution and soil sediments, and/or because of the EH-dependent changes in soil pH, chemistry of (Fe)(hydr)oxides, and complexation with soil organic carbon. Release dynamics of vanadium in soils may also be affected positively by soil pH and the release of aromatic organic compounds. X-ray absorption spectroscopy (XAS) is a powerful tool to investigate the speciation of vanadium present in soil. X-ray absorption near edge structure (XANES) is often used to constrain the average valence state of vanadium in soils and sediments, and in limited cases extended X-ray absorption fine structure (EXAFS) analysis has been used to determine the average molecular coordination environment of vanadium in soil components. In conclusion, this review presents the state of the art about the redox geochemistry of vanadium and thus contributes to a better understanding of the speciation, potential mobilization, and environmental hazards of vanadium in the near-surface environment of uplands, wetlands, and agricultural ecosystems as affected by various colloidal particles. Further research is needed to elucidate the geochemistry and speciation of vanadium in the dissolved, colloidal, and soil sediments phases, including the determination of factors that control the redox geochemistry of vanadium.

To overcome the drawback of low pH requirement of the classical Fenton reaction, researchers have applied chelating agents to form complexes with Fe and enable Fenton reaction at high pHs, which is reviewed in this article. The chelating agents reviewed include humic substances, polycarboxylates, aminopolycarboxylic acids, and polyoxometalates. Ligands affect the reactivity of Fe-complexes by changing their redox potentials, promoting their reaction with H2O2, and competing with target contaminants for the oxidative species. Fe(III)-complexes are reduced to Fe(II)-complexes by O2- not H2O2, as indicated by their redox potentials. The stability constants of Fe-complexes increase with increasing pKa values of the corresponding ligands and also with increasing charge density of the metal ions. A higher stability constant of Fe(III)-complex indicates higher reaction rate of corresponding Fe(II)-complex with H2O2 and lower reduction rate of Fe(III)-complex to Fe(II)-complex. OH, O2-, and ferryl species were reported to be the reactive species on the contaminant removal in the chelate-modified Fenton process. The generation of these species depends on the chelating agents and reaction conditions. The process is very efficient in degrading contaminants, indicating a potential treatment approach for the pollution remediation at natural pH.

Metal contaminated wastewater posts great health and environmental concerns, but it also provides opportunities for precious metal recovery, which may potentially make treatment processes more cost-effective and sustainable. Conventional metal recovery technologies include physical, chemical and biological methods, but they are generally energy and chemical intensive. The recent development of bioelectrochemical technology provides a new approach for efficient metal recovery, because it offers a flexible platform for both oxidation and reduction reaction oriented processes. While dozens of recent studies demonstrated the feasibility of the bioelectrochemical metal recovery concept, the mechanisms have been different and confusing. This study provides a review that summarizes and discusses the different fundamental mechanisms of metal conversion, with the aim of facilitating the scientific understanding and technology development. While the general approach of bioelectrochemical metal recovery is using metals as the electron acceptor in the cathode chamber and organic waste as the electron donor in the anode chamber, there are so far four mechanisms that have been reported: (1) direct metal recovery using abiotic cathodes; (2) metal recovery using abiotic cathodes supplemented by external power sources; (3) metal conversion using bio-cathodes; and (4) metal conversion using bio-cathodes supplemented by external power sources.