Redox chemistry of vanadium in soils and sediments: Interactions with colloidal materials, mobilization, speciation, and relevant environmental implications- A review.

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 (E). 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 E: 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 HS and organic matter and by metal-reducing microorganisms. On the other hand, dissolved concentrations of vanadium can increase at low E 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 E on vanadium speciation in soil solution and soil sediments, and/or because of the E-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.