Solid Phase Speciation and Solubility of Vanadium in Highly Weathered Soils

Vanadium (V) is increasingly recognized both as a medical trace element with essential biological functions and as a potentially toxic environmental pollutant, yet the current knowledge on V speciation in soils is limited. Here, we investigated the chemical speciation and extractability of V in highly weathered tropical soils, which are often rich in V compared to soils of temperate climatic regions. Vanadium K-edge X-ray absorption near edge structure (XANES) spectra of soil samples, along with a range of reference compounds differing in V-oxidation state and coordination chemistry, revealed the predominance of V^4+/5+ in a primarily octahedral or tetrahedral coordination. The soil spectra were best fitted with linear combinations of reference spectra of V⁴⁺ in the structure of kaolinite, V⁵⁺ adsorbed to kaolinite, and other V⁵⁺-sorbed solids. Vanadate adsorbed to goethite, ferrihydrite, gibbsite, and/or Fe(III)-natural organic matter complexes and V⁴⁺ in the structure of goethite may be present, but cannot unequivocally be distinguished from each other by XANES spectroscopy. Sequential and single chemical extractions provided complementary information on the solubility of V under various conditions. The most labile V fractions, interpreted as weakly and strongly adsorbed V⁵⁺, are the most relevant to V mobility and bioavailability in the environment, and accounted for only ∼2% of total soil V. Our results demonstrate that kaolinite and Fe oxides can effectively sequester V in highly weathered soils by mechanisms of adsorption and structural incorporation and are relevant to other Fe-oxide-rich environments under acidic and oxic conditions.