Environmental contextVanadium, a metal pollutant from fossil fuels and slags, may be toxic, thereby necessitating an understanding of its environmental chemistry. One important factor that controls the mobility and bioavailability of vanadium is its binding to iron oxides. This study focuses on the characterization and modelling of vanadium adsorption onto ferrihydrite. The new model can be used to simulate the transport and bioavailability of vanadium in the environment. AbstractThe mobility of vanadium in the environment is influenced by sorption to metal (hydr)oxides, especially those containing iron. The aim of this study is to understand the adsorption behaviour of vanadium on poorly ordered (two-line) ferrihydrite (Fh). A further objective was to determine the binding mechanism of vanadate(V) to ferrihydrite surfaces in aqueous suspension to constrain the CD-MUSIC surface complexation model. Vanadium adsorption to ferrihydrite was evaluated by batch experiments which included series with different Fh-to-V ratios and pH values. Vanadate(V) adsorption was also evaluated in the presence of phosphate to compete with vanadate(V) for the available surface sites on ferrihydrite. In agreement with earlier studies, vanadate(V) was strongly adsorbed to ferrihydrite and the adsorption increased with decreasing pH. In the presence of phosphate, less vanadate(V) was adsorbed. Analysis by X-ray absorption near-edge structure spectroscopy revealed that the adsorbed vanadium was tetrahedral vanadate(V), VO4, regardless of whether vanadate(V) or vanadyl(IV) was added to the system. Spectra collected by extended X-ray absorption fine structure spectroscopy showed that vanadate(V) is bound primarily as an edge-sharing bidentate complex with V⋯Fe distances around 2.8Å. Based on this information, a surface complexation model was set up in which three bidentate vanadate(V) complexes with different degrees of protonation were included. The model provided a satisfactory description of vanadate(V) adsorption over most of the pH and concentration ranges studied, also in the presence of competing phosphate ions.

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Total vanadium (V) concentrations in soils commonly range from 20 to 120 mg kg−1. Vanadium added directly to soils is more soluble than geogenic V and can be phytotoxic at doses within this range of background concentrations. However, it is unknown how slow sorption reactions change the fate and effect of added V in soils. This study addresses the changes in V solubility, toxicity and bioavailability in soils over time. Four soils were amended with pentavalent V in the form of a soluble vanadate salt, and extractable V concentrations were monitored over 100 days. The toxicity to barley and tomato plants was evaluated in freshly spiked soils and in the corresponding aged soils that were equilibrated for up to 330 days after spiking. The V concentrations in 0.01 m CaCl2 soil extracts decreased approximately two‐fold between 14 and 100 days after soil spiking, and the reaction kinetics were similar for all soils. The phytotoxicity of added V decreased on average two‐fold between freshly spiked and aged soils. The reduced toxicity was associated with a corresponding decrease in V concentrations in the isolated soil solutions and in the shoots. The V speciation in the soil solution of the aged soils was dominated by V(V); less than 8% was present as V(IV). Oxalate extractions suggest that the V(V) added to soils is predominantly sorbed onto poorly crystalline oxyhydroxides. It is concluded that the toxicity of V measured in freshly spiked soils may not be representative of soils subject to a long‐term V contamination in the field.

The toxicity of vanadium in soils depends on its sorption to soil components. Here we studied the vanadate(V) sorption properties of 26 mineral soils. The data were used to optimise parameters for a Freundlich equation with a pH term. Vanadium K-edge XANES spectroscopy for three selected soils confirmed that the added vanadate(V) had accumulated mostly as adsorbed vanadate(V) on Fe and Al hydrous oxides, with only minor contributions from organically complexed vanadium(IV). Data on pH-dependent V solubility for seven soils showed that on average 0.36 H accompanied each V during adsorption and desorption. The resulting model provided reasonable fits to the V sorption data, with r > 0.99 for 20 of 26 soils. The observed K value, i.e. the ratio of total to dissolved V, was strongly dependent on V addition and soil; it varied between 3 and 4 orders of magnitude. The model was used to calculate the Freundlich sorption strength (FSS), i.e. the amount of V sorbed at [V] = 2.5 mg L, in the concentration range of observed plant toxicities. A close relationship between FSS and oxalate-extractable Fe and Al was found (r = 0.85) when one acidic soil was removed from the regression. The FSS varied between 27 and 8718 mg V kg, showing that the current environmental guidelines can be both under- and overprotective for vanadium.

24A field-trial with different application rates of converter lime (0.2, 0.7 and 1.0 kg m -2 ) was set up 25 in a pine forest stand in southern Sweden in 1984. The lime contained 14.6 g kg -1 vanadium. The aim 26 with this study was to evaluate the vanadium concentration and speciation in the soil 26 years after 27 application. Samples of the organic mor layer and the mineral soil were analysed separately. The 28 vanadium concentration decreased with soil depth, from 680 to 8 mg kg -1 soil. Analysis by vanadium 29 K-edge XANES spectroscopy showed that vanadium(IV) was the predominant species in the mor 30 layer. Further, iron and/or aluminium (hydr)oxides were important sorbents for vanadium(V) in the 31 mineral soil. The speciation of dissolved vanadium, as determined by HPLC-ICP-MS, was dominated 32 by vanadium(V), which is considered the most toxic vanadium species. However, the vanadium 33 sorption capacity of the soil was sufficient to reduce the total bioavailable vanadium below phytotoxic 34 levels. By combining two different vanadium speciation methods, this study was able to conclude that 35 vanadium speciation in soils is governed by soil properties such as pH. organic matter content and the 36 content of metal (hydr)oxides, but not by the vanadium species added to the soil. 37

Blast furnace (BF) slags are commonly applied as soil amendments and in road fill material. In Sweden they are also naturally high in vanadium. The aim of this study was to assess the vanadium bioavailability in BF slags when applied to soil. Two soils were amended with up to 29 % BF slag (containing 800 mg V kg -1 ) and equilibrated outdoors for 10 months before conducting a barley shoot growth assay. Additional soil samples were spiked with dissolved vanadate(V) for which assays were conducted two weeks (freshly spiked) and 10 months (aged) after spiking. The BF slag vanadium was dominated by vanadium(III) as shown by V K-edge XANES spectroscopy. In contrast, results obtained by HPLC-ICP-MS showed that vanadium(V), the most toxic vanadium species, was predominant in the soil solution. Barley shoot growth was not affected by the BF slag additions. This was likely due to limited dissolution of vanadium from the BF slag, preventing an increase of dissolved vanadium above toxic thresholds. The difference in vanadium bioavailability among treatments was explained by the vanadium concentration in the soil solution. It was concluded that the vanadium in BF slag is sparingly available. These findings should be of importance in environmental risk assessment.

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