Influence of As(V) on Fe(II)-catalyzed Fe oxide recrystallization

Human exposure to arsenic in groundwater is a global concern, and arsenic mobility in groundwater is often controlled by Fe mineral dissolution and precipitation. Additionally, Fe(II)-catalyzed recrystallization of Fe oxides has been shown to enable trace element release from and incorporation into Fe oxides. However, the effect of As(V) on the Fe(II)-catalyzed recrystallization of Fe oxides such as goethite, magnetite, and ferrihydrite remains unclear. Here, we measured the extent of Fe atom exchange between aqueous Fe(II) and magnetite, goethite, or ferrihydrite in the presence of As(V) by reacting isotopically "normal" Fe oxides with ⁵⁷Fe-enriched aqueous Fe(II). At lower levels of adsorption (≤13.3 μM), As(V) had little influence on the rate or extent of Fe(II)-catalyzed Fe atom exchange in goethite or magnetite. However, Fe atom exchange was increasingly inhibited as As(V) concentration increased above 100 μM. Additionally, adsorbed As(V) may be incorporated into magnetite over time in the presence and absence of added aqueous Fe(II) as indicated by X-ray absorption spectroscopy (XAS) and chemical extraction data, with more rapid incorporation in the absence of added Fe(II). XAS and chemical extraction data are also consistent with the incorporation of As(V) during goethite and magnetite precipitation. Additionally, atom exchange data indicated that low levels of As(V) coprecipitation (As:Fe = 0.0005-0.0155) had little influence on the rate or extent of Fe(II)-catalyzed Fe atom exchange in goethite or magnetite. Atom exchange data indicated that ferrihydrite likely transforms via a dissolution-reprecipitation mechanism both to lepidocrocite at 0.2 mM Fe(II) and to magnetite at 5 mM Fe(II). The presence of 206 μM As(V) slowed the transformation of ferrihydrite to more crystalline iron minerals and slowed the rate of atom exchange between aqueous Fe(II) and ferrihydrite. However, the degree of atom exchange did not directly correlate with the amount of ferrihydrite transformed. In summary, Fe oxide recrystallization processes may affect As(V) uptake and release in the environment, and As(V) may inhibit Fe(II)-catalyzed Fe oxide recrystallization.