Molecular-level modes of As binding to Fe(III) (oxyhydr)oxides precipitated by the anaerobic nitrate-reducing Fe(II)-oxidizing Acidovorax sp. strain BoFeN1

Sorption of contaminants such as arsenic (As) to natural Fe(III) (oxyhydr)oxides is very common and has been demon- strated to occur during abiotic and biotic Fe(II) oxidation. The molecular mechanism of adsorption- and co-precipitation of As has been studied extensively for synthetic Fe(III) (oxyhydr)oxide minerals but is less documented for biogenic ones. In the present study, we used Fe and As K-edge X-ray Absorption Near Edge Structure (XANES), extended X-ray Absorp- tion Fine Structure (EXAFS) spectroscopy, Mossbauer spectroscopy, XRD, and TEM in order to investigate the interactions of As(V) and As(III) with biogenic Fe(III) (oxyhydr)oxide minerals formed by the nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1. The present results show the As immobilization potential of strain BoFeN1 as well as the influ- ence of As(III) and As(V) on biogenic Fe(III) (oxyhydr)oxide formation. In the absence of As, and at low As loading (As:Fe 6 0.008 mol/mol), goethite (Gt) formed exclusively. In contrast, at higher As/Fe ratios (As:Fe = 0.020-0.067), a fer- rihydrite (Fh) phase also formed, and its relative amount systematically increased with increasing As:Fe ratio, this effect being stronger for As(V) than for As(III). Therefore, we conclude that the presence of As influences the type of biogenic Fe(III) (oxyhydr)oxide minerals formed during microbial Fe(II) oxidation. Arsenic-K-edge EXAFS analysis of biogenic As-Fe-min- eral co-precipitates indicates that both As(V) and As(III) form inner-sphere surface complexes at the surface of the biogenic Fe(III) (oxyhydr)oxides. Differences observed between As-surface complexes in BoFeN1-produced Fe(III) (oxyhydr)oxide samples and in abiotic model compounds suggest that associated organic exopolymers in our biogenic samples may compete with As oxoanions for sorption on Fe(III) (oxyhydr)oxides surfaces. In addition HRTEM-EDXS analysis suggests that As(V) preferentially binds to poorly crystalline phases, such as ferrihydrite, while As(III) did not show any preferential association regarding Fh or Gt. 2011 Elsevier Ltd. All rights reserved.