X-ray Absorption Fine Structure (XAFS) spectroscopy was used in combination with high resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), X-ray energy dispersive spectroscopy (XEDS), Xray powder diffraction, and Mossbauer spectroscopy to obtain detailed information on arsenic and iron speciation in the products of anaerobic reduction of pure and As(V)- or As(III)-adsorbed lepidocrocite (gamma-FeOOH) by Shewanella putrefaciens ATCC 12099. We found that this strain of S. putrefaciens is capable of using Fe(III) in lepidocrocite and As(V) in solution or adsorbed on lepidocrocite surfaces as electron acceptors. Bioreduction of lepidocrocite in the absence of arsenic resulted in the formation of hydroxycarbonate green rust 1 [(Fe4Fe2III)-Fe-II(OH)(12)CO3: GR1(CO3)], which completely converted into ferrous-carbonate hydroxide (Fe-2(II)(OH)(2)CO3: FCH) over nine months. This study thus provides the first evidence of bacterial reduction of stoichiometric GR1(CO3) into FCH. Bioreduction of As(III)-adsorbed lepidocrocite also led to the formation of GR1(CO3) prior to formation of FCH, but the presence of As(III) slows down this transformation, leading to the co-occurrence of both phases after 22-month of aging. At the end of this experiment, As(III) was found to be adsorbed on the surfaces of GR1(CO3) and FCH. After five months, bioreduction of As(V)-bearing lepidocrocite led directly to the formation of FCH in association with nanometer-sized particles of a minor As-rich Fe(OH)(2) phase, with no evidence for green rust formation. In this five-month experiment, As(V) was fully converted to As(III), which was dominantly sorbed at the surface of the Fe(OH)(2) nanoparticles as oligomers binding to the edges of Fe(OH)(6) octahedra at the edges of the octahedral layers of Fe(OH)(2). These multinuclear As(III) surface complexes are characterized by As-As pairs at a distance of 3.32 +/- 0.02 angstrom and by As-Fe pairs at a distance of 3.50 +/- 0.02 angstrom and represent a new type of As(III) surface complex. Chemical analyses show that the majority of As(III) produced in the experiments with As present is associated with iron-bearing hydroxycarbonate or hydroxide solids, reinforcing the idea that, at least under some circumstances, bacterial reduction can promote As(III) sequestration instead of mobilizing it into solution. (C) 2008 Elsevier Ltd. All rights reserved.