Spatial and seasonal variations of the oxidation of Fe(II) and As(III) have been previously documented in the Carnoules (Gard, France) Acid Mine Drainage (AMD) by bulk analyses. These variations may be correlated with the variations in the activity of indigenous As(III)- and Fe(II)-oxidizing bacteria living in the As-rich Carnoules water. The activity of these bacteria indeed plays an important role in the nature and composition of the solid phases that sequester arsenic at this site. In order to better understand the interactions of microbes with Fe and As in the Carnoules AMD, we combined Transmission Electron Microscopy (TEM) and Scanning Transmission X-ray Microscopy (STXM) to collect near-edge X-ray absorption fine structure (NEXAFS) spectra at high spatial and energy resolution and to perform high spatial resolution imaging at the 30-50 nm scale. Spectromicroscopy was performed at the C K-edge, Fe L-2,L-3-edge, and As L-2,L-3-edge, which allowed us to locate living and/or mineralized bacterial cells and to characterize Fe and As oxidation states in the vicinity of those cells. TEM was used to image the same areas, providing higher resolution images and complementary crystallographic and compositional information through electron diffraction and EDXS analysis. This approach provides unique information on heterogeneous geochemical processes that occur in a complex microbial community in an AMD environment at the micrometer and submicrometer-scale. Bacterial cells in the Carnoules AMD were frequently associated with mineral precipitates, and a variety of biomineralization patterns were observed. While many mineral precipitates were not associated with bacterial cells, they were associated with pervasive organic carbon. Finally, abundant biomineralized organic vesicles were observed in the Carnoules AMD. Such vesicles may have been overlooked in highly mineralized extreme environments in the past and may represent an important component in a common biomineralization process in such environments. (C) 2008 Elsevier Ltd. All rights reserved.