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The arsenic biogeochemical cycle is greatly dependent on microbial transformations that affect both the distribution and mobility of arsenic species in the environment. In this study, a microbial biofilm from volcanic rocks was characterized on the basis of its bacterial composition and ability to mobilize arsenic under circumneutral pH. Biofilm microstructure was analyzed by scanning electron microscopy (SEM)-energy-dispersive spectroscopy (EDS). Strains were isolated from biofilms and identified by 16S rDNA sequences analysis. Arsenic oxidation and reduction capacity was assayed with high-performance liquid chromatography coupled to gaseous formation performing the detection by atomic absortion in a quartz bucket (HPLC/HG/QAAS), and polymerase chain reaction was used to detect aox and ars genes. Bacterial communities associated with volcanic rocks were studied by denaturing gradient gel electrophoresis (DGGE). The SEM-EDS studies showed the presence of biofilm after 45 days of incubation. The relative closest GenBank matches of the DNA sequences, of isolated arsenic-resistant strains, showed the existence of four different genus: Burkholderia, Pseudomonas, Erwinia, and Pantoea. Four arsenite-resistant strains were isolates, and only three strains were able to oxidize > 97% of the As(III) present (500 uM). All arsenate-resistant isolates were able to reduce between 69 and 86% of total As(V) (1000 uM). Analysis of 16S rDNA sequences obtained by DGGE showed the presence of four bacterial groups (ae-proteobacteria, gamma-proteobacteria, Firmicutes, and Actinobacteria). Experiments demonstrate that epilithic bacterial communities play a key role in the mobilization of arsenic and metalloids speciation.