Arsenic in aquifers poisons more than 100 million people in Asia alone, as aquifers remain the primary source of water for drinking and farming. Previous studies have suggested a link between the mobilisation of arsenic in aquifers and biochemical processes. As a result of the complex interaction of microbes with arsenic bearing minerals, the relatively immobile arsenate [As(V)] is reduced to labile and more soluble arsenite [As(III)] in aquifers, resulting in elevated concentrations of the metalloid. The numerous microbial communities capable of multiple-metabolic activities colonising these arsenic impacted aquifers mean that the exact mechanism of arsenic mobilisation in aquifers remains poorly understood. To resolve this ambiguity, this study undertakes a combination of metaomic, geochemical, and statistical analyses of 75 aqueous and sediment samples (three sample sets) from 3 transects with arsenic impacted aquifers in Bangladesh and Cambodia. Key geochemical and physical properties including arsenic speciation, iron speciation, mineral and elemental compositions, pH and Eh were recorded using the state-of-the art techniques of XANES, XRF, ICP-MS and other in situ techniques. Next generation sequencing (NGS) platforms such as MiSeq, HiSeq, Nextseq and Pyrosequencing, were used to sequence and analyse DNA and RNA extracted from field samples, allowing characterisation the extent bacterial communities, including any arsenic related genes and transcripts found in these arsenic impacted aquifers. The biogeochemical findings suggest that direct As redox transformations are central to arsenic fate and transport, and that there is a residual reactive pool of both As(V) and Fe(III) in deeper sediments that could be released by microbial respiration in response to hydrologic perturbation, such as increased groundwater pumping that introduces reactive organic carbon to depth. The main findings of this molecular investigation are (i) the most abundant bacterial species belonging to the families of Comamonadaceae, Moraxellaceae, Rhodocyclaceae, Gallionellaceae etc, not known for dissimilatory arsenic reduction, might possess arrA genes and thus have the potential to mobilise arsenic through dissimilatory arsenate reduction; (ii) the bacterial community structure revealed through 16S rRNA gene based sequencing and analysis, resembles the family level community structure revealed through the WGS based community analysis; (iii) although arsenic resistant genes are found in many organisms, they are transcribed only in a few organisms; (iv) the application of O2-PLS analyses may be useful for not only identifying novel organisms associated with key biogeochemical process, but also has clear potential to predict the physical/chemical environment in situ associated with microbial samples via community profiling. In conclusion, the results obtained from this study help establish the identity of microorganisms potentially playing a role in arsenic mobilisation in aquifers, and help decipher the underpinning mechanisms. This deeper level of understanding will in turn help to better target measures that can be applied to arsenic mitigation.