Site characterisation of subsurface contaminant transport is often hampered by a lack of knowledge of site heterogeneity and temporal variations in hydrogeochemistry. The use of a regional-scale data compilation derived from satellite imaging is discussed with respect to directing design of site characterisation to monitor the fate of a Dense Non-Aqueous Phase Liquid (DNAPL) plume in Nevada. Evaluation of the drainage basin contributing to the groundwater flux into the study site was used to re-assess the site conceptual model and re-direct the characterisation effort. The use of highly resolved measurements of subsurface hydrogeochemistry in space and time were employed to identify the predominant biogeochemical processes controlling arsenic transport during discharge of groundwater into a pond at a site in Massachusetts. Direct-push conductivity measurements coupled with vertically-resolved sampling within the pond and adjoining aquifer demonstrated spatial and temporal variations in dissolved arsenic within groundwater and the pond water column and sediment pore water. Spatial variability was observed over the scale of centimetres to metres, and temporal variations were observed over the scales of days (following storm events) to seasons. Microbially-driven redox processes maintained anoxic conditions in groundwater and at the sediment-water interface (iron and sulfate reduction) and exerted both a direct and indirect influence on arsenic solution speciation and partitioning to surface water sediments.