AbstractThe study area is located on the western part of the alluvium‐filled gap between the Rajmahal hills on the west and the Garo hills on the east. Groundwater occurs under unconfined condition in a thick zone of saturation within the Quaternary alluvial sediments. Three hydrochemical facies with distinct characteristics have been identified which are dominated in general by alkaline earths and weak acids. The major‐ion chemistry of the area is controlled by weathering of silicate minerals, rainfall recharge, ion‐exchange processes and anthropogenic activities such as irrigation return flow and the application of inorganic fertilizers and pesticides. A stoichiometric approach suggests that mineral dissolution and anthropogenic activities contribute 79% and 21% of the total cations dissolved in groundwater. Principal component analysis (PCA) of 42 groundwater samples using 13 chemical parameters indicates that the combined processes of recharge of groundwater from rainfall, sediment water interaction, groundwater flow, infiltration of irrigation return water (which is arsenic rich due to the use of arsenic‐bearing pesticides, wood preservatives, etc. and the pumping of arsenic‐rich groundwater for agriculture purpose), oxidation of natural or anthropogenic organic matter and the reductive dissolution of ferric iron and manganese oxides play a key role in the evolution of groundwater in the study area. Factor 2 scores, associated with the infiltration of irrigation return water and spatial distribution of arsenic concentration reveal that the groundwater of the municipal area will not be affected by arsenic in the future in spite of heavy groundwater abstraction. Another PCA with geologic, geomorphic, anthropogenic, geochemical and landuse factors indicates that arsenic concentration in groundwater increases with increasing area of mango orchards, sand lithofacies and nitrate and decreases with increasing distance of paleochannel from the monitored well and depth of bore wells. High loading on nitrate may be attributed to the use of fertilizer, pesticides, etc. in mango orchards and agricultural land. High loadings on log pCO2, mango orchards (with negative sign) and phosphate (with positive sign) indicate that mango orchards provide the organic waste material which is decomposed to form organic carbon. The organic carbon undergoes oxidative carbon degeneration by different oxidants and increases the concentration of CO2 in the aquifer. The reducing condition thus developed in the aquifer helps to dissolve the arsenic adsorbed on iron hydroxide or oxy‐hydroxide coated margins of sand, iron rich heavy mineral grain margins, clay minerals and Fe–Mn concretions present in the aquifer matrix. Copyright © 2007 John Wiley & Sons, Ltd.