Summary The present study interprets the groundwater solute chemistry, hydrogeochemical evolution, arsenic (As) enrichment and aquifer characterization in Brahmaputra River Basin (BRB) involving three geologically and tectono-morphically distinct regions located in northeastern India. These study regions consist of the northwestern (NW) and the northern (N) region, both located along the western and eastern parts of Eastern Himalayas and the southern (S) region (near Indo–Burmese Range and Naga hills) of the Brahmaputra basin which show distinct tectonic settings and sediment provenances in the Himalayan orogenic belt. Stable isotopic composition (δ2H and δ18O) in groundwater suggests that some evaporation may have taken place through recharging of ground water in the study areas. The major-ion composition shows that groundwater composition of the NW and N parts are between Ca HCO3 and Ca Na HCO3 while the S-region is dominated by Na Ca HCO3 hydrochemical facies. The major mineralogical composition of aquifer sediments indicates the dominant presence of iron(Fe)-oxide and oxyhydroxides, mica (muscovite and biotite), feldspar, pyroxene, amphibole, abundance of quartz and clay minerals whereas clay is predominantly present in sediments of S-aquifers. These mafic minerals, aluminosilicates and clay minerals might offer available reactive surface for As-adsorption and co-precipitatation with amorphous Fe. These associated adsorbed and co-precipitated As might be released due to reductive dissolution of Fe-oxide and oxyhydroxides in groundwater. These minerals are assumed to be possible sources of As in groundwater. The stability diagrams of groundwater data suggest that solute might have been introduced into groundwater from weathering of K-feldspar, plagioclase, pyroxene of Himalayan rocks, the Siwalik Group and Eastern Syntaxes in NW and N-regions. However, basic cations might be derived from weathering of K-feldspar, plagioclase, pyroxene and olivine those being major constituents in a gabbroic complex (ophiolite) and basalt terrain in S-region. The aquifers of S-region are severely contaminated with dissolved As compared to NW and N regions. Almost more than 92% of groundwater samples in the southern part (maximum 5.53 μM or 415 μg/L) are enriched with As, which draws a distinct difference from the NW and N parts of BRB aquifers. The redox-sensitive solutes (i.e., Fe, Mn, HCO3− and TOC) are positively correlated with As in NW and N-parts; whereas EH shows negative to very weak positive correlation which suggests that a redox-dependent mobilization plays important role in As liberation in NW and N parts of the basin. However, As in southern aquifers is not showing any correlation or weak negative correlation with redox-sensitive solutes; suggesting that multiple reactions and hydrogeochemical processes and their interaction control As mobilization and fate in the S-region of BRB. The occurrence of high concentrations of arsenic in groundwater of Brahmaputra basin is described through a crustal recycling model and tectonic movement between the Indian–Eurasian plates and Burmese micro-continents. As-enriched groundwater in Himalayan foreland basin in the BRB is probably a result of crustal evolution through which As is subsequently mobilized from aquifer matrix to solution in groundwater by water–sediment reaction under favorable biogeochemical conditions. The results of the study indicate geological control (i.e. change in lithofacies, tectonic set-up) on groundwater chemistry and distribution of redox-sensitive solutes such as As.
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