Forty-six deep groundwater samples from highly arsenic affected areas in Bangladesh were analyzed in order to evaluate the processes controlling geochemical constituents in the deep aquifer system. Spatial trends of solutes, geochemical modeling and principal component analysis indicate that carbonate dissolution, silicate weathering and ion exchange control the major-ion chemistry. The groundwater is dominantly of Na-Cl type brackish water. Approximately 17% of the examined groundwaters exhibit As concentrations higher than the maximum acceptable limit of 10 mu g/L for drinking water. Strong correlation (R-2 = 0.67) of Fe with dissolved organic carbon (DOC) and positive saturation index of siderite suggests that the reductive dissolution of Fe-oxyhydroxide in presence of organic matter is considered to be the dominant process to release high content of Fe (median 0.31 mg/L) in the deep aquifer. In contrast, As is not correlated with Fe and DOC. Boron concentration in the 26% samples exceeds the standard limit of 500 mu g/L, for water intended for human consumption. Negative relationships of B/Cl ratio with Cl and boron with Na/Ca ratio demonstrate the boron in deep groundwater is accompanied by brackish water and cation exchange within the clayey sediments. (C) 2010 Elsevier B.V. All rights reserved.