Geochemical occurrence of arsenic in groundwater of Bangladesh: sources and mobilization processes

Abstract

Total arsenic, dissolved organic carbon (DOC), iron, major cations and anions were measured in tube-well waters used for drinking by people to investigate the geochemical condition of subsurface aquifer, source of arsenic and mechanism of arsenic release to groundwater of Bangladesh. Solid phases of total arsenic, iron, manganese and aluminum oxide and organic carbon (TOC) content in sediments were determined to find out their interrelationships. Arsenic concentrations in groundwaters vary from 0.03 to 0.75 mg/l with the mean value of 0.41 mg/l that exceed the maximum permissible limit of WHO (0.01 mg/l) and Bangladesh (0.05 mg/l) for drinking water. Arsenic concentrations demonstrate negative covariation with the concentrations of sulfate and nitrate but correlate weakly with iron concentrations and positively with those of ammonium ions. Dissolved iron exhibits a negative covariance with the concentrations of sulfate. Very low concentrations of nitrate and sulfate and high concentrations of dissolved iron and ammonium ions demonstrate the reducing condition of subsurface aquifer. These relationships suggest that oxidation of arsenic-rich pyrite is not responsible for the increased concentrations of arsenic but reflect the dependence of As concentration on the reductive processes. Arsenic is strongly correlated with DOC concentrations. Borehole data demonstrate the arsenic enrichment in organic matter-rich fine-grained clayey silt and silty sand than in sandy sediments. Arsenic contents are well correlated with those of iron, manganese and aluminum oxides in fine particle fraction of sediments, whereas arsenic is significantly correlated with TOC in large particle fraction. Sequential chemical leaching exhibits that arsenic is mainly present in three phases: (1) oxide phase of Fe and Mn, (2) organic matter and (3) sulfide and silicate phases. Since the distribution of arsenic in the subsurface sediments is not solely controlled by a single solid phase, the dissolution–desorption from different phases contributes to the total arsenic concentrations in groundwater. Microbial oxidation of organic matter (including localized peat layer) and reductive dissolution of Fe and Mn oxyhydroxide are the important processes to mobilize arsenic. The combined effects of NaHCO 3 and high pH values also play a significant role to mobilize arsenic from surface of iron oxides, other minerals and subsurface sediments. The very strong relationship between arsenic and bicarbonate concentrations in groundwater of Bangladesh and high pH values (8.03–8.7) of the Ganges sediments support the hypothesis. This paper reports first about arsenic leaching by the combined effects of NaHCO 3 and high pH values in Bangladesh.