Redox Zonation and Oscillation in the Hyporheic Zone of the Ganges-Brahmaputra-Meghna Delta: Implications for the Fate of Groundwater Arsenic during Discharge.

Riverbank sediment cores and pore waters, shallow well waters, seepage waters and river waters were collected along the Meghna Riverbank in Gazaria Upazila, Bangladesh in Jan. 2006 and Oct.-Nov. 2007 to investigate hydrogeochemical processes controlling the fate of groundwater As during discharge. Redox transition zones from suboxic (0-2 m depth) to reducing (2-5 m depth) then suboxic conditions (5-7 m depth) exist at sites with sandy surficial deposits, as evidenced by depth profiles of pore water (n=7) and sediment (n=11; diffuse reflectance, Fe(III)/Fe ratios and Fe(III) concentrations). The sediment As enrichment zone (up to ~700 mg kg-1) is associated with the suboxic zones mostly between 0-2 m depth and less frequently between 5-7 m depth. The As enriched zones consist of several 5 to 10 cm-thick dispersed layers and span a length of ~5-15 m horizontally from the river shore. Depth profiles of riverbank pore water deployed along a 32 m transect perpendicular to the river shore show elevated levels of dissolved Fe (11.6±11.7 mg L-1) and As (118±91 µg L-1, mostly as arsenite) between 2-5 m depth, but lower concentrations between 0-2 m depth (0.13±0.19 mg L-1 Fe, 1±1 µg L-1 As) and between 5-6 m depth (1.14±0.45 mg L-1 Fe, 28±17 µg L-1 As). Because it would take more than a few hundred years of steady groundwater discharge (~10 m yr-1) to accumulate hundreds of mg kg-1 of As in the riverbank sediment, it is concluded that groundwater As must have been naturally elevated prior to anthropogenic pumping of the aquifer since the 1970s. Not only does this lend unequivocal support to the argument that As occurrence in the Ganges-Brahmaputra-Meghna Delta groundwater is of geogenic origin, it also calls attention to the fate of this As enriched sediment as it may recycle As into the aquifer.

Mobilization of arsenic during one-year incubations of grey aquifer sands from Araihazar, Bangladesh.

Elevated As concentrations in shallow groundwater pose a major health threat in Bangladesh and similarly affected countries, yet there is little consensus on the mechanism of As release to groundwater or how it might be influenced by human activities. In this study, the rate of As release was measured directly with incubations lasting 11 months, using sediment and groundwater collected simultaneously in Bangladesh and maintained under anaerobic conditions throughout the study. Groundwater and gray sediment were collected as diluted slurries between 5 and 38 m in depth, a range over which ambient groundwater As concentrations increased from 20 to 100 microg L(-1). Arsenic was released to groundwater in slurries from 5 and 12 m in depth at a relatively constant rate of 21 +/- 4 (2 sigma) and 23 +/- 6 microg As kg(-1) yr(-1), respectively. Amendment with a modest level of acetate increased the rate of As release only at 12 m (82 +/- 18 mirog kg(-1) yr(-1)). Although the groundwater As concentration was initially highest at 38 m depth, no release of As was observed. These results indicate that the spatial distribution of dissolved As in Bangladesh and local rates of release to groundwater are not necessarily linked. Iron release during the incubations did not occur concurrently with As release, providing further confirmation thatthe two processes are not directly coupled. Small periodic additions of oxygen suppressed the release of As from sediments at all three depths, which supports the notion that anoxia is a prerequisite for accumulation of As in Bangladesh groundwater.