Decoupling of As and Fe release to Bangladesh groundwater under reducing conditions. Part 1: Evidence from sediment profiles

This study reexamines the notion that extensive As mobilization in anoxic groundwater of Bangladesh is intimately linked to the dissolution of Fe oxyhydroxides on the basis of analyses performed on a suite of freshly collected samples of aquifer material. Detailed sediment profiles extending to 40 to 70 m depth below the surface were obtained at six sites where local groundwater As concentrations were known to span a wide range. The sediment properties that were measured include (1) the proportion of Fe(II) in the Fe fraction leached in hot 1.2 N HCl, (2) diffuse spectral reflectance, and (3) magnetic susceptibility. In parallel with local concentrations of dissolved As ranging from <5 to 600 mug/L, Fe(II)/Fe ratios in shallow (gray) Holocene sands tended to gradually increase with depth from values of 0.3 to 0.5 to up to 0.9. In deeper (orange) aquifers of presumed Pleistocene age that were separated from shallow sands by a clay layer and contained <5 mug/L dissolved As, leachable Fe(II)/Fe ratios averaged similar to0.2. There was no consistent relation between sediment Fe(II)/Fe and dissolved Fe concentrations in groundwater in nearby wells. The reflectance measurements indicate a systematic linear relation (R-2 of 0.66; n = 151) between the first derivative transform of the reflectance at 520 nm and Fe(II)/Fe. The magnetic susceptibility of the shallow aquifer sands ranged from 200 to 3600 (x 10(-9) m(3)/kg SI) and was linearly related (R-2 of 0.75; n = 29) to the concentrations of minerals that could be magnetically separated (0.03 to 0.79% dry weight). No systematic depth trends in magnetic susceptibility were observed within the shallow sands, although the susceptibility of deeper low-As aquifers was low (up to similar to200 x 10(-9) m(3)/kg SI). This set of observations, complemented by incubation results described in a companion paper by van Geen et al. (this volume), suggests that the release of As is linked to the transformation of predominantly Fe (III) oxyhydroxide coatings on sand particles to Fe(II) or mixed Fe(II/III) solid phases with a flatter reflectance spectrum such as siderite, vivianite, or magnetite, without necessarily resulting in the release of Fe to groundwater. The very low As/Fe ratio of magnetically separated minerals compared to the As/Fe of bulk acid leachate (2 vs. 40 10(-6), respectively) suggests that such a transformation could be accompanied by a significant redistribution of As to a mobilizable phase on the surface of aquifer particles. Copyright (C) 2004 Elsevier Ltd