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 Ͻ5 to 600 g/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 Ͻ5 g/L dissolved As, leachable Fe(II)/Fe ratios averaged ϳ0.2. 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 ϭ 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 ϭ 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 ϳ200 ϫ 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.

[1] Arsenic concentrations measured by graphite furnace atomic absorption range from < 5 to 900 mg/L in groundwater pumped from 6000 wells within a 25 km 2 area of Bangladesh. The proportion of wells that exceed the Bangladesh standard for drinking water of 50 mg/L arsenic increases with depth from 25% between 8 and 10 m to 75% between 15 and 30 m, then declines gradually to less than 10% at 90 m. Some villages within the study area do not have a single well that meets the standard, while others have wells that are nearly all acceptable. In contrast to the distribution of arsenic in the 8-30 m depth range which does not follow any obvious geological feature, the arsenic content of groundwater associated with relatively oxic Pleistocene sand deposits appears to be consistently low. The depth of drilling necessary to reach these low-As aquifers ranges from 30 to 120 m depth within the study area.

No abstract

No abstract

[1] The elevated arsenic (As) content of groundwater from wells across Bangladesh and several other South Asian countries is estimated to slowly poison at least 100 million people. The heterogeneous distribution of dissolved arsenic in the subsurface complicates understanding of its release from the sediment matrix into the groundwater, as well as the design of mitigation strategies. Using the tritium-helium ( 3 H/ 3 He) groundwater dating technique, we show that there is a linear correlation between groundwater age at depths <20 m and dissolved As concentration, with an average slope of 19 mg L À1 yr À1 (monitoring wells only). We propose that either the kinetics of As mobilization or the removal of As by groundwater flushing is the mechanism underlying this relationship. In either case, the spatial variability of As concentrations in the top 20 m of the shallow aquifers can to a large extent be attributed to groundwater age controlled by the hydrogeological heterogeneity in the local groundwater flow system.