Retardation of arsenic transport through a Pleistocene aquifer

Groundwater drawn daily from shallow alluvial sands by millions of wells over large areas of south and southeast Asia exposes an estimated population of over a hundred million people to toxic levels of arsenic1. Holocene aquifers are the source of widespread arsenic poisoning across the region2, 3. In contrast, Pleistocene sands deposited in this region more than 12,000 years ago mostly do not host groundwater with high levels of arsenic. Pleistocene aquifers are increasingly used as a safe source of drinking water4 and it is therefore important to understand under what conditions low levels of arsenic can be maintained. Here we reconstruct the initial phase of contamination of a Pleistocene aquifer near Hanoi, Vietnam. We demonstrate that changes in groundwater flow conditions and the redox state of the aquifer sands induced by groundwater pumping caused the lateral intrusion of arsenic contamination more than 120 metres from a Holocene aquifer into a previously uncontaminated Pleistocene aquifer. We also find that arsenic adsorbs onto the aquifer sands and that there is a 16–20-fold retardation in the extent of the contamination relative to the reconstructed lateral movement of groundwater over the same period. Our findings suggest that arsenic contamination of Pleistocene aquifers in south and southeast Asia as a consequence of increasing levels of groundwater pumping may have been delayed by the retardation of arsenic transport.National Science Foundation (U.S.) (NSF grant EAR09-11557)Swiss Agency for Development and Cooperation (Grant NAFOSTED 105-09-59-09 to CETASD, the Centre for Environmental Technology and Sustainable Development (Vietnam))National Institute of Environmental Health Sciences (NIEHS grant P42 ES010349)National Institute of Environmental Health Sciences (NIEHS grant P42 ES016454

Field, Experimental, and Modeling Study of Arsenic Partitioning across a Redox Transition in a Bangladesh Aquifer

To understand redox-dependent arsenic partitioning, we performed batch sorption and desorption experiments using aquifer sands subjected to chemical and mineralogical characterization. Sands collected from the redox transition zone between reducing groundwater and oxic river water at the Meghna riverbank with HCl extractable Fe(III)/Fe ratio ranging from 0.32 to 0.74 are representative of the redox conditions of aquifers common in nature. One brown suboxic sediment displayed a partitioning coefficient (K_d) of 7-8 L kg^-1 at equilibrium with 100 μg L^-1 As(III), while two gray reducing sediments showed K_d of 1-2 L kg^-1. Lactate amendment to aquifer sands containing 91 mg kg^-1 P-extractable As resulted in the reduction of As and Fe with sediment Fe(III)/Fe decreasing from 0.54 to 0.44, and mobilized an equivalent of 64 mg kg^-1 As over a month. Desorption of As from nonlactate-amended sediment was negligible with little change in sediment Fe(III)/Fe. This release of As is consistent with microbial reduction of Fe(III) oxyhydroxides and the resulting decrease in the number of surface sites on Fe(III) oxyhydroxides. Arsenic partitioning (K_d) in iron-rich, sulfur-poor aquifers with circumneutral pH is redox-dependent and can be estimated by HCl leachable sediment Fe(III)/Fe ratio with typical Fe concentrations

Immobilization of toxic metals and radionuclides in porous and fractured media: Optimizing biogeochemical reduction versus geochemical oxidation. 1997 annual progress report

'The purpose of the authors research is to provide an improved understanding and predictive capability of the mechanisms that allow metal-reducing bacteria to be effective in the bioremediation of subsurface environments contaminated with toxic metals and radionuclides. The research findings of the work plan will (1) provide new insights into the previously unexplored areas of competing geochemical and microbiological oxidation/reduction reactions that govern the fate and transport of redox sensitive contaminants in subsurface environments and (2) provide basic knowledge to define the optimum conditions for the microbial reduction and concomitant immobilization of toxic metals and radionuclides in the subsurface. Strategies that use in situ contaminant immobilization can be efficient and cost-effective remediation options. This project will focus on the following specific objectives. Develop an improved understanding of the rates and mechanisms of competing geochemical and microbiological oxidation/reduction reactions that govern the fate and transport of uranium (U), chromium (Cr), and cobalt-EDTA (Co-EDTA) in the subsurface. Quantify the conditions that optimize the microbial reduction of toxic metals and radionuclides for the purpose of contaminant containment and remediation in heterogeneous systems that have competing geochemical oxidation, sorption, and organic ligands.