Surface Flooding as a Key Driver of Groundwater Arsenic Contamination in Southeast Asia.

Chronic exposure to groundwater contaminated with geogenic arsenic (As) poses a significant threat to human health worldwide, especially for those living on floodplains in South and Southeast (S-SE) Asia. In the alluvial and deltaic aquifers of S-SE Asia, aqueous As concentrations vary sharply over small spatial scales (10-100 m), making it challenging to identify where As contamination is present and mitigate exposure. Improved mechanistic understanding of the factors that control groundwater As levels is essential to develop models that accurately predict spatially variable groundwater As concentrations. Here we demonstrate that surface flooding duration and interannual frequency are master variables that integrate key hydrologic and biogeochemical processes that affect groundwater As levels in S-SE Asia. A machine-learning model based on high-resolution, satellite-derived, long-term measures of surface flooding duration and frequency effectively predicts heterogeneous groundwater As concentrations at fine spatial scales in Cambodia, Vietnam, and Bangladesh. Our approach can be reliably applied to identify locations of safe and unsafe groundwater sources with sufficient accuracy for making management decisions by solely using remotely sensed information. This work is important to evaluate levels of As exposure, impacts to public health, and to shed light on the underlying hydrogeochemical processes that drive As mobilization into groundwater.

Aquifer-Scale Observations of Iron Redox Transformations in Arsenic-Impacted Environments to Predict Future Contamination.

Iron oxides control the mobility of a host of contaminants in aquifer systems, and the microbial reduction of iron oxides in the subsurface is linked to high levels of arsenic in groundwater that affects greater than 150 million people globally. Paired observations of groundwater and solid-phase aquifer composition are critical to understand spatial and temporal trends in contamination and effectively manage changing water resources, yet field-representative mineralogical data are sparse across redox gradients relevant to arsenic contamination. We characterize iron mineralogy using X-ray absorption spectroscopy across a natural gradient of groundwater arsenic contamination in Vietnam. Hierarchical cluster analysis classifies sediments into meaningful groups delineating weathering and redox changes, diagnostic of depositional history, in this first direct characterization of redox transformations in the field. Notably, these groupings reveal a signature of iron minerals undergoing active reduction before the onset of arsenic contamination in groundwater. Pleistocene sediments undergoing postdepositional reduction may be more extensive than previously recognized due to previous misclassification. By upscaling to similar environments in South and Southeast Asia via multinomial logistic regression modeling, we show that active iron reduction, and therefore susceptibility to future arsenic contamination, is more widely distributed in presumably pristine aquifers than anticipated.

Geochemical transformations beneath man-made ponds: Implications for arsenic mobilization in South Asian aquifers.

The role of man-made ponds on arsenic mobilization was examined in Bangladesh. Here, we describe a field experiment that shows how recharge from a newly constructed pond creates a reactive front that moves downward into the underlying aquifer, but only advances slowly, less than 8 cm/year. We found that pond recharge introduces organic carbon that likely drives the reduction of sulfate and solid-phase iron. However, over the six-year period of the study the pond did not drive arsenic contamination of the underlying groundwater. An electron balance indicates that significant precipitation of ferrous iron and sulfide minerals may immobilize arsenic despite the shift towards more reducing conditions, explaining the very low observed aqueous arsenic concentrations. We additionally found that the amount of solid-phase electron acceptors available in the shallow sediments strongly retards the advance of a reduced sediment front. Our results suggest that labile organic carbon introduced by man-made ponds is efficiently mineralized in the sediments immediately below the pond bottom and thus is unlikely to drive arsenic mobilization deeper within the aquifer. We suggest that the excavation of man-made ponds removes young surficial sediments, leaving aged and less reactive sediments beneath the pond, so that recharge through excavated ponds does not mobilize arsenic at the high rates observed in recharge through natural wetlands and river banks.

Groundwater Pumping Is a Significant Unrecognized Contributor to Global Anthropogenic Element Cycles.

Quantifying anthropogenic contributions to elemental cycles provides useful information regarding the flow of elements important to industrial and agricultural development and is key to understanding the environmental impacts of human activity. In particular, when anthropogenic fluxes reach levels large enough to influence an element's overall cycle the risk of adverse environmental impacts rises. While intensive groundwater pumping has been observed to affect a wide-range of environmental processes, the role of intensive groundwater extraction on global anthropogenic element cycles has not yet been characterized. Relying on comprehensive datasets of groundwater and produced water (groundwater pumped during oil/gas extraction) chemistry from the U.S. Geological Survey along with estimates of global groundwater usage, I estimate elemental fluxes from global pumping, consumptive use, and depletion of groundwater. I find that groundwater fluxes appreciably contribute to a number of elements overall cycles and thus these cycles were underestimated in prior studies, which did not recognize groundwater pumping's role. I also estimate elemental loadings to agricultural soils in the United States and find that in some regions, groundwater may provide a significant portion (more than 10%) of crop requirements of key nutrients (K, N). With nearly 40% of globally irrigated land under groundwater irrigation, characterizing nutrient and toxic element fluxes to these soils, which ultimately influence crop yields, is important to our understanding of agricultural production. Thus, this study improves our basic understanding of anthropogenic elemental cycles and demonstrates that quantification of groundwater pumping elemental fluxes provides valuable information about the potential for environmental impacts from groundwater pumping.

Quantifying Riverine Recharge Impacts on Redox Conditions and Arsenic Release in Groundwater Aquifers Along the Red River, Vietnam.

Widespread contamination of groundwater with geogenic arsenic is attributed to microbial dissolution of arsenic-bearing iron (oxyhydr)oxides minerals coupled to the oxidation of organic carbon. The recharge sources to an aquifer can influence groundwater arsenic concentrations by transport of dissolved arsenic or reactive constituents that affect arsenic mobilization. To understand how different recharge sources affect arsenic contamination-in particular through their influence on organic carbon and sulfate cycling-we delineated and quantified recharge sources in the arsenic affected region around Hanoi, Vietnam. We constrained potential end-member compositions and employed a novel end-member mixing model using an ensemble approach to apportion recharge sources. Groundwater arsenic and dissolved organic carbon concentrations are controlled by the dominant source of recharge. High arsenic concentrations are prevalent regardless of high dissolved organic carbon or ammonium levels, indicative of organic matter decomposition, where the dominant recharge source is riverine. In contrast, high dissolved organic carbon and significant organic matter decomposition are required to generate elevated groundwater arsenic where recharge is largely nonriverine. These findings suggest that in areas of riverine recharge, arsenic may be efficiently mobilized from reactive surficial environments and carried from river-aquifer interfaces into groundwater. In groundwaters derived from nonriverine recharge areas, significantly more organic carbon mineralization is required to obtain equivalent levels of arsenic mobilization within inland sediments. This method can be broadly applied to examine the connection between hydrology, geochemistry and groundwater quality.

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 arsenic. Holocene aquifers are the source of widespread arsenic poisoning across the region. 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 water 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.