Origin of Groundwater Arsenic in a Rural Pleistocene Aquifer in Bangladesh Depressurized by Distal Municipal Pumping.

Across South Asia, millions of villagers have reduced their exposure to high-arsenic (As) groundwater by switching to low-As wells. Isotopic tracers and flow modeling are used in this study to understand the groundwater flow system of a semi-confined aquifer of Pleistocene (>10 kyr) age in Bangladesh that is generally low in As but has been perturbed by massive pumping at a distance of about 25 km for the municipal water supply of Dhaka. A 10- to 15-m-thick clay aquitard caps much of the intermediate aquifer (>40- to 90-m depth) in the 3-km2 study area, with some interruptions by younger channel sand deposits indicative of river scouring. Hydraulic heads in the intermediate aquifer below the clay-capped areas are 1-2 m lower than in the high-As shallow aquifer above the clay layer. In contrast, similar heads in the shallow and intermediate aquifer are observed where the clay layer is missing. The head distribution suggests a pattern of downward flow through interruptions in the aquitard and lateral advection from the sandy areas to the confined portion of the aquifer. The interpreted flow system is consistent with 3H-3He ages, stable isotope data, and groundwater flow modeling. Lateral flow could explain an association of elevated As with high methane concentrations within layers of gray sand below certain clay-capped portions of the Pleistocene aquifer. An influx of dissolved organic carbon from the clay layer itself leading to a reduction of initially orange sands has also likely contributed to the rise of As.

Human and livestock waste as a reduced carbon source contributing to the release of arsenic to shallow Bangladesh groundwater.

Recent studies have demonstrated that the supply of relatively young organic carbon stimulates the release of arsenic to groundwater in Bangladesh. This study explores the potential role of human and livestock waste as a significant source of this carbon in a densely populated rural area with limited sanitation. Profiles of aquifer sediment samples were analyzed for phytosterols and coprostanol to assess the relative contributions of plant-derived and human/livestock waste-derived organic carbon at two well-characterized sites in Araihazar. Coprostanol concentrations increased with depth from non-detection (<10m at Site B and <23m at Site F) to maxima of 1.3 and 0.5ng/g in aquifer sands recovered from 17m (Site B) and 26m (Site F), respectively. The commonly used sewage contamination index ([5ß-coprostanol]/([5α-cholestanol]+[5ß-coprostanol])) exceeds 0.7 between 12 and 19m at Site B and between 24 and 26m at Site F, indicating input of human/livestock waste to these depths. Urine/fecal input within the same depth range is supported by groundwater Cl/Br mass ratios >1000 compared to Cl/Br <500 at depths >50m. Installed tube wells in the area's study sites may act as a conduit for DOC and specifically human/livestock waste into the aquifer during flood events. The depth range of maximum input of human/livestock waste indicated by these independent markers coincides with the highest dissolved Fe (10-20mg/L) and As (200-400µg/L) concentrations in groundwater at both sites. The new findings suggest that the oxidation of human/livestock waste coupled to the reductive dissolution of iron-(oxy)-hydroxides and/or arsenate may enhance groundwater contamination with As.

Evidence of Decoupling between Arsenic and Phosphate in Shallow Groundwater of Bangladesh and Potential Implications.

Reductive dissolution of iron oxyhydroxides and reduction of arsenic are often invoked as leading causes of high dissolved As levels in shallow groundwater of Bangladesh. The second of these assumptions is questioned here by comparing the behavior As and phosphate (P), a structural analogue for As (V) which also adsorbs strongly to Fe oxyhydroxides but is not subject to reduction. The first line of evidence is provided by a detailed groundwater time-series spanning two years for three wells in the 6-9 m depth range showing removal of As(III) from shallow groundwater during the monsoon without of loss of P. The data indicate a loss of ~90% of the dissolved As from groundwater in the intermediate well relative to a level of 3 µmol/L As predicted by conservative mixing between groundwater sampled from the shallower and the deeper well. In contrast, P concentrations of ~30 µmol/L in the intermediate well closely match the prediction from conservative mixing. Reduction therefore appears to inhibit the release of As to groundwater at this site relative to P instead of enhancing it. A re-analysis of existing groundwater As and P data from across the country provides a broader context for this finding and confirms that, without reduction, elevated concentrations of As would probably be even more widespread in shallow aquifers of Bangladesh. Without providing definite proof, X-ray absorption spectroscopy of sediment from the time-series site and elsewhere suggests that the loss of As from groundwater may be coupled to precipitation of As sulfide. Further study is needed to assess the implications of these observations for shallow aquifers that have been subjected to increased withdrawals for irrigation in recent decades.

Stimulation of Microbially Mediated Arsenic Release in Bangladesh Aquifers by Young Carbon Indicated by Radiocarbon Analysis of Sedimentary Bacterial Lipids.

The sources of reduced carbon driving the microbially mediated release of arsenic to shallow groundwater in Bangladesh remain poorly understood. Using radiocarbon analysis of phospholipid fatty acids (PLFAs) and potential carbon pools, the abundance and carbon sources of the active, sediment-associated, in situ bacterial communities inhabiting shallow aquifers (<30 m) at two sites in Araihazar, Bangladesh, were investigated. At both sites, sedimentary organic carbon (SOC) Δ(14)C signatures of -631 ± 54‰ (n = 12) were significantly depleted relative to dissolved inorganic carbon (DIC) of +24 ± 30‰ and dissolved organic carbon (DOC) of -230 ± 100‰. Sediment-associated PLFA Δ(14)C signatures (n = 10) at Site F (-167‰ to +20‰) and Site B (-163‰ to +21‰) were highly consistent and indicated utilization of carbon sources younger than the SOC, likely from the DOC pool. Sediment-associated PLFA Δ(14)C signatures were consistent with previously determined Δ(14)C signatures of microbial DNA sampled from groundwater at Site F indicating that the carbon source for these two components of the subsurface microbial community is consistent and is temporally stable over the two years between studies. These results demonstrate that the utilization of relatively young carbon sources by the subsurface microbial community occurs at sites with varying hydrology. Further they indicate that these young carbon sources drive the metabolism of the more abundant sediment-associated microbial communities that are presumably more capable of Fe reduction and associated release of As. This implies that an introduction of younger carbon to as of yet unaffected sediments (such as those comprising the deeper Pleistocene aquifer) could stimulate microbial communities and result in arsenic release.

Inequitable allocation of deep community wells for reducing arsenic exposure in Bangladesh.

Community wells that extend deeper than most private wells are crucial for reducing exposure to groundwater arsenic (As) in rural Bangladesh. This study evaluates the impact on access to safe drinking water of 915 such intermediate (90-150 m) and deep (>150 m) wells across a 180 km2 area where a total of 48,790 tubewells were tested with field kits in 2012-13. Half the shallow private wells meet the Bangladesh standard of 50 µg/L for As in drinking water, whereas 92% of the intermediate and deep wells meet the more restrictive World Health Organization guideline for As in drinking water of 10 µg/L. As a proxy for water access, distance calculations show that 29% of shallow wells with >50 µg/L As are located within walking distance (100 m) of at least one of the 915 intermediate or deep wells. Similar calculations for a hypothetical more even distribution of deep wells show that 74% of shallow wells with >50 µg/L As could have been located within 100 m of the same number deep wells. These observations and well-usage data suggest that community wells in Araihazar, and probably elsewhere in Bangladesh, were not optimally allocated by the government because of elite capture.

Arsenic migration to deep groundwater in Bangladesh influenced by adsorption and water demand.

Drinking shallow groundwater with naturally elevated concentrations of arsenic is causing widespread disease in many parts of South and Southeast Asia. In the Bengal Basin, growing reliance on deep (>150 m) groundwater has lowered exposure. In the most affected districts of Bangladesh, shallow groundwater concentrations average 100 to 370 µg L(-1), while deep groundwater is typically < 10 µg L(-1). Groundwater flow simulations have suggested that, even when deep pumping is restricted to domestic use, deep groundwater in some areas of the Bengal Basin is at risk of contamination. However, these simulations have neglected the impedance of As migration by adsorption to aquifer sediments. Here we quantify for the first time As sorption on deeper sediments in situ by replicating the intrusion of shallow groundwater through injection of 1,000 L of deep groundwater modified with 200 µg L(-1) of As into a deeper aquifer. Arsenic concentrations in the injected water were reduced by 70% due to adsorption within a single day. Basin-scale modelling indicates that while As adsorption extends the sustainable use of deep groundwater, some areas remain vulnerable; these areas can be prioritized for management and monitoring.

Seasonal fluctuations in zinc speciation within a contaminated wetland.

The cycling of common sorbents such as metal (hydr)- oxides, carbonates, and sulfides in redox-active environments influences the partitioning of associated trace elements such as zinc. Consequently, fluctuations in redox status may in part determine the availability and mobility of Zn and other trace elements. This research examines changes in Zn speciation in a contaminated wetland soil that undergoes seasonal flooding. X-ray absorption spectroscopy (XAS) was employed to identify and quantify Zn species from soil cores collected over a 1-year cycle as a function of water depth, location, and soil depth. Zinc associated with (hydr)oxide phases in dry, oxidized soils and with sulfides and carbonates in flooded systems. An increase in water level was accompanied by a reversible change in Zn fractionation toward ZnS and ZnC03. However, a small, recalcitrant fraction of Zn associated with (hydr)oxides remained even when the soils were exposed to highly reducing conditions. Water depth and redox potential were the most important factors in determining Zn speciation, although spatial variation was also important. These data indicate that zinc sorption is a dynamic process influenced by environmental changes.