Sulfate reduction accelerates groundwater arsenic contamination even in aquifers with abundant iron oxides.

Groundwater contamination by geogenic arsenic is a global problem affecting nearly 200 million people. In South and Southeast Asia, a cost-effective mitigation strategy is to use oxidized low-arsenic aquifers rather than reduced high-arsenic aquifers. Aquifers with abundant oxidized iron minerals are presumably safeguarded against immediate arsenic contamination, due to strong sorption of arsenic onto iron minerals. However, preferential pumping of low-arsenic aquifers can destabilize the boundaries between these aquifers, pulling high-arsenic water into low-arsenic aquifers. We investigate this scenario in a hybrid field-column experiment in Bangladesh where naturally high-arsenic groundwater is pumped through sediment cores from a low-arsenic aquifer, and detailed aqueous and solid-phase measurements are used to constrain reactive transport modelling. Here we show that elevated groundwater arsenic concentrations are induced by sulfate reduction and the predicted formation of highly mobile, poorly sorbing thioarsenic species. This process suggests that contamination of currently pristine aquifers with arsenic can occur up to over 1.5 times faster than previously thought, leading to a deterioration of urgently needed water resources.

Recommended Sampling Intervals for Arsenic in Private Wells.

Geogenic arsenic in drinking water is a worldwide problem. For private well owners, testing (e.g., private or government laboratory) is the main method to determine arsenic concentration. However, the temporal variability of arsenic concentrations is not well characterized and it is not clear how often private wells should be tested. To answer this question, three datasets, two new and one publicly available, with temporal arsenic data were utilized: 6370 private wells from New Jersey tested at least twice since 2002, 2174 wells from the USGS NAWQA database, and 391 private wells sampled 14 years apart from Bangladesh. Two arsenic drinking water standards are used for the analysis: 10 µg/L, the WHO guideline and EPA standard or maximum contaminant level (MCL) and 5 µg/L, the New Jersey MCL. A rate of change was determined for each well and these rates were used to predict the temporal change in arsenic for a range of initial arsenic concentrations below an MCL. For each MCL and initial concentration, the probability of exceeding an MCL over time was predicted. Results show that to limit a person to below a 5% chance of drinking water above an MCL, wells that are ½ an MCL and above should be tested every year and wells below ½ an MCL should be tested every 5 years. These results indicate that one test result below an MCL is inadequate to ensure long-term compliance. Future recommendations should account for temporal variability when creating drinking water standards and guidance for private well owners.

Arsenic contamination of Bangladesh aquifers exacerbated by clay layers.

Confining clay layers typically protect groundwater aquifers against downward intrusion of contaminants. In the context of groundwater arsenic in Bangladesh, we challenge this notion here by showing that organic carbon drawn from a clay layer into a low-arsenic pre-Holocene (>12 kyr-old) aquifer promotes the reductive dissolution of iron oxides and the release of arsenic. The finding explains a steady rise in arsenic concentrations in a pre-Holocene aquifer below such a clay layer and the repeated failure of a structurally sound community well. Tritium measurements indicate that groundwater from the affected depth interval (40-50 m) was recharged >60 years ago. Deeper (55-65 m) groundwater in the same pre-Holocene aquifer was recharged only 10-50 years ago but is still low in arsenic. Proximity to a confining clay layer that expels organic carbon as an indirect response to groundwater pumping, rather than directly accelerated recharge, caused arsenic contamination of this pre-Holocene aquifer.

Similar retardation of arsenic in gray Holocene and orange Pleistocene sediments: Evidence from field-based column experiments in Bangladesh.

Groundwater flow has the potential to introduce arsenic (As) in previously uncontaminated aquifers. The extent to which As transport is retarded by adsorption is particularly relevant in Bangladesh where low-As wells offer the best chance of reducing chronic exposure to As of a large rural population dependent on groundwater. In this study, column experiments were conducted with intact cores in the field to measure As retardation. Freshly collected cores of reduced iron (Fe-II) dominated gray sediment of Holocene age as well as oxidized Fe (III)-coated orange sediment of Pleistocene age were eluted at pore-water velocities of 40-230 cm/day with anoxic groundwater pumped directly from a well and containing 320 µg/L As. Up to 100 µg/L As was immediately released from gray sand but the main As breakthrough for both gray and orange sand occurred between 30 and 70 pore volumes, depending on flow rate. The early release of As from gray sand is attributed to the presence of a weakly bound pool of As. The sorption of As was kinetically limited in both gray and orange sand columns. We used a reversible multi-reaction transport model to simulate As breakthrough curves while keeping the model parameters as constant as possible. Contrary to the notion that dissolved As is sorbed more strongly to orange sands, we show that As was similarly retarded in both gray and orange sands in the field.