Iron (Fe) and dissolved organic matter (DOM) cycling have been implicated in arsenic mobilization via microbially mediated Fe oxide reduction. To evaluate the sources and multiple roles of DOM in Bangladesh aquifers, we conducted spectroscopic analyses on various types of surface water and groundwater samples from a site representative of aquifer chemistry and hydrology. Surface water contained humic substances with oxidized quinone-like moieties and high concentrations of labile microbially derived DOM. In contrast, in shallow groundwater where dissolved iron and arsenic concentrations were high, the quinone-like moieties of humic substances were more reduced, with less abundant labile DOM than that of surface water. Instead, DOM at these depths was characterized by terrestrial (plant/soil) signatures. A sediment microcosm experiment demonstrated that Fe(II) and terrestrially derived DOM were released from sediment over time. The results provide new evidence to support a dual role of natural DOM in Bangladesh aquifers (1) as a labile substrate for Fe- and humic-reducing bacteria and (2) as an electron shuttle via humic substances to enhance microbial iron reduction. Fluorescence index, amino acid-like fluorescence, and redox index may serve as useful indicators of the type of DOM likely to be involved in Fe solubilization and potentially As mobilization reactions.

In some high As groundwater systems, correlations are observed between dissolved organic matter (DOM) and As concentrations, but in other systems such relationships are not observed. The role of labile DOM as the main driver of microbial reductive dissolution does not explain the variation in these relationships. Other processes that may also influence arsenic mobility include complexation of As by dissolved humic substances, and competitive sorption and electron shuttling reactions mediated by humics. To evaluate such humic interactions, we characterized the optical properties of whole waters sampled from groundwater, spanning an age gradient in Araihazar, Bangladesh. Further, we analyzed fulvic acids (FA) isolated from large volume samples for optical properties, C and N content and 13C-NMR spectroscopic distribution. Old groundwater (> 30 years old) contained primarily sediment-derived DOM and had significantly higher (p < 0.001) dissolved arsenic concentration than groundwater that was < 5 years old. Younger groundwater had DOM spectroscopic signatures similar to surface water DOM and characteristic of a sewage pollution influence. Associations between dissolved arsenic, iron, and FA concentration, and fluorescence properties of isolated FA suggest that aromatic, terrestrially-derived FAs promote arsenic-iron-FA complexation reactions that enhance arsenic mobility.

Arsenic in groundwater has been a concern in South and Southeast Asia for more than a decade. We explore here the possibility that hydrogeologic factors recently shown to influence the distribution of arsenic might also affect the level of contamination of shallow (<20 m) wells with microbial pathogens. A total of 96 shallow tube wells in two nearby villages of Bangladesh were surveyed during the wet and dry seasons, along with 55 deeper wells in neighboring villages. One of the two villages is located in a particularly sandy environment where recharge is rapid and shallow wells contain little arsenic. Shallow aquifers in the other village are capped with an impermeable clay layer, recharge is an order of magnitude slower, and arsenic levels are high. The fecal indicator E. coli was detected in 43% of shallow wells, compared with 12% of deeper wells. More shallow wells contained E. coli during the wet season (61%) than during the dry season (9%). In the wet season, a higher proportion of shallow wells in the village with low arsenic levels (72%) contained E. coli compared with the village having high arsenic levels (43%). Differences in arsenic and E. coli distributions between the two sites are likely due to the differences in permeability of near-surface sediments although differences in average well-depth between the two villages (9 ± 4 vs. 15 ± 3 m) may play a role as well. Hydrogeologic conditions that favor high levels of fecal contamination but low levels of arsenic in shallow groundwater should be taken into account during arsenic mitigation throughout South and Southeast Asia.

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The spatial heterogeneity of dissolved arsenic (As) concentrations in shallow groundwater of the Bengal Basin has been attributed to transport of As (and reactive carbon) from external sources or to the release of As from within grey sand formations. We explore the latter scenario in this detailed hydrological and geochemical study along a 300 m transect of a shallow aquifer extending from a groundwater recharge area within a sandy channel bar to its discharge into a nearby stream. Within the 10–20 m depth range, groundwater ages along the transect determined by the 3H–3He method increase from <10 yr in the recharge area to a maximum of 40 yr towards the stream. Concentrations of groundwater As within the same grey sands increase from 10 to 100 to ∼500 µg/L along this transect. Evidence of reversible adsorption of As between the groundwater and sediment was obtained from a series of push–pull experiments, traditional batch adsorption experiments, and the accidental flooding of a shallow monitoring well. Assuming reversible adsorption and a distribution coefficient, Kd, of 0.15–1.5 L/kg inferred from these observations, a simple flushing model shows that the increase in As concentrations with depth and groundwater age at this site, and at other sites in the Bengal and Red River Basins, can be attributed to the evolution of the aquifer over 100–1000 years as aquifer sands are gradually flushed of their initial As content. A wide range of As concentrations can thus be maintained in groundwater with increases with depth governed by the history of flushing and local recharge rates, without external inputs of reactive carbon or As from other sources.

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1x or (4) 10x the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.

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Bacterial communities can exert significant influence on the biogeochemical cycling of arsenic (As). This has globally important implications since As in drinking water affects the health of over 100 million people worldwide, including in the Ganges–Brahmaputra Delta region of Bangladesh where geogenic arsenic in groundwater can reach concentrations of more than 10 times the World Health Organization’s limit. Thus, the goal of this research was to investigate patterns in bacterial community composition across gradients in sediment texture and chemistry in an aquifer with elevated groundwater As concentrations in Araihazar, Bangladesh. We characterized the bacterial community by pyrosequencing 16S rRNA genes from aquifer sediment samples collected at three locations along a groundwater flow path at a range of depths between 1.5 and 15 m. We identified significant differences in bacterial community composition between locations in the aquifer. In addition, we found that bacterial community structure was significantly related to sediment grain size, and sediment carbon (C), manganese (Mn), and iron (Fe) concentrations. Deltaproteobacteria and Chloroflexi were found in higher proportions in silty sediments with higher concentrations of C, Fe, and Mn. By contrast, Alphaproteobacteria and Betaproteobacteria were in higher proportions in sandy sediments with lower concentrations of C and metals. Based on the phylogenetic affiliations of these taxa, these results may indicate a shift to more Fe-, Mn-, and humic substance-reducers in the high C and metal sediments. It is well-documented that C, Mn, and Fe may influence the mobility of groundwater arsenic, and it is intriguing that these constituents may also structure the bacterial community.