Saugata Datta

Perennial ponds are not an important source of water or dissolved organic matter to groundwaters with high arsenic concentrations in West Bengal, India

excess of 4600 m gk g −1 . Stable isotope ratios of waters from constructed, perennial ponds indicate the ponds are chiefly recharged during the summer monsoon, and subsequently undergo extensive evaporation during the dry (winter) season. In contrast, groundwaters with high As concentrations plot along the local meteoric water line (LMWL) near where the annual, volume‐weighted mean precipitation values for d 2 Ha ndd 18 O would plot. The stable isotope data demonstrate that groundwaters are directly recharged by local precipitation without significant evaporation, and thus are not recharged by, nor mixed with, the pond waters. Furthermore, reactive transport modeling indicates that dissolved organic matter (DOM) derived from pond waters does not fuel microbial respiration and As mobilization at depth in the underlying aquifer because travel times for pond‐derived DOM exceed groundwater ages by thousands of years. Instead, organic matter within the aquifer sediments must drive dissimilatory iron reduction and As release to groundwaters. Citation: Datta, S., A. W. Neal, T. J. Mohajerin, T. Ocheltree, B. E. Rosenheim, C. D. White, and K. H. Johannesson (2011), Perennial ponds are not an important source of water or dissolved organic matter to groundwaters with high arsenic concentrations in West Bengal, India, Geophys. Res. Lett., 38, L20404, doi:10.1029/2011GL049301.

Biogeochemical Controls on the Release and Accumulation of Mn and As in Shallow Aquifers, West Bengal, India

The prevalence of manganese (Mn) in Southeast Asian drinking water has recently become a topic of discussion, particularly when concurrent with elevated arsenic (As). Although Mn groundwater geochemistry has been studied, the link between dissolved organic matter (DOM) quality and Mn release is less understood. This work evaluates characteristics of DOM, redox chemistry, and the distribution of Mn within Murshidabad, West Bengal, India. Shallow aquifer samples were analyzed for cations, anions, dissolved organic carbon, and DOM properties using 3-dimensional fluorescence excitation emission matrices followed by parallel factor modeling analyses. Two biogeochemical regimes are apparent, separated geographically by the river Bhagirathi. East of the river, where Eh and nitrate (NO3-) values are low, humic-like DOM coexists with high dissolved Mn, As, and Fe. West of the river, lower dissolved As and Fe concentrations are coupled with more protein-like DOM and higher NO3- and Eh values. Dissolved Mn concentrations are elevated in both regions. Based on the distribution of available electron acceptors, it is hypothesized that groundwater east of the Bhagirathi, which are more reducing and enriched in dissolved Fe and Mn but depleted in NO3-, are chemically dominated by Mn(IV) / Fe(III) reduction processes. West of the river where NO3- is abundant yet dissolved Fe is absent, NO3- and Mn(IV) likely buffer redox conditions such that Eh values are not sufficiently reducing to release Fe into the dissolved phase. The co-occurrence of humic-like DOM with dissolved As, Fe, and Mn in the more reducing aquifers may reflect complex formation between humic DOM and metals, as well as electron shuttling processes involving humic DOM, which may enhance metal(loid) release. Saturation indices of rhodochrosite (MnCO3) suggest that precipitation is thermodynamically favorable in a greater proportion of the more reducing sites, however humic DOM–Mn complexes may be inhibiting MnCO3 precipitation. Where dissolved arsenic concentrations are low, it is postulated that Mn(IV) reduction is oxidizing As(III) to As(V), increasing the potential for re-adsorption of As(V) onto relatively stable, un-reduced or newly precipitated Fe-oxides. Manganese release appears to be independent of DOM quality, as it persists in both humic and protein-like DOM environments.

Tungsten Contamination of Soils and Sediments: Current State of Science

Tungsten (W) is commonly employed as a non-toxic alternative to lead in a broad variety of industrial and military applications. However, correlations between environmental contamination through soil, water and airborne pathways, and biological effects such as epithelial damage, bioaccumulation, and trophic mobility, have led to its classification as an “emerging contaminant.” Of particular concern are recent clusters of childhood leukemia and lung cancer in the vicinity of tungsten mines and processing facilities. High environmental tungsten availability has also been associated with altered thyroid function, cardiovascular disease, and prolonged elevation of concentrations in blood, breath, and urine. Tungsten’s use as a replacement for lead (Pb) in military munitions has resulted in leaching of tungsten into soil and into soft tissues in which bullet fragments are embedded. Despite these associations, no consensus has been reached regarding the mechanisms by which tungsten affects the human body. Particularly confounding are the issues of co-toxicity with other known contaminants such as arsenic, cobalt, and cadmium, and differences resulting from the various methods of ingestion. The present paper summarizes the current behavior of tungsten in the environment, its occurrence within the pedosphere, biosphere, and atmosphere, and discusses its potential effects on exposed biota (especially humans). In particular, knowledge gaps are identified regarding the biological mechanisms of tungsten-related disease, which urgently require further elucidation in order to develop appropriate policies and management practices for the use of this element.

Changing recharge pathways within an intensively pumped aquifer with high fluoride concentrations in Central Mexico

Fluoride (F), naturally found in aquifers around the world at toxic concentrations, causes disease in millions of people. The long-term stability, however, of those concentrations within intensively pumped aquifers is poorly characterized. We assessed long-term stability in the spatial distribution of F concentrations in an intensively pumped aquifer within the semi-arid, inter-montane Independence Basin in central Mexico between 1999 and 2016. Although stable in 16 re-sampled wells, F concentrations increased in some localities across the basin by as much as 4mg/L. Changes in recharge pathways to the deep aquifer were identified by analyzing changes in δ2H, δ18O and Cl/Br mass ratios. In 1999, δ2H and δ18O values suggested the aquifer was recharged in the mountains. In 2016, however, substantial increases in δ18O values in the center of the basin suggest recharge water is derived from rainfall that had experienced increased evaporation. In 1999, the mass ratio Cl/Br in groundwater was slightly enriched over local rainfall, and followed a single mixing line on a plot of Cl. vs. Cl/Br. In 2016, however, three distinct groupings of wells were evident, all following different mixing lines. These changes suggest input from new sources including urban sewage, evaporate dissolution, connate sea water and geothermal waters. Step-wise multiple regression was used to quantify the impact of physical and chemical parameters on F concentrations. In 1999, Li (6.8±1.7) and Na (0.01±0.004) drove F concentrations (R2=0.54). In 2016, Na (0.013±0.0018), HCO3 (0.004±0.001), Ca (-0.0018±0.00045), and Mg (-0.055±0.023) drove F concentrations (0.78). Irrigation pumping and urban expansion within semi-arid, groundwater-dependent, inter-montane basins drive mixing of disparate groundwater chemistries and introduces new sources of recharge to aquifers inducing changes in aquifer chemistry including increasing concentrations of geogenic toxic elements.

Influence of monsoonal recharge on arsenic and dissolved organic matter in the Holocene and Pleistocene aquifers of the Bengal Basin

Arsenic (As) mobilization in the Bengal Basin aquifers has been studied for several decades due to the complex redox bio-geochemistry, dynamic hydrogeology and complex nature of dissolved organic matter (DOM). Earlier studies have examined the changes in groundwater As in the dry season before monsoon and during the wet season after monsoonal recharge. To investigate the more immediate influence of recharge during the active monsoon period on As mobilization and DOM character, groundwater samples were analyzed in the pre-monsoon and during the active monsoon period. Groundwater samples were collected from shallow (<40 m) and deep (>40 m) tube-wells in West Bengal, India. Dissolved AsT in shallow groundwater ranged from 50 to 315 μg/L exceeding the WHO guideline of 10 μg/L. Shallow groundwater also showed high total dissolved nitrogen, carbon to nitrogen (C:N) <1, and humic-like DOM with a humic:protein ratio >1. By contrast, deep groundwaters contained AsT between 0.5 and 11 μg/L with carbonaceous and protein-like DOM, C:N >1, and humic:protein <1. Stable isotopes of δ18O and δ2H and Cl/Br results indicated three recharge scenarios in the shallow aquifer including direct recharge of dilute rainwater, evaporated surface water, and anthropogenically impacted surface water. Monsoonal recharge did not cause notable changes in AsT in deep or shallow groundwater, including two As hotspots in the Pleistocene aquifer. However, the monsoon did result in a two-fold decrease in SUVA254, increase in nitrite and nitrate in the shallow groundwater. The DOM in the deep groundwater at the two As hotspots (with AsT 132 and 715 μg/L) had optical properties with much greater humic-like DOM than the surrounding groundwater, which had low AsT and highly protein-like DOM. Overall, these results support that protein-like DOM associated with low groundwater As concentrations and suggest that the monsoonal influence on nitrate and nitrite is limited to shallow aquifers.

The fate of arsenic in groundwater discharged to the Meghna River, Bangladesh

Environmental context Arsenic contamination of groundwater is a major environmental problem in many areas of the world. In south-east Asia, iron-rich reducing groundwater mixes with oxidising river water in hyporheic zones, precipitating iron oxides. These oxides can act as a natural reactive barrier capable of accumulating elevated solid-phase concentrations of arsenic. Abstract Shallow, anoxic aquifers within the Ganges–Brahmaputra–Meghna Delta (GBMD) commonly contain elevated concentrations of arsenic (As), iron (Fe) and manganese (Mn). Highly enriched solid-phase concentrations of these elements have been observed within sediments lining the banks of the Meghna River. This zone has been described as a Natural Reactive Barrier (NRB). The impact of hydrological processes on NRB formation, such as transient river levels, which drive mixing between rivers and aquifers, is poorly understood. We evaluated the impact of groundwater flow dynamics on hydrobiogeochemical processes that led to the formation of an Fe- and Mn-rich NRB containing enriched As, within a riverbank aquifer along the Meghna River. The NRB dimensions were mapped using four complementary elemental analysis methods on sediment cores: X-ray fluorescence (XRF), aqua regia bulk extraction, and HCl and sodium phosphate leaching. It extended from 1.2 to 2.4 m in depth up to 15 m from the river’s edge. The accumulated As was advected to the NRB from offsite and released locally in response to mixing with aged river water. Nearly all of the As was subsequently deposited within the NRB before discharging to the Meghna. Significant FeII release to the aqueous phase was observed within the NRB. This indicates the NRB is a dynamic zone defined by the interplay between oxidative and reductive processes, causing the NRB to grow and recede in response to rapid and seasonal hydrologic processes. This implies that natural and artificially induced changes in river stages and groundwater-tables will impact where As accumulates and is released to aquifers.