Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

Decoupling of As and Fe release to Bangladesh groundwater under reducing conditions. Part I: Evidence from sediment profiles

This study reexamines the notion that extensive As mobilization in anoxic groundwater of Bangladesh is intimately linked to the dissolution of Fe oxyhydroxides on the basis of analyses performed on a suite of freshly collected samples of aquifer material. Detailed sediment profiles extending to 40 to 70 m depth below the surface were obtained at six sites where local groundwater As concentrations were known to span a wide range. The sediment properties that were measured include (1) the proportion of Fe(II) in the Fe fraction leached in hot 1.2 N HCl, (2) diffuse spectral reflectance, and (3) magnetic susceptibility.In parallel with local concentrations of dissolved As ranging from <5 to 600 μg/L, Fe(II)/Fe ratios in shallow (gray) Holocene sands tended to gradually increase with depth from values of 0.3 to 0.5 to up to 0.9. In deeper (orange) aquifers of presumed Pleistocene age that were separated from shallow sands by a clay layer and contained <5 μg/L dissolved As, leachable Fe(II)/Fe ratios averaged ∼0.2. There was no consistent relation between sediment Fe(II)/Fe and dissolved Fe concentrations in groundwater in nearby wells. The reflectance measurements indicate a systematic linear relation (R² of 0.66; n = 151) between the first derivative transform of the reflectance at 520 nm and Fe(II)/Fe. The magnetic susceptibility of the shallow aquifer sands ranged from 200 to 3600 (x 10⁻⁹ m³/kg SI) and was linearly related (R² of 0.75; n = 29) to the concentrations of minerals that could be magnetically separated (0.03 to 0.79% dry weight). No systematic depth trends in magnetic susceptibility were observed within the shallow sands, although the susceptibility of deeper low-As aquifers was low (up to ∼200 × 10⁻⁹ m³/kg SI).This set of observations, complemented by incubation results described in a companion paper by van Geen et al. (this volume), suggests that the release of As is linked to the transformation of predominantly Fe (III) oxyhydroxide coatings on sand particles to Fe(II) or mixed Fe(II/III) solid phases with a flatter reflectance spectrum such as siderite, vivianite, or magnetite, without necessarily resulting in the release of Fe to groundwater. The very low As/Fe ratio of magnetically separated minerals compared to the As/Fe of bulk acid leachate (2 vs. 40 10⁻⁶, respectively) suggests that such a transformation could be accompanied by a significant redistribution of As to a mobilizable phase on the surface of aquifer particles.     

Hydrogeological typologies of the Indo-Gangetic basin alluvial aquifer,South Asia

The Indo-Gangetic aquifer is one of the world’s most important transboundary water resources, and the most heavily exploited aquifer in the world. To better understand the aquifer system, typologies have been characterized for the aquifer, which integrate existing datasets across the Indo-Gangetic catchment basin at a transboundary scale for the first time, and provide an alternative conceptualization of this aquifer system. Traditionally considered and mapped as a single homogenous aquifer of comparable aquifer properties and groundwater resource at a transboundary scale, the typologies illuminate significant spatial differences in recharge, permeability, storage, and groundwater chemistry across the aquifer system at this transboundary scale. These changes are shown to be systematic, concurrent with large-scale changes in sedimentology of the Pleistocene and Holocene alluvial aquifer, climate, and recent irrigation practices. Seven typologies of the aquifer are presented, each having a distinct set of challenges and opportunities for groundwater development and a different resilience to abstraction and climate change. The seven typologies are: (1) the piedmont margin, (2) the Upper Indus and Upper-Mid Ganges, (3) the Lower Ganges and Mid Brahmaputra, (4) the fluvially influenced deltaic area of the Bengal Basin, (5) the Middle Indus and Upper Ganges, (6) the Lower Indus, and (7) the marine-influenced deltaic areas.     

Delineating low-arsenic groundwater environments in the Bengal Aquifer System, Bangladesh

Studies within the As-affected Bengal Basin have indicated that low-As groundwater can be found in a variety of geological and geomorphological settings. The hydrogeological environments that host low-As groundwater may be interpreted within a geological framework determined by the Quaternary evolution of the Bengal Aquifer System (BAS). This provides the basis for delineating the position and extent of shallow low-As groundwater, low-As groundwater in oxidised ‘red-bed’ sediments, and deep low-As groundwater. Data available on a national scale allow a preliminary delineation of these low-As groundwater environments across Bangladesh, based on empirical associations of low-As groundwater occurrences with topography, water table elevation, surface sediment lithology, geology and the screen depth of deep wells in low-As zones.     

The influence of groundwater abstraction on interpreting climate controls and extreme recharge events from well hydrographs in semi-arid South Africa

There is a scarcity of long-term groundwater hydrographs from sub-Saharan Africa to investigate groundwater sustainability, processes and controls. This paper presents an analysis of 21 hydrographs from semi-arid South Africa. Hydrographs from 1980 to 2000 were converted to standardised groundwater level indices and rationalised into four types (C1–C4) using hierarchical cluster analysis. Mean hydrographs for each type were cross-correlated with standardised precipitation and streamflow indices. Relationships with the El Niño–Southern Oscillation (ENSO) were also investigated. The four hydrograph types show a transition of autocorrelation over increasing timescales and increasingly subdued responses to rainfall. Type C1 strongly relates to rainfall, responding in most years, whereas C4 notably responds to only a single extreme event in 2000 and has limited relationship with rainfall. Types C2, C3 and C4 have stronger statistical relationships with standardised streamflow than standardised rainfall. C3 and C4 changes are significantly (p <?0.05) correlated to the mean wet season ENSO anomaly, indicating a tendency for substantial or minimal recharge to occur during extreme negative and positive ENSO years, respectively. The range of different hydrograph types, sometimes within only a few kilometres of each other, appears to be a result of abstraction interference and cannot be confidently attributed to variations in climate or hydrogeological setting. It is possible that high groundwater abstraction near C3/C4 sites masks frequent small-scale recharge events observed at C1/C2 sites, resulting in extreme events associated with negative ENSO years being more visible in the time series.

     

The impact of intensive groundwater abstraction on recharge to a shallow regional aquifer system: evidence from Bangladesh

Quantitative evaluations of the impact of groundwater abstraction on recharge are rare. Over a period (1975??007) during which groundwater abstraction increased dramatically in the Bengal Basin, changes in net groundwater recharge in Bangladesh are assessed using the water-table fluctuation method. Mean annual groundwater recharge is shown to be higher (300??00?mm) in northwestern and southwestern areas of Bangladesh than in southeastern and northeastern regions (<100?mm) where rainfall and potential recharge are greater. Net recharge in many parts of Bangladesh has increased substantially (5??5?mm/year between 1985 and 2007) in response to increased groundwater abstraction for irrigation and urban water supplies. In contrast, net recharge has slightly decreased (??.5 to ???mm/year) in areas where groundwater-fed irrigation is low (<30% of total irrigation) and where abstraction has either decreased or remained unchanged over the period of 1985??007. The spatio-temporal dynamics of recharge in Bangladesh illustrate the fundamental flaw in definitions of “safe yield??based on recharge estimated under static (non-pumping) conditions and reveal the areas where (1) further groundwater abstraction may increase actual recharge to the shallow aquifer, and (2) current groundwater abstraction for irrigation and urban water supplies is unsustainable.     

Mineralogical profiling of alluvial sediments from arsenic-affected Ganges-Brahmaputra floodplain in central Bangladesh

Mineral assemblages (heavy and light fractions) and sedimentological characteristics of the Quaternary alluvial aquifers were examined in the central Bengal Basin where As concentrations in groundwater are highly variable in space but generally decrease downward. Chemical compositions of sediment samples from two vertical core profiles (2-150 m below ground level, bgl) were analyzed along with groundwater in moderately As-enriched aquifers in central Bangladesh (Manikganj district), and the As mobilization process in the alluvial aquifer is described. Heavy minerals such as biotite, magnetite, amphibole, apatite and authigenic goethite are abundant at shallow (<100 m below ground level (mbgl)) depths but less abundant at greater depths. It is interpreted that principal As-bearing minerals were derived from multiple sources, primarily from ophiolitic belts in the Indus-Tsangpo suture in the northeastern Himalayan and Indo-Burman Mountain ranges. Authigenic and amorphous Fe-(oxy)hydroxide minerals that are generally formed in river channels in the aerobic environment are the major secondary As-carriers in alluvial sediments. Reductive dissolution (mediated by Fe-reducing bacteria) of Fe-(oxy)hydroxide minerals under anoxic chemical conditions is the primary mechanism responsible for releasing As into groundwater. Authigenic siderite that precipitates under reducing environment at greater depths decreases Fe and possibly As concentrations in groundwater. Presence of Fe(III) minerals in aquifers shows that reduction of these minerals is incomplete and this can release more As if further Fe-reduction takes place with increased supplies of organic matter (reactive C). Absence of authigenic pyrite suggests that SO₄ reduction (mediated by SO₄-reducing bacteria) in Manikganj groundwater is limited in contrast to the southeastern Bengal Basin where precipitation of arsenian pyrite is thought to sequester As from groundwater.     

Near surface lithology and spatial variation of arsenic in the shallow groundwater: southeastern Bangladesh

This study investigated the relationship between near-surface lithology and the spatial variability of As concentrations using sediment grain-size analysis and electromagnetic induction survey in the southeast Bangladesh. It has been observed that the aquifers overlain by finer sediments have higher concentrations of As in groundwater, whereas As concentrations are remarkably low in aquifers having permeable sandy materials or thinner silt/clay layer at the surface. The near-surface lithology acts as a controlling factor for spatial distributions of groundwater As within the very shallow depths (<15 m). Shallow alluvial aquifers can provide low-As drinking water in many areas of the country when tube wells are properly installed after investigation of the overlying near-surface sediment attributes and hydraulic properties.     

Spatial relationship of groundwater arsenic distribution with regional topography and water-table fluctuations in the shallow aquifers in Bangladesh

The present study has examined the relationship of groundwater arsenic (As) levels in alluvial aquifers with topographic elevation, slope, and groundwater level on a large basinal-scale using high-resolution (90 m × 90 m) Shuttle Radar Topography Mission (SRTM) digital elevation model and water-table data in Bangladesh. Results show that high As (>50 μg/l) tubewells are located in low-lying areas, where mean surface elevation is approximately 10 m. Similarly, high As concentrations are found within extremely low slopes (<0.7°) in the country. Groundwater elevation (weekly measured by Bangladesh Water Development Board) was mapped using water-table data from 950 shallow (depth <100 m) piezometers distributed over the entire country. The minimum, maximum and mean groundwater elevation maps for 2003 were generated using Universal Kriging interpolation method. High As tubewells are located mainly in the Ganges–Brahmaputra–Meghna delta, Sylhet Trough, and recent floodplains, where groundwater elevation in shallow aquifers is low with a mean value of 4.5 m above the Public Works Datum (PWD) level. Extremely low groundwater gradients (0.01–0.001 m/km) within the GBM delta complex hinder groundwater flow and cause slow flushing of aquifers. Low elevation and gentle slope favor accumulation of finer sediments, As-carrying iron-oxyhydroxide minerals, and abundant organic matter within floodplains and alluvial deposits. At low horizontal hydraulic gradients and under reducing conditions, As is released in groundwater by microbial activity, causing widespread contamination in the low-lying deltaic and floodplain areas, where As is being recycled with time due to complex biogeochemical processes.     

Groundwater depletion in northern India: Impacts of the sub-regional anthropogenic land-use,socio-politics and changing climate

Understanding the key drivers behind intensive use of groundwater resources and subsequent depletion in northern India is important for future food security of India. Although spatio-temporal changes of groundwater storage (GWS) and its depletion in northern India are mapped using the NASA's GRACE (Gravity Recovery and Climate Experiment) records, the sub-regional diverse socio-political and environmental factors contributing to the variability in groundwater withdrawals and renewals are not well documented. Here, we provide new evidence on changes in GWS at different spatial scales using both observations and satellite-based measurements applying both parametric and non-parametric statistical analyses. The substantial loss of GWS has occurred since the beginning of the 21st century, and the decline in GWS is associated with some record-breaking dry and hot climate events. We present how certain state-based policy decisions, such as supplying free electricity for irrigation, prompted farmers to extract groundwater unsustainably and thus led to widespread GWS deletion, which has been also accelerated by frequent dryness and rising temperatures. In the hotspot of Punjab, Haryana and Delhi of northern India, the extracted groundwater during 1985–2013 is equivalent to a metre-high layer if spread uniformly across its geographical domain. We find that the groundwater storage loss in northern India has increased rapidly from 17 km³ to 189 km³ between the pre-2002 and 2002–2013 periods. This loss in northern India is, therefore, an excellent example of rapid surface greening and sub-surface drying—a result of an interplay of socio-political and environmental factors. As groundwater continues to be treated as a common natural resource and no clear definition exists to guide policymaking, this study also illustrates how the administrative district level approach can solve the widespread problem of depletion.