Exploring sustainability of aquifers based on predictive modeling of sorption characteristics of arsenic enriched Holocene sediments in Bangladesh

The importance of accessing safe aquifers in areas with high As is being increasingly recognized. The present study aims to investigate the sorption and mobility of As at the sediment-groundwater interface to identify a likely safe aquifer in the Holocene deposit in southwestern Bangladesh. The upper, shallow aquifer at around 18 m depth, which is composed mainly of very fine, grey, reduced sand and contains 24.3 μg/g As, was found to produce highly enriched groundwater (190 μg/L As). In contrast, deeper sediments are composed of partly oxidized, brownish, medium sand with natural adsorbents like Fe- and Al-oxides; they contain 0.76 μg/g As and impart low As concentrations to the water (4 μg/L). These observations were supported by spectroscopic studies with SEM, TEM, XRD and XRF, and by adsorption, leaching, column tests and sequential extraction. A relatively high in-situ dissolution rate (R_r) of 1.42 × 10⁻¹⁶ mol/m²/s was derived for the shallower aquifer from the inverse mass-balance model. The high R_r may enhance As release processes in the upper sediment. The field-based reaction rate (K_r) was extrapolated to be roughly 1.23 × 10⁻¹³ s⁻¹ and 6.24 × 10⁻¹⁴ s⁻¹ for the shallower and deeper aquifer, respectively, from the laboratory-obtained adsorption/desorption data. This implies that As is more reactive in the shallower aquifer. The partition coefficient for the distribution of As at the sediment-water interface (K_d-As) was found to range from 5 to 235 L/kg based on in-situ, batch adsorption, and flow-through column techniques. Additionally, a parametric equation for K_d-As (R² = 0.67) was obtained from the groundwater pH and the logarithm of the leachable Fe and Al concentrations in sediment. A one-dimensional finite-difference numerical model incorporating K_d and K_r showed that the shallow, leached As can be immobilized and prevented from reaching the deeper aquifer (∼150 m) after 100 year by a natural filter of oxidizing sand and adsorbent minerals like Fe and Al oxides; in this scenario, 99% of the As in groundwater is reduced. The deeper aquifer appears to be an adequate source of sustainable, safe water.     

Evaluation of hydrogeochemical processes in the Pleistocene aquifers of Middle Ganga Plain, Uttar Pradesh, India

Evaluation of major ion chemistry and solute acquisition process controlling water chemical composition were studied by collecting a total of fifty-one groundwater samples in shallow (<25 m) and deep aquifer (>25 m) in the Varanasi area. Hydrochemical facies, Mg-HCO₃ dominated in the largest part of shallow groundwater followed by Na-HCO₃ and Ca-HCO₃ whereas Ca-HCO₃ is dominated in deep groundwater followed by Mg-HCO₃ and Na-HCO₃. High As concentration (>50 μg/l) is found in some of the villages situated in northeastern parts (i.e. adjacent to the concave part of the meandering Ganga river) of the Varanasi area. Arsenic contamination is confined mostly in tube wells (hand pump) within the Holocene newer alluvium deposits, whereas older alluvial aquifers are having arsenic free groundwater. Geochemical modeling using WATEQ4F enabled prediction of saturation state of minerals and indicated dissolution and precipitation reactions occurring in groundwater. Majority of shallow and deep groundwater samples of the study area are oversaturated with carbonate bearing minerals and under-saturated with respect to sulfur and amorphous silica bearing minerals. Sluggish hydraulic conductivity in shallow aquifer results in higher mineralization of groundwater than in deep aquifer. But the major processes in deep aquifer are leakage of shallow aquifer followed by dominant ion-exchange and weathering of silicate minerals.     

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.     

Paleowaters in Silurian-Devonian carbonate aquifers: Geochemical evolution of groundwater in the Great Lakes region since the Late Pleistocene

Changes in the climatic conditions during the Late Quaternary and Holocene greatly impacted the hydrology and geochemical evolution of groundwaters in the Great Lakes region. Increased hydraulic gradients from melting of kilometer-thick Pleistocene ice sheets reorganized regional-scale groundwater flow in Paleozoic aquifers in underlying intracratonic basins. Here, we present new elemental and isotopic analyses of 134 groundwaters from Silurian-Devonian carbonate and overlying glacial drift aquifers, along the margins of the Illinois and Michigan basins, to evaluate the paleohydrology, age distribution, and geochemical evolution of confined aquifer systems. This study significantly extends the spatial coverage of previously published groundwaters in carbonate and drift aquifers across the Midcontinent region, and extends into deeper portions of the Illinois and Michigan basins, focused on the freshwater-saline water mixing zones. In addition, the hydrogeochemical data from Silurian-Devonian aquifers were integrated with deeper basinal fluids, and brines in Upper Devonian black shales and underlying Cambrian-Ordovician aquifers to reveal a regionally extensive recharge system of Pleistocene-age waters in glaciated sedimentary basins. Elemental and isotope geochemistry of confined groundwaters in Silurian-Devonian carbonate and glacial drift aquifers show that they have been extensively altered by incongruent dissolution of carbonate minerals, dissolution of halite and anhydrite, cation exchange, microbial processes, and mixing with basinal brines. Carbon isotope values of dissolved inorganic carbon (DIC) range from −10 to −2‰, ⁸⁷Sr/⁸⁶Sr ratios range from 0.7080 to 0.7090, and δ³⁴S-SO₄ values range from +10 to 30‰. A few waters have elevated δ¹³C_DIC values (>15‰) from microbial methanogenesis in adjacent organic-rich Upper Devonian shales. Radiocarbon ages and δ¹⁸O and δD values of confined groundwaters indicate they originated as subglacial recharge beneath the Laurentide Ice Sheet (14-50 ka BP, −15 to −13‰ δ¹⁸O). These paleowaters are isolated from shallow flow systems in overlying glacial drift aquifers by lake-bed clays and/or shales. The presence of isotopically depleted waters in Paleozoic aquifers at relatively shallow depths illustrates the importance of continental glaciation on regional-scale groundwater flow. Modern groundwater flow in the Great Lakes region is primarily restricted to shallow unconfined glacial drift aquifers. Recharge waters in Silurian-Devonian and unconfined drift aquifers have δ¹⁸O values within the range of Holocene precipitation: −11 to −8‰ and −7 to −4.5‰ for northern Michigan and northern Indiana/Ohio, respectively. Carbon and Sr isotope systematics indicate shallow groundwaters evolved through congruent dissolution of carbonate minerals under open and closed system conditions (δ¹³C_DIC = −14.7 to−11.1‰ and ⁸⁷Sr/⁸⁶Sr = 0.7080-0.7103). The distinct elemental and isotope geochemistry of Pleistocene- versus Holocene-age waters further confirms that surficial flow systems are out of contact with the deeper basinal-scale flow systems. These results provide improved understanding of the effects of past climate change on groundwater flow and geochemical processes, which are important for determining the sustainability of present-day water resources and stability of saline fluids in sedimentary basins.     

Mobilisation of arsenic and other trace elements in fluviolacustrine aquifers of the Huhhot Basin,Inner Mongolia

Observed As concentrations in groundwater from boreholes and wells in the Huhhot Basin of Inner Mongolia, northern China, range between <1 μg l⁻¹ and 1480 μg l⁻¹. The aquifers are composed of Quaternary (largely Holocene) lacustrine and fluvial sediments. High concentrations are found in groundwater from both shallow and deep boreholes as well as from some dug wells (well depths ranging between <10 m and 400 m). Populations from the affected areas experience a number of As-related health problems, the most notable of which are skin lesions (keratosis, melanosis, skin cancer) but with internal cancers (lung and bladder cancer) also having been reported. In both the shallow and deep aquifers, groundwaters evolve down the flow gradient from oxidising conditions along the basin margins to reducing conditions in the low-lying central part of the basin. High As concentrations occur in anaerobic groundwaters from this low-lying area and are associated with moderately high dissolved Fe as well as high Mn, NH₄, dissolved organic C (DOC), HCO₃ and P concentrations. Many of the deep groundwaters have particularly enriched DOC concentrations (up to 30 mg l⁻¹) and are often brown as a result of the high concentrations of organic acid. In the reducing groundwaters, inorganic As(III) constitutes typically more than 60% of the total dissolved As. The highest As concentrations tend to be found in groundwater with low SO₄ concentrations and indicate that As mobilisation occurs under strongly reducing conditions, where SO₄ reduction has been an active process. High concentrations of Fe, Mn, NH₄, HCO₃ and P are a common feature of reducing high-As groundwater provinces (e.g. Bangladesh, West Bengal). High concentrations of organic acid (humic, fulvic acid) are not a universal feature of such aquifers, but have been found in groundwaters from Taiwan and Hungary for example. The observed range of total As concentrations in sediments is 3–29 mg kg⁻¹ (n=12) and the concentrations correlate positively with total Fe. Up to 30% of the As is oxalate-extractable and taken to be associated largely with Fe oxides. The release of As into solution under the reducing conditions is believed to be by desorption coupled with reductive dissolution of the Fe oxide minerals. The association of dissolved As with constituents such as HCO₃, DOC and P may be a coincidence related to the prevalent reducing conditions and slow groundwater flow, but they may also be directly involved because of their competition with As for binding sites on the Fe oxides. The Huhhot groundwaters also have some high concentrations of dissolved U (up to 53 μg l⁻¹) and F⁻ (up to 6.8 mg l⁻¹). In contrast to As, U occurs predominantly under the more oxidising conditions along the basin margins. Fluoride occurs dominantly in the shallow groundwaters which have Na and HCO₃ as the dominant ions. The combination of slow flow of groundwater and the young age of the aquifer sediments are also considered potentially important causes of the high dissolved As concentrations observed as the sediments are likely to contain newly-formed and reactive minerals and have not been well flushed since burial.     

Hydrogeochemical and isotopic evidence of groundwater evolution and recharge in aquifers in Beijing Plain, China

An investigation was conducted in Beijing to identify the groundwater evolution and recharge in the quaternary aquifers. Water samples were collected from precipitation, rivers, wells, and springs for hydrochemical and isotopic measurements. The recharge and the origin of groundwater and its residence time were further studied. The groundwater in the upper aquifer is characterized by Ca-Mg-HCO₃ type in the upstream area and Na-HCO₃ type in the downstream area of the groundwater flow field. The groundwater in the lower aquifer is mainly characterized by Ca-Mg-HCO₃ type in the upstream area and Ca-Na-Mg-HCO₃ and Na-Ca-Mg-HCO₃ type in the downstream area. The δD and δ¹⁸O in precipitation are linearly correlated, which is similar to WMWL. The δD and δ¹⁸O values of river, well and spring water are within the same ranges as those found in the alluvial fan zone, and lay slightly above or below LMWL. The δD and δ¹⁸O values have a decreasing trend generally following the precipitation → surface water → shallow groundwater → spring water → deep groundwater direction. There is evidence of enrichment of heavy isotopes in groundwater due to evaporation. Tritium values of unconfined groundwater give evidence for ongoing recharge in modern times with mean residence times <50 a. It shows a clear renewal evolution along the groundwater flow paths and represents modern recharge locally from precipitation and surface water to the shallow aquifers (<150 m). In contrast, according to ¹⁴C ages in the confined aquifers and residence time of groundwater flow lines, the deep groundwater is approximately or older than 10 ka, and was recharged during a period when the climate was wetter and colder mainly from the piedmont surrounding the plain. The groundwater exploitation is considered to be “mined unsustainably” because more water is withdrawn than it is replenished.     

Hydrogeologic characteristics of groundwater aquifers in Kathmandu Valley,Nepal

This paper reviews, compiles and comprehensively analyzes spatial variations in hydrogeologic characteristics of shallow and deep groundwater aquifers in Kathmandu Valley. To estimate transmissivity (T) (and then hydraulic conductivity) as a function of specific capacity (SC), an empirical relationship between T and SC is developed for shallow and deep aquifer. The results show that T and SC are log linearly related by an equation T = 0.8857(SC)^1.1624 [R ² = 0.79] in shallow and T = 1.1402(SC)^1.0068 [R ² = 0.85] in deep aquifer. The estimated T ranges from 163 to 1,056 m²/day in shallow aquifer and 22.5 to 737 m²/day in deep aquifer. Finally, mapping of spatial distribution in hydrogeologic characteristics (thickness, T, hydraulic conductivity and storage coefficient) in shallow and deep aquifers are accomplished using ArcGIS9.2 and such maps would be useful in delineating potential areas for groundwater development and simulating groundwater flow in the aquifer system.     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.     

Groundwater chemistry and redox processes: Depth dependent arsenic release mechanism

Patchy occurrences of elevated As are often encountered in groundwater from the shallow aquifers (<50 m) of the Bengal Delta Plain (BDP). A clear understanding of various biogeochemical processes, responsible for As mobilization, is very important to explain this patchy occurrence and thus to mitigate the problem. The present study deals with the periodical monitoring of groundwater quality of five nested piezometeric wells between December 2008 and July 2009 to investigate the temporal changes in groundwater chemistry vis-a-vis the prevalent redox processes in the aquifer. Geochemical modeling has been carried out to identify key phases present in groundwater. A correlation study among different aqueous redox parameters has also been performed to evaluate prevailing redox processes in the aquifer. The long term monitoring of hydrochemical parameters in the multilevel wells together with hydrogeochemical equilibrium modeling has shown more subtle differences in the geochemical environment of the aquifer, which control the occurrence of high dissolved As in BDP groundwater. The groundwater is generally of Ca-HCO₃ type. The dissolved As concentration in groundwater exceeded both WHO and National drinking water standard (Bureau of Indian Standards; BIS, 10 μg L⁻¹) throughout the sampling period. The speciation of As and Fe indicate persistent reducing conditions within the aquifer [As(III): 87-97% of As_T and Fe(II): 76-96% of Fe_T]. The concentration of major aqueous solutes is relatively high in the shallow aquifer (wells A and B) and gradually decreases with increasing depth in most cases. The calculation of SI indicates that groundwater in the shallow aquifer is also relatively more saturated with carbonate minerals. This suggests that carbonate mineral dissolution is possibly influencing the groundwater chemistry and thereby controlling the mobilization of As in the monitored shallow aquifer. Hydrogeochemical investigation further suggests that Fe and/or Mn oxyhydroxide reduction is the principal process of As release in groundwater from deeper screened piezometric wells. The positive correlations of U and V with As, Fe and Mn indicate redox processes responsible for mobilization of As in the deeper screened piezometric wells are possibly microbially mediated. Thus, the study advocates that mobilization of As is depth dependent and concentrations of As in groundwater depends on single/combined release mechanisms.     

Elevated arsenic in deeper groundwater of the western Bengal basin, India: Extent and controls from regional to local scale

The deeper groundwater (depending on definition) of the Bengal basin (Ganges-Brahmaputra delta) has long been considered as an alternate, safe drinking-water source in areas with As-enrichment in near-surface groundwater. The present study provides the first collective discussion on extent and controls of elevated As in deeper groundwater of a regional study area in the western part of the Bengal basin. Deeper groundwater is defined here as non-brackish, potable (Cl⁻ ? 250 mg/L) groundwater available at the maximum accessed depth (∼80-300 m). The extent of elevated As in deeper groundwater in the study area seems to be largely controlled by the aquifer-aquitard framework. Arsenic-enriched deeper groundwater is mostly encountered north of 22.75°N latitude, where an unconfined to semi-confined aquifer consisting of Holocene- to early Neogene-age gray sand dominates the hydrostratigraphy to 300 m depth below land surface. Aquifer sediments are not abnormally enriched in As at any depth, but sediment and water chemistry are conducive to As mobilization in both shallow and deeper parts of the aquifer(s). The biogeochemical triggers are influenced by complex redox disequilibria. Results of numerical modeling and profiles of environmental tracers at a local-scale study site suggest that deeper groundwater abstraction can draw As-enriched water to 150 m depth within a few decades, synchronous with the advent of wide-scale irrigational pumping in West Bengal (India).     

Hydrogeochemical contrast between two study areas of Bengal delta,India: A comparative insight to understand arsenic mobilization process in shallow aquifers

A comparative hydrogeochemical study evaluated arsenic release mechanism and differences in contamination levels in the shallow groundwater of two areas within the deltaic environment of West Bengal (i.e. Karimpur and Tehatta blocks of Nadia district) in India. Groundwaters from both the areas are Ca-Na(K)-Cl-HCO₃ type with highly reducing character (−110.16 ± 16.85 to −60.77 ± 16.93 mV). Low correlations among As, Fe, and Mn and the higher association between As and DOC are indicative of microbial decomposition of organic matter enhancing the weathering of shallow aquifer materials. Arsenic contamination in groundwater is higher in Karimpur (95 ± 81.17 μg/L) than that in Tehatta (43.05 ± 41.06 μg/L). The release mechanism of arsenic into groundwater is very complex. Low Fe (0.27–4.78 mg/L and 0.81–4.13 mg/L), Mn (0.08–0.2 mg/L and 0.03–0.22 mg/L), and SO₄²⁻ (3.82 ± 0.31 and 2.78 ± 0.40 mg/L) suggest that the mechanism of arsenic release is not a single mechanistic pathway. Clustering of redox-active parameters in the principal component planes indicate that the reductive dissolution, and/or weathering/co-precipitation of Fe/Mn-bearing minerals in the shallow aquifer sediments control the dominant mechanistic pathway of arsenic release.     

Characterisation of organic matter and microbial communities in contrasting arsenic-rich Holocene and arsenic-poor Pleistocene aquifers,Red River Delta,Vietnam

High concentrations of geogenic As in the groundwaters of south and SE Asia, which are used as drinking waters, are causing severe health impacts to the exposed human populations. It is widely accepted that As mobilisation from sediments into these shallow reducing groundwaters requires active metal-reducing microbes and electron donors such as organic matter (OM). Although OM in such Holocene aquifers has been characterised, there is a dearth of data on Pleistocene aquifers from the same areas. Reported here are preliminary studies of OM and microbial communities present in two aquifers, one of Pleistocene and one of Holocene age, with contrasting concentrations of As (viz. Pleistocene: low As <10 μg/L; Holocene: high As up to 600 μg/L) from Van Phuc village in the Red River Delta, Vietnam. Results revealed OM inputs from multiple sources, including potential contributions from naturally occurring petroleum seeping into the shallow aquifer sediments from deeper thermally mature source rocks. Although concentrations vary, no noticeable systematic differences in biomarker distribution patterns within the OM were observed between the two sites. Microbial analyses did not show a presence of microbial communities previously associated with As mobilisation. All clone libraries were dominated by α-, β-, and γ-Proteobacteria not known to be able to reduce Fe(III) or sorbed As(V). Furthermore, representatives of the Fe(III)-reducing genus Geobacter could only be detected at very low abundance by PCR, using highly selective 16S rRNA gene primers, supporting the hypothesis that metal reduction is not a dominant in situ process in these sediments. No correlation between As concentration in groundwater and OM composition nor microbial community in the host sediments was found. This suggests that either (i) As is not being significantly mobilised in situ in these sediments, instead As appears to be mobilised elsewhere and transported by groundwater flow to the sites or (ii) sorption/desorption processes, as implicated by geochemical data from the cores, play a critical role in controlling As concentrations at these sites.     

Cation exchange processes and human activities in unconfined aquifers

During the 1999–2002 water years, a hydrogeological research project was carried out on the unconfined aquifer of Trifilia in the Peloponnese. Seawater intrusion due to overpumping, and intensive use of fertilizers caused the groundwater quality degradation that is a typical case for the coastal aquifers in Greece. Isopiezometric maps along with ion distribution balances, ion distribution maps and factor analysis indicate the existence of three zones of groundwater quality. In the first zone of saline water, a cation exchange process between the Ca²⁺ of sediments and the Na⁺ of groundwater contribute to the formation of the water type Na⁺-Ca²⁺-Cl^–. In the second zone, which is considered as a transition zone, dominate the Ca²⁺-Na⁺-HCO₃^–-Cl^– water type. In the third zone of Ca²⁺-HCO₃^–-SO₄^2– water type, relationships among Ca²⁺, SO₄^2–, NO₃^– and NH₄ can be attributed to the dissociation of ammonium nitrate and sulfate fertilizers on one hand, and Ca²⁺ derivation from cation exchange processes between water, rocks and clay minerals, such as smectite and illite, on the other.     

Hydrogeochemical and multi-tracer investigations of arsenic-affected aquifers in semi-arid West Africa

The semi-arid Sahel regions of West Africa rely heavily on groundwater from shallow to moderately deep(100 m b.g.l.)crystalline bedrock aquifers for drinking water production.Groundwater quality may be affected by high geogenic arsenic(As)concentrations(10μg/L)stemming from the oxidation of sulphide minerals(pyrite,arsenopyrite)in mineralised zones.These aquifers are still little investigated,especially concerning groundwater residence times and the influence of the annual monsoon season on groundwater chemistry.To gain insights on the temporal aspects of As contamination,we have used isotope tracers(noble gases,~3H,stable water isotopes(~2 H,~(18)O))and performed hydrochemical analyses on groundwater abstracted from tube wells and dug wells in a small study area in southwestern Burkina Faso.Results revealed a great variability in groundwater properties(e.g.redox conditions,As concentrations,water level,residence time)over spatial scales of only a few hundred metres,characteristic of the highly heterogeneous fractured underground.Elevated As levels are found in oxic groundwater of circum-neutral pH and show little relation with any of the measured parameters.Arsenic concentrations are relatively stable over the course of the year,with little effect seen by the monsoon.Groundwater residence time does not seem to have an influence on As concentrations,as elevated As can be found both in groundwater with short(50 a)and long(10~3 a)residence times as indicated by ~3He/~4He ratios spanning three orders of magnitude.These results support the hypothesis that the proximity to mineralised zones is the most crucial factor controlling As concentrations in the observed redox/pH conditions.The existence of very old water portions with residence times10~3 years already at depths of50 m b.g.l.is a new finding for the shallow fractured bedrock aquifers of Burkina Faso,suggesting that overexploitation of these relatively low-yielding aquifers may be an issue in the future.     

Geochemistry and mineralogy of shallow alluvial aquifers in Daudkandi upazila in the Meghna flood plain, Bangladesh

The shallow alluvial aquifers of the delta plains and flood plains of Bangladesh, comprises about 70% of total land area are mostly affected by elevated concentrations of arsenic (As) in groundwater exposing a population of more than 35 million to As toxicity. Geochemical studies of shallow alluvial aquifer in the Meghna flood plain show that the uppermost yellowish grey sediment is low in As (1.03 mg/kg) compared to the lower dark grey to black sediment (5.24 mg/kg) rich in mica and organic matter. Sequential extraction data show that solid phase As bound to poorly crystalline and amorphous metal (Fe, Mn, Al)-oxyhydroxides is dominant in the grey to dark grey sediment and reaches its maximum level (3.05 mg/kg) in the mica rich layers. Amount of As bound to sulphides and organic matter also peaks in the dark grey to black sediment. Vertical distributions of major elements determined by X-ray fluorescence (XRF) show that iron (Fe₂O₃), aluminum (Al₂O₃) and manganese (MnO) follow the general trend of distribution of As in the sediments. Concentrations of As, Mn, Fe, HCO₃ ⁻, SO₄ ²⁻ and NO₃ ⁻ in groundwater reflect the redox status of the aquifer and are consistent with solid phase geochemistry. Mineralogical analysis by X-ray diffraction (XRD) and scanning electron microscopy (SEM) fitted with energy dispersive X-ray spectrometer (EDS) revealed dominance of crystalline iron oxides and hydroxides like magnetite, hematite and goethite in the oxidised yellowish grey sediment. Amorphous Fe-oxyhydroxides identified as grain coating in the mica and organic matter rich sediment suggests weathering of biotite is playing a critical role as the source of Fe(III)-oxyhydroxides which in turn act as sink for As. Presence of authigenic pyrite in the dark grey sediment indicates active reduction in the aquifer.     

Hydrogeochemistry and groundwater quality assessment of the multilayered aquifer in Lower Kelantan Basin,Kelantan, Malaysia

Continual expansion of population density, urbanization, agriculture, and industry in most parts of the world has increased the generation of pollution, which contributes to the deterioration of surface water quality. This causes the dependence on groundwater sources for their daily needs to accumulate day by day, which raises concerns about their quality and hydrogeochemistry. This study was carried out to increase understanding of the geological setup and assess the groundwater hydrogeochemical characteristics of the multilayered aquifers in Lower Kelantan Basin. Based on lithological data correlation of exploration wells, the study area can be divided into three main aquifers: shallow, intermediate and deep aquifers. From these three aquifers, 101 groundwater samples were collected and analyzed for various parameters. The results showed that pH values in the shallow, intermediate and deep aquifers were generally acidic to slightly alkaline. The sequences of major cations and anions were Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and HCO₃^? > Cl^? > SO₄^2? > CO₃^2?, respectively. In the intermediate aquifer, the influence of ancient seawater was the primary factor that contributed to the elevated values of electrical conductivity (EC), Cl^? and total dissolved solids (TDS). The main facies in the shallow aquifer were Ca–HCO₃ and Na–HCO₃ water types. The water types were dominated by Na–Cl and Na–HCO₃ in the intermediate aquifer and by Na–HCO₃ in the deep aquifer. The Gibbs diagram reveals that the majority of groundwater samples belonged to the deep aquifer and fell in the rock dominance zone. Shallow aquifer samples mostly fell in the rainfall zone, suggesting that this aquifer is affected by anthropogenic activities. In contrast, the results suggest that the deep aquifer is heavily influenced by natural processes.     

Deciphering interaction of regional aquifers in Southern Tunisia using hydrochemistry and isotopic tools

Groundwater is the most important source of water supply in southern Tunisia. Previous hydrogeologic and isotopic studies carried out in this region revealed the existence of two major aquifer systems: the “Complex Terminal” (CT) and the “Continental Intercalaire” (CI). Turonian carbonates constitute one of the major aquifer levels of the CT multilayered aquifer. It extends over most of southern Tunisia, and its hydrodynamic regime is largely influenced by tectonics, lithology and recharge conditions. Forty-eight groundwater samples from the CI and Turonian aquifers were collected between January and April 2004 for chemical and isotopic analyses. Hydrochemistry and isotopic tools were combined to get an insight into the processes controlling chemical composition of groundwater and wide-scale interaction of these two aquifer systems. Analysis of the dissolved constituents revealed that several processes control the observed chemical composition: (i) incongruent dissolution of carbonate minerals, (ii) dissolution of evaporitic minerals, and (iii) cation exchange. Dissolution alone cannot account for the observed high supersaturation states of groundwater with respect to calcite and dolomite. The observed supersaturation is most probably linked to geogenic CO₂ entering water-bearing horizons of the CT and CI aquifers via deep tectonic faults and discontinuities and subsequent degassing in the exploitation wells. Presence of geogenic CO₂ in the investigated region was confirmed by C isotope data of the DIC reservoir. The radiocarbon content of the Turonian samples varied between 9.5 and 43 pmc. For CI samples generally lower values were recorded, between 3.8 and 22.5 pmc. Stable isotope composition of Turonian groundwater samples varied from −8.3 to −5.3‰ for δ¹⁸O and from −60 to −25‰ for δ²H. The corresponding ranges of δ values for the Continental Intercalaire samples were from −8.9‰ to −6.9‰ for δ¹⁸O and from −68.2‰ to −45.7‰ for δ²H. Stable isotope composition of groundwater representing CT and CI aquifers provide strong evidence for regional interaction between both systems.     

Hydrochemical characterization,mechanism of mobilization,and natural background level evaluation of arsenic in the aquifers of upper Gangetic plain,India

Although arsenic (As) contamination has been extensively investigated in the aquifers of the lower and middle Gangetic plains, less attention has been given to the distribution and fate of As in the groundwater of the upper Gangetic plain, India. In the current study, groundwater samples (n = 40) were collected from Moradabad district in the upper Gangetic plain and analyzed for several physicochemical parameters to characterize the groundwater chemistry and evaluate various geogenic and anthropogenic factors controlling the occurrence, mobilization, and fate of As in the plain. Arsenic concentrations in groundwater ranged from 0.17 μg/L to 139 μg/L, with the majority of high-As groundwater associated with high Fe, Mn, and HCO₃⁻ and low NO₃⁻, SO₄²⁻, and negative Eh values, implying that As was released via reductive dissolution of Fe and Mn oxyhydroxides in reducing conditions under the influence of organic matter degradation. Interrelationships between various geochemical variables and the natural background level (NBL) quantification of As suggested the influence of anthropogenic processes on the mobility of As in groundwater. Piper and Gibbs diagrams and various bivariate plots revealed that the majority of groundwater was of the Ca²⁺ − Mg²⁺ − HCO₃⁻ type and that the major ions in groundwater were derived from carbonate and silicate weathering, cation exchange and reverse ion exchange processes, and anthropogenic activities. Moreover, the results of principal component analysis (PCA), and hierarchical cluster analysis (HCA) also suggested geogenic and anthropogenic sources for the ion concentration in groundwater. The health risk assessment showed a higher non-carcinogenic risk for children and a higher carcinogenic risk for adults, respectively, due to the daily intake of As contaminated groundwater. Overall, this study represents the first systematic investigation of the distribution, geochemical behavior, and release process of As in groundwater in the study area and provides a strong base for future research in the alluvial aquifers of the upper Gangetic plain.     

Hydrochemistry and isotopic studies to identify Ganges River and riverbank groundwater interaction, southern Bangladesh

The Ganges River water and riverbank shallow groundwater were studied during a single wet season using the hydrochemical and isotopic composition of its dissolved load. The dissolved concentrations of major ions (Cl^?, SO₄ ^2?, NO₃ ^?, HCO₃ ^?, Ca²⁺, Na⁺, Mg²⁺, and K⁺), trace elements (barium (Ba) and strontium (Sr)) and stable isotopes (O and D) were determined on samples collected from the Ganges River and its riverbank shallow aquifers. In the present study, the shallow groundwater differs significantly from the Ganges River water; it shows distinct high concentrations of Ca²⁺, Mg²⁺, HCO₃ ^?, Ba, and Sr due to water–rock interaction and this in particular suggests that the Ganges River may not contribute significantly to the riverbank shallow aquifers during wet season. Besides, the sum of the total cationic charge (∑⁺, in milliequivalents per liter) in the groundwater shows high values (2.48 to 13.91 meq/L, average 9.12 meq/L), which is much higher than the sum of the cations observed in the Ganges water (1.36 to 3.10 meq/L, average 1.94 meq/L). Finally, the more depleted stable isotopic (δ ¹⁸O and δ ²H) compositions of the Ganges River water are in contrast to those of the riverbank aquifer having enriched stable isotopic values during the wet season and the riverbank groundwater thus has a purely local origin from precipitation.