Holocene Aquifer Research Articles

Chlorite^|^mdash;source of arsenic groundwater pollution in the Holocene aquifer of Bangladesh

Chlorite^|^mdash;source of arsenic groundwater pollution in the Holocene aquifer of Bangladesh

Groundwater Dynamics of Fongafale Islet, Funafuti Atoll, Tuvalu

Geoelectric and hydrologic surveys during spring tides revealed the spatiotemporal distribution of groundwater quality produced by tidal forcing in Fongafale Islet, Funafuti Atoll, Tuvalu. The observed low resistivity showed that saline water largely immersed the surficial Holocene aquifer, indicating that there is no thick freshwater lens in Fongafale Islet, unlike in other atoll islands of comparable size. Half of the islet was constructed by reclaiming the original swamp with porous, highly permeable coral blocks; this reclaimed area should not be considered as part of the islet width for calculation of the expected thickness of the freshwater lens. The degree of aquifer salinization depends on the topographic characteristics and the hydrologic controls on the inland propagation of the tidal forcing. Large changes in bulk resistivity and the electrical conductivity of groundwater from wells indicate that periodic salinization in phase with the semidiurnal tides was occurring widely, especially in areas at lower elevation than the high-tide level and in reclaimed areas with high permeability. Thin sheets of nearly fresh and brackish water were observed in the surficial aquifer in areas above the high-tide level and in taro swamps, respectively. The thinness of the brackish and freshwater sheets suggests that the taro swamps and the fresh groundwater resources of the islet are highly vulnerable to salinization from anticipated sea-level rise. An understanding of the inherent geologic and topographic features of an atoll is necessary to evaluate the groundwater resources of the atoll and assess the vulnerability of its water resources to climate change.

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.

Effect of groundwater flow on forming arsenic contaminated groundwater in Sonargaon, Bangladesh

Summary Three-dimensional groundwater flow in Sonargaon, Bangladesh is numerically simulated in order to evaluate the flow paths of As-contaminated drinking groundwater in the Holocene aquifer of the Ganges–Blamaptra–Meghna delta plain over a recent 30-year period. The model indicates that vertical infiltration of surface groundwater into the shallow Holocene aquifer occurs frequently in the Ganges–Blamaptra–Meghna delta plain. It predicts that the water recharged from ground surface moves approximately 10–20 m vertically downward beneath the flood plain, with a gradually increasing horizontal flow, toward the underlying Pleistocene middle mud layer (aquitard). The model also predicts that groundwaters containing highest As concentrations (>700 μg/L) are formed on the vertical groundwater flow paths where surface water recharges the Holocene aquifer and not on the horizontal flow paths. Combining with the groundwater chemistry, reducing groundwater condition is not essential for the As-contaminated groundwater of the studied area in the Ganges delta plain.

Arsenic pollution of groundwater in Vietnam exacerbated by deep aquifer exploitation for more than a century

Arsenic contamination of shallow groundwater is among the biggest health threats in the developing world. Targeting uncontaminated deep aquifers is a popular mitigation option although its long-term impact remains unknown. Here we present the alarming results of a large-scale groundwater survey covering the entire Red River Delta and a unique probability model based on three-dimensional Quaternary geology. Our unprecedented dataset reveals that ∼7 million delta inhabitants use groundwater contaminated with toxic elements, including manganese, selenium, and barium. Depth-resolved probabilities and arsenic concentrations indicate drawdown of arsenic-enriched waters from Holocene aquifers to naturally uncontaminated Pleistocene aquifers as a result of > 100 years of groundwater abstraction. Vertical arsenic migration induced by large-scale pumping from deep aquifers has been discussed to occur elsewhere, but has never been shown to occur at the scale seen here. The present situation in the Red River Delta is a warning for other As-affected regions where groundwater is extensively pumped from uncontaminated aquifers underlying high arsenic aquifers or zones.

Redox trapping of arsenic during groundwater discharge in sediments from the Meghna riverbank in Bangladesh.

Groundwater arsenic (As) is elevated in the shallow Holocene aquifers of Bangladesh. In the dry season, the shallow groundwater discharges to major rivers. This process may influence the chemistry of the river and the hyporheic zone sediment. To assess the fate of As during discharge, surface (0-5 cm) and subsurface (1-3 m) sediment samples were collected at 9 sites from the bank of the Meghna River along a transect from its northern source (25 degrees N) to the Bay of Bengal (22.5 degrees N). Bulk As concentrations of surface sediment averaged 16 +/- 7 mg/kg (n = 9). Subsurface sediment contained higher mean concentrations of As of 4,000 mg/kg (n = 14), ranging from 1 to 23,000 mg/kg As, with >100 mg/kg As measured at 8 sites. X-ray absorption near-edge structure spectroscopy indicated that As was mainly arsenate and arsenite, not As-bearing sulfides. We hypothesize that the elevated sediment As concentrations form as As-rich groundwater discharges to the river, and enters a more oxidizing environment. A significant portion of dissolved As sorbs to iron-bearing minerals, which form a natural reactive barrier. Recycling of this sediment-bound As to the Ganges-Brahmaputra-Meghna Delta aquifer provides a potential source of As to further contaminate groundwater. Furthermore, chemical fluxes from groundwater discharge from the Ganges-Brahmaputra-Meghna Delta may be less than previous estimates because this barrier can immobilize many elements.

Variations in the redox state of As and Fe measured by X-ray absorption spectroscopy in aquifers of Bangladesh and their effect on As adsorption

Groundwater enrichment with naturally occurring As is a very serious problem. In Bangladesh, many thousands of people are drinking such groundwater. Household well waters generally show a large variation of concentration of As even within a small village. This variation creates difficulty in the design of mitigation strategies. It was hypothesized that the concentration of As in each well is controlled by an adsorption–desorption equilibrium between sediment and groundwater. To verify the hypothesis, two factors are focused upon in this study: (i) speciation of As and Fe in the solid phase, and (ii) the adsorption properties of As(III) and As(V) to sediment. By this approach, it is possible to understand the variation of aqueous As in groundwater. Sediment core samples were collected from an As-enriched aquifer at Sonargaon, central eastern Bangladesh. The oxidation states of As and Fe in the sediments determined by X-ray absorption near edge structure (XANES) showed a distinct redox boundary below 5 m from the ground surface, whereas the peak of the concentration of dissolved As is observed below 15 m. The apparent distribution coefficient (Kd = Csolid/Csolution) of As(V) is always larger than that of As(III) at all the depths. Simulated concentrations of As in the groundwater obtained by multiplying the amount of P-extracted As and Kd-1 with consideration of the oxidation state of As is consistent with the depth profile of As in the groundwater. This suggests that the concentration of dissolved As is controlled by an adsorption–desorption equilibrium between sediment and groundwater. Variation in Kd is primarily controlled by the concentration of Fe oxyhydroxides, whereas surface area is also important for As(III). The discrepancy between the depth of the redox boundary and the peak of dissolved As is attributed to the difference in the abundance of P-extracted As rather than to a variation of Kd. The adsorption equilibrium model proposed in this study can be applied to the evaluation of the large variation in aqueous As concentration in groundwater from Holocene aquifers.

Geological controls on groundwater chemistry and arsenic mobilization: Hydrogeochemical study along an E–W transect in the Meghna basin, Bangladesh

Summary Hydrogeochemical investigations along an E–W transect in the middle Meghna basin show groundwater chemistry and redox condition vary considerably with the change in geology. Groundwater in the Holocene shallow ( 10 μg/l) and salinity. On the other hand, groundwater from the Pliocene Dupi Tila sandy aquifer in the eastern part is fresh and low in As ( HCO 3 - , Fe and dissolved organic carbon (DOC), but generally low in SO 4 2 - and NO 3 - . High HCO 3 - concentrations (250–716 mg/l) together with high DOC concentrations (1.4–21.7 mg/l) in these aquifers reflect active sources of degradable natural organic matter that drives the biogeochemical process. There is generally de-coupling of As from other redox-sensitive elements. In contrast, the Pliocene aquifers are low in As, HCO 3 - and DOC. Molar ratio of HCO 3 - /H4SiO4 suggests that silicate weathering is dominant in the deeper Holocene aquifers and in the Pliocene aquifers. Molar ratios of Cl−/ HCO 3 - and Na+/Cl− suggest mixing of relict seawater with the fresh water as the origin of groundwater salinity. Speciation calculations show that saturation indices for siderite and rhodochrosite vary significantly between the Holocene and Pliocene aquifers. Stable isotopes (δ2H and δ18O) in groundwater indicate rapid infiltration without significant effects of evaporation. The isotopic data also indicates groundwater recharge from monsoonal precipitation with some impact of altitude effect at the base of the Tripura Hills in the east. The results of the study clearly indicate geological control (i.e. change in lithofacies) on groundwater chemistry and distribution of redox-sensitive elements such as As along the transect.

Numerical Modeling of Atoll Island Hydrogeology

We implemented Ayers and Vachers' (1986) inclusive conceptual model for atoll island aquifers in a comprehensive numerical modeling study to evaluate the response of the fresh water lens to selected controlling climatic and geologic variables. Climatic factors include both constant and time-varying recharge rates, with particular attention paid to the effects of El Niño and the associated drought it brings to the western Pacific. Geologic factors include island width; hydraulic conductivity of the uppermost Holocene-age aquifer, which contains the fresh water lens; the depth to the contact with the underlying, and much more conductive, Pleistocene karst aquifer, which transmits tidal signals to the base of the lens; and the presence or absence of a semiconfining reef flat plate on the ocean side. Sensitivity analyses of steady-steady simulations show that lens thickness is most strongly sensitive to the depth to the Holocene-Pleistocene contact and to the hydraulic conductivity of the Holocene aquifer, respectively. Comparisons between modeling results and published observations of atoll island lens thicknesses suggest a hydraulic conductivity of approximately 50 m/d for leeward islands and approximately 400 m/d for windward islands. Results of transient simulations show that lens thickness fluctuations during average seasonal conditions and El Niño events are quite sensitive to island width, recharge rate, and hydraulic conductivity of the Holocene aquifer. In general, the depletion of the lens during drought conditions is most drastic for small, windward islands. Simulation results suggest that recovery from a 6-month drought requires about 1.5 years.

Characterization of geochemical constituents and bacterial populations associated with As mobilization in deep and shallow tube wells in Bangladesh

While millions of people drink arsenic-contaminated tube well water across Bangladesh, there is no recent scientific explanation which is able to either comprehensively explain arsenic mobilization or to predict the spatial distribution of affected wells. Rather, mitigation strategies have focused on the sinking of deep tube wells into the currently arsenic-free Pleistocene aquifer. In this study, Bangladesh shallow tube wells identified as contaminated and uncontaminated, as well as deep tube wells, were analyzed for geochemical and in situ microbiological composition. Whereas arsenic was detected in all Holocene aquifer wells, no arsenic was found in wells accessing the Pleistocene aquifer. Bacterial genera, including Comamonadaceae, Acidovorax, Acinetobacter, and Hydrogenophaga, associated with tolerance of high arsenic concentrations, rather than dissimilatory Fe(III) or As(V) reduction, were identified in shallow tube wells, indicating that mobilization may not occur at depth, but is rather due to drawdown of surface contaminated water. Deep tube wells contained microbes indicative of aerobic conditions, including the genera Aquabacterium, Limnobacter, and Roseomonas. It is concluded that through drawdown of arsenic or organic matter, further utilization of the Pleistocene aquifer could result in contamination similar to that observed in the Holocene aquifer.

Integrated biogeochemical and hydrologic processes driving arsenic release from shallow sediments to groundwaters of the Mekong delta

Abstract Arsenic is contaminating the groundwater of Holocene aquifers throughout South and Southeast Asia. To examine the biogeochemical and hydrological processes influencing dissolved concentrations and transport of As within soils/sediments in the Mekong River delta, a ∼50 km2 field site was established near Phnom Penh, Cambodia, where aqueous As concentrations are dangerously high and where groundwater retrieval for irrigation is minimal. Dissolved As concentrations vary spatially, ranging up to 1300 μg/L in aquifer groundwater and up to 600 μg/L in surficial clay pore water. Groundwaters with high As concentrations are reducing with negligible dissolved O2 and high concentrations of Fe(II), NH 4 + , and dissolved organic C. Within near-surface environments, these conditions are most pronounced in sediments underlying permanent wetlands, often found within oxbow channels near the Mekong River. There, labile C, co-deposited with As-bearing Fe (hydr)oxides under reducing conditions, drives the reductive mobilization (inclusive of Fe and As reduction) of As. Here, conditions are described under which As is mobilized from these sediments, and near-surface As release is linked to aquifer contamination over long time periods (100s to 1000s of years). Site biogeochemistry is coupled with extensive hydrologic measurements, and, accordingly, a comprehensive interpretation of spatial As release and transport within a calibrated hydraulic flow-field is provided of an As-contaminated aquifer that is representative of those found throughout South and Southeast Asia.

Arsenic mobilisation in a new well field for drinking water production along the Red River, Nam Du, Hanoi

Arsenic enrichment of groundwater in the Red River (Song Hong) delta in Vietnam was discovered in 1998. Several studies performed in this area found concentrations of As exceeding the WHO-guideline of 10 μg/L. This study focuses on an area south of Hanoi city, Nam Du, where a new well field came into operation in 2004. The new well field is situated on the bank along the Red River in order to facilitate induced infiltration. The Nam Du area receives surface water with a high load of nutrients and organic matter from the Hanoi sewage system, and is subject to recently increased groundwater extraction from the Pleistocene aquifer system. The objective of the study was (1) to assess the situation in the Nam Du area by mapping the distribution of As, (2) to identify possible sources of As in the groundwater and (3) to investigate the mobilisation processes releasing As into the groundwater. Two main field campaigns were carried out, in 2006 and 2007, both during the dry season. Groundwater and surface water levels were measured and water- and sediment samples were collected. The water in the Pleistocene aquifer shows the same water-level variations as the Red River at a distance of 2.5 km from the riverbank, while the Holocene aquifer heads are recharged by surface water ponds and show less seasonal variation. The concentration of As in the groundwater in Nam Du exceeded the WHO provisional guideline value at all sampled locations. The main conclusions are summarised as (i) the distribution of As is highly variable but the zones with the highest concentrations of As are near the Red River in the Holocene aquifer and just down gradient from this in the Pleistocene aquifer, (ii) the sediments within the aquifers are considered to be the source of the As, where the Holocene aquifer is believed to act as the main source of As into the Pleistocene aquifer as reduced groundwater containing As from the Holocene aquifer is flowing downwards due to the downward gradient, and (iii) two different processes appear to take part in the mobilisation process. In the Holocene aquifer, reductive dissolution of FeOOH and the release of adsorbed As appear to be the main mobilisation processes. In the Pleistocene, however, mobilisation of adsorbed As due to competition from HCO3- ions for surface sites on FeOOH may be a major mechanism of As mobilisation. It is suggested that the drinking water supplier undertakes the following actions to ensure acceptable levels of As in the treated drinking water: (a) to implement a long-term monitoring program, (b) implement alternative treatment technologies; and (c) to possibly consider an alternative drinking water source.

Hydrological and geochemical constraints on the mechanism of formation of arsenic contaminated groundwater in Sonargaon, Bangladesh

Abstract The geochemical characteristics and hydrological constraints of high As groundwater in Sonargaon, in mid-eastern Bangladesh were investigated in order to ascertain the mechanism of As release into the groundwaters from host sediments in the Ganges–Brahmaputra delta. Samples of groundwater were collected from ca. 230 tube wells in both the rainy and dry seasons. Similar to previous studies, high As groundwater was found in the Holocene unconfined aquifer but not in the Pleistocene aquifer. Groundwaters in the Holocene aquifer were of the Ca–Mg–HCO3 type with major solutes derived from chemical weathering of detrital minerals such as plagioclase and biotite. Groundwater with high As was generally characterized by high NH 4 + , possibly derived from the agricultural application of fertilizer as suggested by the small variation of δ 15 N NH 4 (mostly 2–4‰). Concentrations of Fe changed between the rainy and dry seasons by precipitation/dissolution of Fe oxyhydroxide and siderite, whilst there was not an apparent concomitant change in As. Inhomogeneous spatial distribution of δ18O in the Holocene unconfined aquifer indicates poor mixing of groundwater in the horizontal direction. Spatial variation of redox conditions is associated with localized variations in subsurface permeability and the recharge/discharge cycle of groundwater. Hydrogeochemical data presented in this paper suggest that reduction of Fe oxyhydroxide is not the only mechanism of As mobilization, and chemical weathering of biotite and/or other basic minerals in the Holocene aquifer could also be important as a primary cause of As mobilization.

Controlling geological and hydrogeological processes in an arsenic contaminated aquifer on the Red River flood plain, Vietnam

Geological and hydrogeological processes controlling recharge and the mobilization of As were investigated in a shallow Holocene aquifer on the Red River flood plain near Hanoi, Vietnam. The geology was investigated using surface resistivity methods, geophysical borehole logging, drilling of boreholes and installation of more than 200 piezometers. Recharge processes and surface–groundwater interaction were studied using (i) time-series of hydraulic head distribution in surface water and aquifers, (ii) the stable isotope composition of waters and (iii) numerical groundwater modeling. The Red River and two of its distributaries run through the field site and control the groundwater flow pattern. For most of the year, there is a regional groundwater flow towards the Red River. During the monsoon the Red River water stage rises up to 6 m and stalls the regional groundwater flow. The two distributaries recharge the aquifer from perched water tables in the dry season, whilst in the flooding period surface water enters the aquifer through highly permeable bank sediments. The result is a dynamic groundwater flow pattern with rapid fluctuations in the groundwater table. A transient numerical model of the groundwater flow yields an average recharge rate of 60–100 mm/a through the confining clay, and a total recharge of approximately 200 mm/a was estimated from 3H/3He dating of the shallow groundwater. Thus in the model area, recharge of surface water from the river distributaries and recharge through a confining clay is of the same magnitude, being on average around 100 mm/a. The thickness of the confining clay varies between 2 and 10 m, and affects the recharge rate and the transport of electron acceptors (O2, NO3- and SO42-) into the aquifer. Where the clay layer is thin, an up to 2 m thick oxic zone develops in the shallow aquifer. In the oxic zone the As concentration is less than 1 μg/L but increases in the reduced zone below to 550 μg/L. In the Holocene aquifer, As is mobilized at a rate of around 14 μg/L/a. An As mass balance for the field site shows that around 1100 kg of As is annually leached from the Holocene sand and discharged into the Red River, corresponding to 0.01% of the total pool of As now present in the Holocene sand.

Palaeo-hydrogeological control on groundwater As levels in Red River delta, Vietnam

To study the geological control on groundwater As concentrations in Red River delta, depth-specific groundwater sampling and geophysical logging in 11 monitoring wells was conducted along a 45 km transect across the southern and central part of the delta, and the literature on the Red River delta's Quaternary geological development was reviewed. The water samples (n=30) were analyzed for As, major ions, Fe 2+ , H 2 S, NH 4 , CH 4 , δ 18 Ο and 8D, and the geophysical log suite included natural gamma-ray, formation and fluid electrical conductivity. The SW part of the transect intersects deposits of grey estuarine clays and deltaic sands in a 15-20 km wide and 50-60m deep Holocene incised valley. The NE part of the transect consists of 60-120 m of Pleistocene yellowish alluvial deposits underneath 10-30m of estuarine clay overlain by a 10-20m veneer of Holocene sediments. The distribution of δ 18 O-values (range -12.2‰ to -6.3%o) and hydraulic head in the sample wells indicate that the estuarine clay units divide the flow system into an upper Holocene aquifer and a lower Pleistocene aquifer. The groundwater samples were all anoxic, and contained Fe 2+ (0.03-2.0mM), Mn (0.7-320μM), SO 4 (<2.1μM-0.75mM), H 2 S (<0.1-7.0μM), NH 4 (0.03-4.4 mM), and CH 4 (0.08-14.5 mM). Generally, higher concentrations of NH 4 and CH 4 and low concentrations of SO 4 were found in the SW part of the transect, dominated by Holocene deposits, while the opposite was the case for the NE part of the transect. The distribution of the groundwater As concentration (<0.013-11.7 μM; median 0.12 μM (9μg/L)) is related to the distribution of NH 4 , CH 4 and SO 4 . Low concentrations of As (≤0.32μM) were found in the Pleistocene aquifer, while the highest As concentrations were found in the Holocene aquifer. PHRE-EQC-2 speciation calculations indicated that Fe 2+ and H 2 S concentrations are controlled by equilibrium for disordered mackinawite and precipitation of siderite. An elevated groundwater salinity (Cl range 0.19-65.1 mM) was observed in both aquifers, and dominated in the deep aquifer. A negative correlation between aqueous As and an estimate of reduced SO 4 was observed, indicating that Fe sulphide precipitation poses a secondary control on the groundwater As concentration.

Arsenic release from biotite into a Holocene groundwater aquifer in Bangladesh

Abstract Continuous core sediments (to a depth of 90.1 m) taken at a transitional area of Holocene and Pleistocene deposits in Sonargaon, Bangladesh were characterized for their mineralogy and chemistry. Among the sediments of the lower part of the Holocene aquifer (depth: 18–29 m), where most domestic wells are installed, As is mostly fixed in biotite and organic phases. A positive correlation of As concentration with those of Al and Fe but not that of total organic C clearly suggests that biotite is a primary source of As. Although microbial reduction–dissolution of As-containing Fe oxyhydroxides is thought to cause As-enriched groundwater in the Ganges–Brahmaputra–Meghna delta plain, the authors conclude that chemical weathering of biotite is the primary formation mechanism and prevailing reducing conditions contribute to the expansion of As-enriched groundwater in the study area.

Hydrological and sedimentary controls leading to arsenic contamination of groundwater in the Hanoi area, Vietnam: The impact of iron-arsenic ratios, peat, river bank deposits, and excessive groundwater abstraction

Groundwater contamination by arsenic in Vietnam poses a serious health threat to millions of people. In the larger Hanoi area, elevated arsenic levels are present in both, the Holocene and Pleistocene aquifers. Family-based tubewells predominantly tap the Holocene aquifer, while the Hanoi water works extract more than 600,000 m 3/day of groundwater from the Pleistocene aquifer. Detailed groundwater and sediment investigations were conducted at three locations exhibiting distinct geochemical conditions, i.e., i) high levels of dissolved arsenic (av. 121 µg/L) at the river bank, ii) low levels of dissolved arsenic (av. 21 µg/L) at the river bank and, iii) medium levels of dissolved arsenic (60 µg/L) in an area of buried peat and excessive groundwater abstraction. Seasonal fluctuations in water chemistry were studied over a time span of 14 months. Sediment-bound arsenic (1.3–22 µg/g) is in a natural range. Arsenic correlates with iron ( r 2 > 0.8) with variation related to grain size. Sediment leaching experiments showed that arsenic can readily be mobilized at each of the three locations. Low levels of arsenic in groundwater (< 10 µg/L) generally exhibit manganese reducing conditions, whereas elevated levels are caused by reductive dissolution under iron- and sulphate reducing conditions. Average arsenic concentrations in groundwater are twofold higher at the river bank than in the peat area. The lower levels of arsenic contamination in the peat area are likely controlled by the high abundance of iron present in both the aqueous and sediment phases. With median molar Fe/As ratios of 350 in water and 8700 in the sediments of the peat area, reduced iron possibly forms new mineral phases that resorb (or sequester) previously released arsenic to the sediment. Despite similar redox conditions, resorption is much less significant at the river bank (Fe/As(aq) = 68, Fe/As(s) = 4700), and hence, arsenic concentrations in groundwater reach considerably higher levels. Drawdown of Holocene water to the Pleistocene aquifer in the peat area, caused by the pumping for the Hanoi water works, clearly promotes reducing conditions in Pleistocene groundwater. This demonstrates that excessive abstraction of water from deep wells, i.e., wells tapping water below the arsenic burdened depth, can cause a downward shift of iron-reducing conditions and concurrently mobilize arsenic along the way. Vertical migration of reduced groundwater may also impact aquifers under natural hydrological conditions. Seepage of DOC-enriched groundwater derived from degradation of organic matter in the clayey sediments at the river bank was observed to enhance (and maintain) iron-reducing conditions in the aquifer where organic matter is scarce. Once the aquifer becomes reduced, arsenic is released from the aquifer solid-hosts but additionally derives from the arsenic-enriched groundwater seeping from the clay into the aquifer. This behaviour is an important mechanism for arsenic contamination in aquifers that might not necessarily contain enough organic matter in their sediments to induce reducing conditions independently.

Arsenic in groundwater of the Red River floodplain, Vietnam: Controlling geochemical processes and reactive transport modeling

The mobilization of arsenic (As) to the groundwater was studied in a shallow Holocene aquifer on the Red River flood plain near Hanoi, Vietnam. The groundwater chemistry was investigated in a transect of 100 piezometers. Results show an anoxic aquifer featuring organic carbon decomposition with redox zonation dominated by the reduction of Fe-oxides and methanogenesis. Enhanced P CO 2 pressure causes carbonate dissolution to take place but mainly in the soil and unsaturated zone. The concentration of As increases over depth to a concentration of up to 550 μg/L. Most As is present as As(III) but some As(V) is always found. Arsenic correlates well with NH 4, relating its release to organic matter decomposition and the source of As appears to be the Fe-oxides being reduced. Part of the produced Fe(II) is apparently reprecipitated as siderite containing less As. Results from sediment extraction indicate most As to be related to the Fe-oxide fractions. The measured amount of sorbed As is low. In agreement, speciation calculations for a Fe-oxide surface suggest As(III) to constitute only 3% of the surface sites while the remainder is occupied by carbonate and silica species. The evolution in water chemistry over depth is homogeneous and a reactive transport model was constructed to quantify the geochemical processes along the vertical groundwater flow component. A redox zonation model was constructed using the partial equilibrium approach with organic carbon degradation in the sediment as the only rate controlling parameter. Apart from the upper meter a constant degradation rate of 0.15 C mmol/L/yr could explain the redox zonation throughout the aquifer. Modeling also indicates that the Fe-oxide being reduced is of a stable type like goethite or hematite. Arsenic is contained in the Fe-oxides and is first released during their dissolution. Our model further suggests that part of the released As is adsorbed on the surface of the remaining Fe-oxides and in this way may be retarded.

Quaternary shoreline shifting and hydrogeologic influence on the distribution of groundwater arsenic in aquifers of the Bengal Basin

Naturally occurring high arsenic concentration in groundwater of most alluvial aquifers in the Bengal Basin has been causing serious health problems in millions of people. Elevated dissolved arsenic concentrations are mostly confined within a shallow depth (<150 m) of the Middle Holocene aquifers of the GBM delta and the rapidly subsided Sylhet trough. Arsenic-rich zones in the Bengal Basin are located in the south-central parts of Bangladesh and northeastern parts of West Bengal, India, bounded by Chittagong Hills in the east and the Indian Craton to the west. Holocene sea level rise and development of reducing conditions at organic-rich swampy lands are directly linked to epicenters of arsenic distributions. Surface elevation and topographic slope seem to control the distribution of arsenic because higher levels of dissolved arsenic occur mainly within the present-day topographically low areas. Delta lobes that have experienced tidal influx in the recent past do not appear to have high arsenic concentrations in groundwaters. Groundwater quality data suggest that the sulfate-reducing condition in the coastal aquifers may limit the dissolved arsenic and iron concentrations in aquifers.

Elevated iron and manganese concentrations in groundwater derived from the Holocene transgression in the Hang-Jia-Hu Plain, China

Groundwater in the Hang-Jia-Hu Plain, eastern China, is a drinking water source for local residents. Groundwater samples were collected from large-diameter hand-dug wells and boreholes for comparison of their iron and manganese concentrations, as well as other ions. The results show that iron and manganese concentrations are relatively high, exceeding drinking water standards by several times. Aquifer sediment samples contain abundant iron (30,790 mg kg−1) and manganese (602 mg kg−1). The results of correspondence factor analysis of the hydrochemistry data and the liberation experiments (using seawater and rainwater as leachants) suggest that iron and manganese in shallow groundwater come from the sediment in the Holocene aquifer. A reductive environment involving relatively high total dissolved solids and organic carbon in the aquifer system is favorable to iron and manganese transferring from the sediment to groundwater and stabilizes these ions. Shallow, large-diameter hand-dug wells provide oxic conditions that decrease the concentrations of dissolved iron and manganese in the well water.