Mobilization of arsenic and other naturally occurring contaminants in groundwater of the Main Ethiopian Rift aquifers

This study investigates the mechanisms of arsenic (As) and other naturally occurring contaminants (F⁻, U, V, B, and Mo) mobilization from Quaternary sedimentary aquifers of the Main Ethiopian Rift (MER) and their enrichment in the local groundwater. The study is based on systematic measurements of major and trace elements as well as stable oxygen and hydrogen isotopes in groundwater, coupled with geochemical and mineralogical analyses of the aquifer rocks. The Rift Valley aquifer is composed of rhyolitic volcanics and Quaternary lacustrine sediments. X-ray fluorescence (XRF) results revealed that MER rhyolites (ash, tuff, pumice and ignimbrite) and sediments contain on average 72 wt. % and 65 wt. % SiO₂, respectively. Petrographic studies of the rhyolites indicate predominance of volcanic glass, sanidine, pyroxene, Fe-oxides and plagioclase. The As content in the lacustrine sediments (mean = 6.6 mg/kg) was higher than that of the rhyolites (mean: 2.5 mg/kg). The lacustrine aquifers of the Ziway-Shala basin in the northern part of MER were identified as high As risk zones, where mean As concentration in groundwater was 22.4 ± 33.5 (range of 0.60–190 μg/L) and 54% of samples had As above the WHO drinking water guideline value of 10 μg/L. Field As speciation measurements showed that most of the groundwater samples contain predominantly (∼80%) arsenate-As(V) over arsenite-As(III) species. The As speciation together with field data of redox potential (mean Eh = +73 ± 65 mV) and dissolved-O₂ (6.6 ± 2.2 mg/L) suggest that the aquifer is predominantly oxidative. Water-rock interactions, including the dissolution of volcanic glass produces groundwater with near-neutral to alkaline pH (range 6.9–8.9), predominance of Na–HCO₃ ions, and high concentration of SiO₂ (mean: 85.8 ± 11.3 mg/L). The groundwater data show high positive correlation of As with Na, HCO₃¯, U, B, V, and Mo (R² > 0.5; p < 0.001). Chemical modeling of the groundwater indicates that Fe-oxides and oxyhydroxides minerals were saturated in the groundwater, suggesting that the As reactivity is controlled by adsorption/desorption processes with these minerals. The data show that As and other oxyanion-forming elements such as U, B, Mo, and V had typically higher concentrations at pH > ∼8, reflecting the pH-dependence of their mobilization. Based on the geochemical and stable isotope variations we have established a conceptual model for the occurrence of naturally occurring contaminants in MER groundwater: 1) regional groundwater recharge from the Highland, along the Rift margins, followed by lateral flow and water–rock interactions with the aquifer rocks resulted in a gradual increase of the salinity and naturally occurring contaminants towards the center of the valley; and (2) local δ¹⁸O-rich lake water recharge into adjacent shallow aquifers, followed by additional mobilization of As and other oxyanion-forming elements from the aquifer rocks. We posit that the combined physical-chemical conditions of the aquifers such as oxidizing state, Na–HCO₃ composition, and pH>∼8 lead to enhanced mobilization of oxyanion-forming elements from Fe-oxides and consequently contamination of local groundwater. These geochemical conditions characterize groundwater resources along the Eastern African Rift and thus constitute a potential threat to the quality of groundwater in larger areas of Eastern Africa.     

Groundwater geochemistry and its implications for arsenic mobilization in shallow aquifers of the Hetao Basin, Inner Mongolia

Arsenic concentrations in shallow groundwaters from the Hetao Basin of Inner Mongolia range between 0.6 and 572 microg/L. High As groundwaters generally occur in the shallow alluvial-lacustrine aquifers, which are mainly composed of black (or dark grey) fine sands in a reducing environment. They are characterized by high concentrations of dissolved Fe, Mn, HCO(3)(-), P and S(2-), and low concentrations of NO(3)(-) and SO(4)(2-). Low SO(4)(2-) coupled with high S(2-) suggests that SO(4)(2-) reduction has been an active process. In the reducing groundwaters, inorganic As(III) accounts for around 75% of total dissolved As. Total As contents in the sediments from three representative boreholes are observed to be 7.3-73.3 mg/kg (average of 18.9 mg/kg). The total As is mildly-strongly correlated with total Fe and total Mn, while a quite weak correlation exists between total As and total S, suggesting that the As is associated with Fe-Mn oxides, rather than sulfides in the sediments. It is found in the sequential extraction that chemically active As is mainly bound to Fe-Mn oxides, up to 3500 microg/kg. The mobilization of As under reducing conditions is believed to include reductive dissolution of Fe-Mn oxides and reduction of adsorbed As. Although exchangeable As is labile and very vulnerable to hydrogeochemical condition, the contribution is relatively limited due to the low concentrations. The competition between As and other anions (such as HPO(4)(2-)) for binding sites on Fe-Mn oxides may also give rise to the release of As into groundwater. Slow groundwater movement helps accumulation of the released As in the groundwaters.     

Erratum to “Effects of intensive urbanization on the intrusion of shallow groundwater into deep groundwater: Examples from Bangkok and Jakarta”

Asian megacities have severe pollution problems in both coastal and urban areas. In addition, the groundwater potential has decreased and land subsidence has occurred because of intensive groundwater pumping in urban areas. To prevent the adverse effects of urbanization on groundwater quality, it is necessary to confirm the changes in groundwater flow and contaminant transport caused by urbanization. We examined the effects of urbanization on contaminant transport in groundwater. The research areas were located around Bangkok, Thailand, and akarta, Indonesia, cities with populations of approximately 8 and 12 million, respectively. Each metropolitan city is located on a river delta and is adjacent to a bay. We measured the water level and collected water samples at boreholes at multiple depths (100 to 200 m) in 2004 and 2006 in Bangkok and Jakarta, respectively. The current hydraulic potential is below sea level in both cities because of prior excess abstraction of groundwater. As a result, the direction of groundwater flow is now downward in the coastal area. The Cl⁻ concentration and δ¹⁸O distributions in groundwater suggest that the decline in hydraulic potential has caused the intrusion of seawater and shallow groundwater into deep groundwater. Concentrations of Mn and NO3⁻-N in groundwater suggest the intrusion of these contaminants from shallow to deep aquifers with downward groundwater flow and implies an accumulation of contaminants in deep aquifers. Therefore, it is important to recognize the possibility of future contaminant transport with the discharge of deep groundwater into the sea after the recovery of groundwater potential in the coastal areas.     

Processes releasing arsenic to groundwater in the Caldes de Malavella geothermal area, NE Spain

Arsenic concentrations exceeding the World Health Organization drinking water guideline (10 μg/L) have been measured in thermal and non-thermal groundwaters from the Caldes de Malavella geothermal area (La Selva graben, NE Spain). The CO₂-rich Na-HCO₃ thermal waters (up to 60 °C at the spring) have elevated arsenic concentrations ([As_T] from 50 to 80 μg/L). The non-thermal waters are of Ca-Na-HCO₃-Cl type and have [As_T] between <1 and 200 μg/L, defining a hot-spot distribution. The present-day contribution of As from CO₂-rich thermal waters to non-thermal aquifers is very limited, as shown by the concentration of geothermal tracers such as Li and B. Redox-controlling processes appear to govern the mobility of As in the non-thermal waters. Arsenate is clearly predominant in most oxidizing groundwaters (>85% of As(V) over total As), whereas reducing, high-As groundwater reaches up to 100% in arsenite. The reductive dissolution of Fe(III) oxyhydroxides and the coupled release and reduction of adsorbed As explain the elevated dissolved arsenite (up to 190 μg/L) and Fe (up to 14 mg/L) content in the more reducing non-thermal groundwater. Conversely, the high levels of nitrate (up to 136 mg/L) ensure an oxidizing environment in most non-thermal groundwaters ([As_T] between <1 and 60 μg/L). Under these conditions, Fe(III) oxyhydroxides are stable and As release to groundwater is not related to their dissolution. Instead, dissolved arsenate concentrations up to 60 μg/L are explained by a competition for sorption sites with other species, mainly bicarbonate and silicic acid, while arsenate desorption due to pH increase is not considered a major process.     

Manganese concentrations in Scottish groundwater

Groundwater is increasingly being used for public and private water supplies in Scotland, but there is growing evidence that manganese (Mn) concentrations in many groundwater supplies exceed the national drinking water limit of 0.05 mg l^− 1. This study examines the extent and magnitude of high Mn concentrations in groundwater in Scotland and investigates the factors controlling Mn concentrations. A dataset containing 475 high quality groundwater samples was compiled using new data from Baseline Scotland supplemented with additional high quality data where available. Concentrations ranged up to 1.9 mg l^− 1; median Mn concentration was 0.013 mg l^− 1 with 25th and 75th percentiles 0.0014 and 0.072 mg l^− 1 respectively. The Scottish drinking water limit (0.05 mg l^− 1) was exceeded for 30% of samples and the WHO health guideline (0.4 mg l^− 1) by 9%; concentrations were highest in the Carboniferous sedimentary aquifer in central Scotland, the Devonian sedimentary aquifer of Morayshire, and superficial aquifers. Further analysis using 137 samples from the Devonian aquifers indicated strong redox and pH controls (pH, Eh and dissolved oxygen accounted for 58% of variance in Mn concentrations). In addition, an independent relationship between Fe and Mn was observed, suggesting that Fe behaviour in groundwater may affect Mn solubility. Given the redox status and pH of Scottish groundwaters the most likely explanation is sorption of Mn to Fe oxides, which are released into solution when Fe is reduced.Since the occurrence of elevated Mn concentrations is widespread in groundwaters from all aquifer types, consideration should be given to monitoring Mn more widely in both public and private groundwater supplies in Scotland and by implication elsewhere.     

Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China

High arsenic groundwater in the Quaternary aquifers of Datong Basin, northern China contain As up to 1820 µg/L and the high concentration plume is located in the slow flowing central parts of the basin. In this study we used hydrochemical data and sulfur isotope ratios of sulfate to better understand the conditions that are likely to control arsenic mobilization. Groundwater and spring samples were collected along two flow paths from the west and east margins of the basin and a third set along the basin flow path. Arsenic concentrations range from 68 to 670 µg/L in the basin and from 3.1 to 44 µg/L in the western and eastern margins. The margins have relatively oxidized waters with low contents of arsenic, relatively high proportions of As(V) among As species, and high contents of sulfate and uranium. By contrast, the central parts of the basin are reducing with high contents of arsenic in groundwater, commonly with high proportions of As(III) among As species, and low contents of sulfate and uranium. No statistical correlations were observed between arsenic and Eh, sulfate, Fe, Mn, Mo and U. While the mobility of sulfate, uranium and molybdenum is possibly controlled by the change in redox conditions as the groundwater flows towards central parts of the basin, the reducing conditions alone cannot account for the occurrence of high arsenic groundwater in the basin but it does explain the characteristics of arsenic speciation. With one exception, all the groundwaters with As(III) as the major As species have low Eh and those with As(V) have high Eh. Reductive dissolution of Fe-oxyhydroxides or reduction of As(V) are consistent with the observations, however no increase in dissolved Fe concentration was noted. Furthermore, water from the well with the highest arsenic was relatively oxidizing and contained mostly As(V). From previous work Fe-oxyhydroxides are speculated to exist as coatings rather than primary minerals.The wide range of δ³⁴S_[SO4] values (from − 2.5 to + 36.1‰) in the basin relative to the margins (from + 8‰ to + 15‰) indicate that sulfur is undergoing redox cycling. The highly enriched values point to sulfate reduction that was probably mediated by bacteria. The presence of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) is also evidence of microbial reactions. The depleted signatures indicate that some oxidation of depleted sulfide occurred in the basin. It must be noted that the samples with depleted sulfur isotope values have very low sulfate concentrations and therefore even a small amount of sulfide oxidation will bias the ratio. No significant correlation was observed between δ³⁴S_[SO4] values and total arsenic contents when all the samples were considered. However, the wells in the central basin do appear to become enriched in δ³⁴S_[SO4] as arsenic concentration increases. Although there is evidence for sulfate reduction, it is clear that sulfate reduction does not co-precipitate or sequester arsenic. The one sample with high arsenic that is oxidizing cannot be explained by oxidation of pyrite and is likely an indication that there are multiple redox zones that control arsenic speciation but not necessarily its mobilization and contradict the possibility that Fe-oxyhydroxides sorb appreciable amounts of arsenic in this study area. It is evident that this basin like other two young sedimentary basins (Huhhot and Hetao in Inner Mongolia) of northern China with high arsenic groundwater is transporting arsenic at a very slow rate. The data are consistent with the possibility that the traditional models of arsenic mobilization, namely reductive dissolution of Fe-oxyhydroxides, reduction of As(V) to more mobile As(III), and bacteria mediated reactions, are active to varying degrees. It is also likely that different processes control arsenic mobilization at different locations of the basin and more detailed studies along major flow paths upgradient of the high arsenic aquifers will shed more light on the mechanisms.     

Implications of organic matter on arsenic mobilization into groundwater: Evidence from northwestern (Chapai-Nawabganj), central (Manikganj) and southeastern (Chandpur) Bangladesh

Boreholes (50 m depth) and piezometers (50 m depth) were drilled and installed for collecting As-rich sediments and groundwater in the Ganges, Brahmaputra, and Meghna flood plains for geochemical analyses. Forty-one groundwater samples were collected from the three areas for the analyses of cations (Ca²⁺, Mg²⁺, K⁺, Na⁺), anions (Cl⁻, NO₃⁻, SO₄²⁻), total organic carbon (TOC), and trace elements (As, Mn, Fe, Sr, Se, Ni, Co, Cu, Mo, Sb, Pb). X-ray powder diffraction (XRD) and X-ray fluorescence (XRF) were performed to characterize the major mineral and chemical contents of aquifer sediments. In all three study areas, results of XRF analysis clearly show that fine-grained sediments contain higher amounts of trace element because of their high surface area for adsorption. Relative fluorescent intensity of humic substances in groundwater samples ranges from 30 to 102 (mean 58 ± 20, n = 20), 54-195 (mean 105 ± 48, n = 10), and 27-243 (mean 79 ± 71, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Arsenic concentration in groundwater (20-50 m of depth) ranges from 3 to 315 μg/L (mean 62.4 ± 93.1 μg/L, n = 20), 16.4-73.7 μg/L (mean 28.5 ± 22.4 μg/L, n = 10) and 4.6-215.4 μg/L (mean 30.7 ± 62.1 μg/L, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Specific ultra violet adsorption (SUVA) values (less than 3 m⁻¹ mg⁻¹ L) indicate that the groundwater in the Ganges flood plain has relatively low percentage of aromatic organic carbon compared to those in the Brahmaputra and Meghna flood plains. Arsenic content in sediments ranges from 1 to 11 mg/kg (mean 3.5 ± 2.7 mg/kg, n = 17) in the three flood plains. Total organic carbon content is 0.5-3.7 g/kg (mean 1.9 ± 1.1 g/kg) in the Ganges flood plain, 0.5-2.1 g/kg (mean: 1.1 ± 0.7 g/kg) in the Brahmaputra flood plain and 0.3-4.4 g/kg (mean 1.9 ± 1.9 g/kg) in the Meghna flood plain. Arsenic is positively correlated with TOC (R² = 0.50, 0.87, and 0.85) in sediments from the three areas. Fourier transform infrared (FT-IR) analysis of the sediments revealed that the functional groups of humic substances in three areas include amines, phenol, alkanes, and aromatic carbon. Arsenic and Fe speciation in sediments were determined using XANES and the results imply that As(V) and Fe(III) are the dominant species in most sediments. The results also imply that As (V) and Fe (III) in most of the sediment samples of the three areas are the dominant species. X-ray absorption fine structure (EXAFS) analysis shows that FeOOH is the main carrier of As in the sediments of three areas. In sediments, As is well correlated with Fe and Mn. However, there is no such correlation observed between As and Fe as well as As and Mn in groundwater, implying that mobilizations of Fe, Mn, and As are decoupled or their concentrations in groundwater have been affected by other geochemical processes following reductive dissolution of Fe or Mn-hydroxides. For example, dissolved Fe and Mn levels may be affected by precipitation of Fe- and Mn-carbonate minerals such as siderite, while liberated As remains in groundwater. The groundwaters of the Brahmaputra and Meghna flood plains contain higher humic substances in relative fluorescence intensity (or fluorescence index) and lower redox potential compared to the groundwater of Ganges flood plain. This leads to the release of arsenic and iron to groundwater of these three plains in considerable amounts, but their concentrations are distributed in spatial variations.     

Migration of As, and H/He ages, in groundwater from West Bengal: Implications for monitoring

From 2002 to 2010 inclusive we monitored concentrations of arsenic (As) and major ions (Ca, Mg, Sr, Na, K, Fe, Mn, Cl, and SO₄) in groundwater from 14 domestic wells and three piezometer nests in a shallow aquifer (<60 m depth), and 3 wells in a deep aquifer (>70 m depth), in southern West Bengal, India. In the deep aquifer, concentrations of As did not change over time despite increases in the concentration of Fe in two wells. The shallow aquifer occurs in two sedimentological settings: palaeo-channel and palaeo-interfluve. At the top of the shallow aquifer of the palaeo-channel, decreases in all constituent concentrations with time, and an ³H/³He age of 1.4 years, proves that the aquifer is beginning to be flushed of pollutants. In As-polluted groundwater (>50 μg/L As) tapped from deeper grey sands of the shallow, palaeo-channel, aquifer, concentrations of As were mostly stable over time, but both increases and decreases occurred with time in response to downward migration of the chemically-stratified water column. In groundwater tapped from Pleistocene brown sands, the concentration of As remained either low and stable (<2 μg/L As), or increased at rates up to 34 μg/L per year. The increases were caused by the flow of As-rich groundwater either downward into brown sand at the base of palaeo-channels, or laterally into a confined, unpolluted, palaeo-interfluvial, aquifer of brown sand that lies regionally beneath a palaeosol.Under the present pumping regime, the prognosis for As-pollution in the shallow aquifer is complex. Wells in brown sand may become polluted over timescales of as little as 2 years, whilst some wells tapping As-polluted groundwater from grey sand will become fit for potable use (<50 μg/L) within a few decades. The evidence of flushing, and of declining As in some of the groundwater from palaeo-channels, which are conduits for recharge of the confined, As-free, palaeo-interfluve aquifer, and probably also the deeper aquifer, offers hopes that the spread of As-pollution will be limited.     

Microbial transformations of arsenic: mobilization from glauconitic sediments to water

In the Inner Coastal Plain of New Jersey, arsenic (As) is released from glauconitic sediment to carbon- and nutrient-rich shallow groundwater. This As-rich groundwater discharges to a major area stream. We hypothesize that microbes play an active role in the mobilization of As from glauconitic subsurface sediments into groundwater in the Inner Coastal Plain of New Jersey. We have examined the potential impact of microbial activity on the mobilization of arsenic from subsurface sediments into the groundwater at a site on Crosswicks Creek in southern New Jersey. The As contents of sediments 33-90 cm below the streambed were found to range from 15 to 26.4 mg/kg, with siderite forming at depth. Groundwater beneath the streambed contains As at concentrations up to 89 μg/L. Microcosms developed from site sediments released 23 μg/L of As, and active microbial reduction of As(V) was observed in microcosms developed from site groundwater. DNA extracted from site sediments was amplified with primers for the 16S rRNA gene and the arsenate respiratory reductase gene, arrA, and indicated the presence of a diverse anaerobic microbial community, as well as the presence of potential arsenic-reducing bacteria. In addition, high iron (Fe) concentrations in groundwater and the presence of iron-reducing microbial genera suggests that Fe reduction in minerals may provide an additional mechanism for release of associated As, while arsenic-reducing microorganisms may serve to enhance the mobility of As in groundwater at this site.     

Temperature-induced impacts on groundwater quality and arsenic mobility in anoxic aquifer sediments used for both drinking water and shallow geothermal energy production

Aquifers used for the production of drinking water are increasingly being used for the generation of shallow geothermal energy. This causes temperature perturbations far beyond the natural variations in aquifers and the effects of these temperature variations on groundwater quality, in particular trace elements, have not been investigated. Here, we report the results of column experiments to assess the impacts of temperature variations (5°C, 11°C, 25°C and 60°C) on groundwater quality in anoxic reactive unconsolidated sandy sediments derived from an aquifer system widely used for drinking water production in the Netherlands. Our results showed that at 5 °C no effects on water quality were observed compared to the reference of 11°C (in situ temperature). At 25°C, As concentrations were significantly increased and at 60 °C, significant increases were observed pH and DOC, P, K, Si, As, Mo, V, B, and F concentrations. These elements should therefore be considered for water quality monitoring programs of shallow geothermal energy projects. No consistent temperature effects were observed on Na, Ca, Mg, Sr, Fe, Mn, Al, Ba, Co, Cu, Ni, Pb, Zn, Eu, Ho, Sb, Sc, Yb, Ga, La, and Th concentrations, all of which were present in the sediment. The temperature-induced chemical effects were probably caused by (incongruent) dissolution of silicate minerals (K and Si), desorption from, and potentially reductive dissolution of, iron oxides (As, B, Mo, V, and possibly P and DOC), and mineralisation of sedimentary organic matter (DOC and P).     

Nitrate contamination of shallow groundwaters in Ontario,Canada

Highly elevated concentrations of NO₃^? have been found in the groundwaters from shallow aquifers at several locations in Ontario. The nitrate is derived either from the fertilizers applied to the agricultural soils, or from industrial point sources, and should be regarded as a major water quality problem. However, the nitrate levels may be reduced by denitrification processes under reducing conditions in the aquifer. The distributions of ammonia, chloride, dissolved oxygen, redox potential, methane, calcium and magnesium are presented and related to the hydrogeochemical changes undergone by the pollutant nitrate during flux along the groundwater flow systems.     

Influence of traditional agricultural practices on mobilization of arsenic from sediments to groundwater in Bengal delta

In the wake of the idea that surface derived dissolved organic carbon (DOC) plays an important role in the mobilization of arsenic (As) from sediments to groundwater and may provide a vital tool in understanding the mechanism of As contamination (mobilization/fixation) in Bengal delta; a study has been carried out. Agricultural fields that mainly cultivate rice (paddy fields) leave significantly large quantities of organic matter/organic carbon on the surface of Bengal delta which during monsoon starts decomposing and produces DOC. The DOC thus produced percolates down with rain water and mobilizes As from the sediments. Investigations on sediment samples collected from a paddy field clearly indicate that As coming on to the surface along with the irrigation water accumulates itself in the top few meters of sediment profile. The column experiments carried out on a 9 m deep sediment profile demonstrates that DOC has a strong potential to mobilize As from the paddy fields and the water recharging the aquifer through such agricultural fields contain As well above the WHO limit thus contaminating the shallow groundwater. Experiment also demonstrates that decay of organic matter induces reducing condition in the sediments. Progressively increasing reducing conditions not only prevent the adsorption of As on mineral surfaces but also cause mobilization of previously sorbed arsenic. There seems to be a cyclic pattern where As from deeper levels comes to the surface with irrigational water, accumulates itself in the sediments, and ultimately moves down to the shallow groundwater. The extensive and continual exploitation of intermediate/deep groundwater accelerates this cyclic process and helps in the movement of shallow contaminated groundwater to the deeper levels.     

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals.The highest concentrations of dissolved As were found in groundwater (up to 1141 μg L^− 1), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S^− 2,0 in the solid phase and a lower dissolved As concentration (70-80 μg L^− 1) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 μg L^− 1 in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.     

Controls on the distribution of rare earth elements in shallow groundwaters

Shallow groundwater samples (<0.22 microm) collected from a small catchment in Western France (Petit Hermitage catchment) were analyzed for their rare earth elements (REE), dissolved organic carbon (DOC) and trace-element (Fe, Mn, Th and U) contents, with the aim to investigate the controlling factors of REE signatures. Two spatially distinct water types are recognized in this catchment based on changes of REE concentrations and variations of Ce anomalies. These include (i) DOC-poor groundwater flowing below the hillslope domains; this type has low REE contents and records conspicuous negative Ce anomalies; (ii) DOC-rich groundwater from the wetland domains, close to the river network; this type displays much higher REE concentrations, and typically lack negative Ce anomalies. Temporal REE concentration variations were assessed in wetland waters. Results show a marked increase of the REE content at the winter-spring transition, along with variations of DOC, Fe and Mn contents and redox potential changes. Using the above data set in conjunction with previously published results on comparable shallow groundwaters, we demonstrate that factors such as aquifer-rock composition or anthropogenic input probably play a minor role in determining the REE signatures of shallow groundwaters. Most likely, the two dominant factors involved are the organic matter content and the redox status of the waters. We suggest that topography might be the ultimate key parameter by its ability to control the DOC content of groundwater at a catchment scale.     

Grundwasser in Nürnberg: Wichtige Einheiten und deren Nutzbarkeit

The use and protection of urban – area aquifers such as the groundwater resources below the city of Nuremberg is becoming increasingly important. Hence, we present a stratigraphic and hydrogeologic overview of the “Nuremberg Syncline”.The Nuremberg Syncline regional aquifer system can be divided into seven units. Geochemical and stable isotope investigations have shown that strict hydraulic separations between aquifers and aquitards do not always exist. Connections may be enhanced, for example, via tectonic discontinuities that enable the rise of CO₂-rich groundwaters from deeper units. This is confirmed by frequent occurrences of artesian well conditions. Important subsurface structures in the near-surface aquifers include four palaeo-valleys that cut deep into the stratigraphic units of Keuper sandstones (Keuper Group; Middle and Late Triassic). These remarkable palaeo-valleys have been investigated with more than 2400 boreholes. The gravel and sand deposits of these aquifers offer, for instance, ideal possibilities for both heating and cooling of buildings by geothermal heat pumps.     

Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using δ³⁴S_[SO4] and δ¹⁸O_[SO4] sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of ³⁴S_[SO4] and ¹⁸O_[SO4] present in Type A, caused by microbial-mediated reduction of sulfate, and high ¹⁸O enrichment factor (ε_[SO4-H2O]), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high δ¹⁸O_[SO4] and low δ³⁴S_[SO4] values under mildly reducing conditions. Base on ¹⁸O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O₂, caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater.     

Arsenic attenuation by oxidized aquifer sediments in Bangladesh

Recognition of arsenic (As) contamination of shallow fluvio-deltaic aquifers in the Bengal Basin has resulted in increasing exploitation of groundwater from deeper aquifers that generally contain low concentrations of dissolved As. Pumping-induced infiltration of high-As groundwater could eventually cause As concentrations in these aquifers to increase. This study investigates the adsorption capacity for As of sediment from a low-As aquifer near Dhaka, Bangladesh. A shallow, chemically-reducing aquifer at this site extends to a depth of 50 m and has maximum As concentrations in groundwater of 900 microg/L. At depths greater than 50 m, geochemical conditions are more oxidizing and groundwater has <5 microg/L As. There is no thick layer of clay at this site to inhibit vertical transport of groundwater. Arsenite [As(III)] is the dominant oxidation state in contaminated groundwater; however, data from laboratory batch experiments show that As(III) is oxidized to arsenate [As(V)] by manganese (Mn) minerals that are present in the oxidized sediment. Thus, the long-term viability of the deeper aquifers as a source of water supply is likely to depend on As(V) adsorption. The adsorption capacity of these sediments is a function of the oxidation state of As and the concentration of other solutes that compete for adsorption sites. Arsenite that was not oxidized did adsorb, but to a much lesser extent than As(V). Phosphate (P) caused a substantial decrease in As(V) adsorption. Increasing pH and concentrations of silica (Si) had lesser effects on As(V) adsorption. The effect of bicarbonate (HCO(3)) on As(V) adsorption was negligible. Equilibrium constants for adsorption of As(V), As(III), P, Si, HCO(3), and H were determined from the experimental data and a quantitative model developed. Oxidation of As(III) was modeled with a first-order rate constant. This model was used to successfully simulate As(V) adsorption in the presence of multiple competing solutes. Results from these experiments show that oxidized sediments have a substantial but limited capacity for removal of As from groundwater.     

Assessment of arsenic exposure from groundwater and rice in Bengal Delta Region, West Bengal, India

Arsenic (As) induced identifiable health outcomes are now spreading across Indian subcontinent with continuous discovery of high As concentrations in groundwater. This study deals with groundwater hydrochemistry vis-à-vis As exposure assessment among rural population in Chakdaha block, West Bengal, India. The water quality survey reveals that 96% of the tubewells exceed WHO guideline value (10 μg/L of As). The groundwaters are generally anoxic (−283 to −22 mV) with circum-neutral pH (6.3 to 7.8). The hydrochemistry is dominated by HCO₃⁻ (208 to 440 mg/L), Ca²⁺ (79 to 178 mg/L) and Mg²⁺ (17 to 45 mg/L) ions along with high concentrations of As_T (As total, below detection limit to 0.29 mg/L), Fe_T (Fe total, 1.2 to 16 mg/L), and Fe(II) (0.74 to 16 mg/L). The result demonstrates that Fe(II)-Fe(III) cycling is the dominant process for the release of As from aquifer sediments to groundwater (and vice versa), which is mainly controlled by the local biogeochemical conditions. The exposure scenario reveals that the consumption of groundwater and rice are the major pathways of As accumulation in human body, which is explained by the dietary habit of the surveyed population. Finally, regular awareness campaign is essential as part of the management and prevention of health outcomes.     

Distribution of volatile organic compounds in Sicilian groundwaters analysed by head space-solid phase micro extraction coupled with gas chromatography mass spectrometry (SPME/GC/MS)

This work presents the results of an assessment of the existence and concentration of 13 volatile organic compounds (VOCs) in groundwaters from 14 hydrological basins in Sicily (25,710km(2)). On the basis of hydrological, hydrogeochemical and geological studies, 324 sampling points were selected. All groundwater sampled were collected twice, from October to December 2004 and from February to May 2005, and were analysed to determine the concentration and spatial distribution of the VOCs in the aquifers. The need to analyze a large number of samples in a short space of time so as to obtain quantitative analyses in trace concentration levels spurred us to create a new analytical method, both simple and sensitive, based on HS-SPME/GC/MS. The concentrations of VOCs measured in industrial and intensive agricultural unconfined aquifers were greater than those found in other aquifers. Tetrachloroethylene, chloroform, trichloroethylene and 1,2-dichloropropane were the most frequently detected VOCs. However, they exceeded the guideline values proposed by the EU in only three aquifers located near to industrial and intense agricultural areas.     

Behaviour of nitrilotriacetic acid during groundwater recharge

A pilot plant study was performed to investigate the behaviour of nitrilotriacetic acid (NTA) during artificial groundwater recharge of river water.The study was designed to investigate the removal of NTA under conditions of artificial groundwater recharge in The Netherlands.The conditions are characterized by relatively low recharge rates and mostly by anaerobic groundwater environments in the aquifers. A further objective of the study was to obtain information on the possible mobilisation of heavy metals from the soil of the aquifer as a result of the formation of NTA-metal complexes.The results suggest that complete removal of NTA during percolation can be expected for concentrations up to 2 mg NTA l⁻¹ in the surface water, even during the period of low water temperatures. The mobilisation of trace elements from the aquifer during the percolation of water containing these low concentrations of NTA was not detected and is considered improbable.