Geochemical and hydrogeological contrasts between shallow and deeper aquifers in two villages of Araihazar, Bangladesh: Implications for deeper aquifers as drinking water sources

Sediment and groundwater profiles were compared in two villages of Bangladesh to understand the geochemical and hydrogeological factors that regulate dissolved As concentrations in groundwater. In both villages, fine-grained sediment layers separate shallow aquifers (< 28 m) high in As from deeper aquifers (40-90 m) containing < 10 μg/L As. In one village (Dari), radiocarbon dating indicates deposition of the deeper aquifer sediments > 50 ka ago and a groundwater age of thousands of years. In the other village (Bay), the sediment is < 20 ka old down to 90 m and the deeper aquifer groundwater is younger, on the order of hundreds of years. The shallow aquifers in both villages that are high in As contain bomb-³H and bomb-¹⁴C, indicating recent recharge. The major and minor ion compositions of the shallow and deeper aquifers also differ significantly. Deeper aquifer water is of the Na⁺-HCO₃^- type, with relatively little dissolved NH₄⁺ (76 ± 192 μmol/L), Fe (27 ± 43 μmol/L) and Mn (3 ± 2 μmol/L). In contrast, shallow aquifer water is of the Ca²⁺-Mg²⁺-HCO₃^- type, with elevated concentrations of dissolved NH₄⁺ (306 ± 355 μmol/L), Fe (191 ± 73 μmol/L), and Mn (27 ± 43 μmol/L). In both villages, the quantity of As extractable from deeper aquifer sands with a 1 mol/L phosphate solution (0.2 ± 0.3 mg/kg, n = 12; 0.1 ± 0.1 mg/kg, n = 5) is 1 order of magnitude lower than P-extractable As from shallow deposits (1.7 ± 1.2 mg/kg, n = 9; 1.4 ± 2.0 mg/kg, n = 11). The differences suggest that the concentration of P-extractable As in the sediment is a factor controlling the concentration of As in groundwater. Low P-extractable As levels are observed in both deeper aquifers that are low in As, even though there is a large difference in the time of deposition of these aquifers in the two villages. The geochemical data and hydrographs presented in this study suggest that both Holocene and Pleistocene deeper aquifers that are low in As should be a viable source of drinking water as long as withdrawals do not exceed recharge rates of ∼1 cm/yr.     

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

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

Metal mobilization from base-metal smelting slag dumps in Sierra Almagrera (Almería,Spain)

Smelting slags associated with base-metal vein deposits of the Sierra Almagrera area (SE Spain) show high concentrations of Ag (<5–180 ppm), As (12–750 ppm), Cu (45–183 ppm), Fe (3.2–29.8%), Pb (511–2150 ppm), Sb (22–620 ppm) and Zn (639–8600 ppm). The slags are mainly composed of quartz, fayalite, barite, melilite, celsian, pyrrhotite, magnetite, galena and Zn–Pb–Fe alloys. No glassy phases were detected. The following weathering-related secondary phases were found: jarosite–natrojarosite, cotunnite, cerussite, goethite, ferrihydrite, chalcanthite, copiapite, goslarite, halotrichite and szomolnokite. The weathering of slag dumps near the Mediterranean shoreline has contaminated the soils and groundwater, which has caused concentrations in groundwater to increase to 0.64 mg/L Cu, 40 mg/L Fe, 0.6 mg/L Mn, 7.6 mg/L Zn, 5.1 mg/L Pb and 19 μg/L As. The results of laboratory leach tests showed major solubilization of Al (0.89–12.6 mg/L), Cu (>2.0 mg/L), Fe (0.22–9.8 mg/L), Mn (0.85–40.2 mg/L), Ni (0.092–2.7 mg/L), Pb (>2.0 mg/L) and Zn (>2.5 mg/L), and mobilization of Ag (0.2–31 μg/L), As (5.2–31 μg/L), Cd (1.3–36.8 μg/L) and Hg (0.2–7 μg/L). The leachates were modeled using the numerical code PHREEQC. The results suggested the dissolution of fayalite, ferrihydrite, jarosite, pyrrhotite, goethite, anglesite, goslarite, chalcanthite and cotunnite. The presence of secondary phases in the slag dumps and contaminated soils may indicate the mobilization of metals and metalloids, and help to explain the sources of groundwater contamination.     

Spatial variation in arsenic and fluoride concentrations of shallow groundwater from the town of Shahai in the Hetao basin,Inner Mongolia

Twenty-nine wells were selected for groundwater sampling in the town of Shahai, in the Hetao basin, Inner Mongolia. Four multilevel samplers were installed for monitoring groundwater chemistry at depths of 2.5–20 m. Results show that groundwater As exhibits a large spatial variation, ranging between 0.96 and 720 μg/L, with 71% of samples exceeding the WHO drinking water guideline value (10 μg/L). Fluoride concentrations range between 0.30 and 2.57 mg/L. There is no significant correlation between As and F⁻ concentrations. Greater As concentrations were found with increasing well depth. However, F⁻ concentrations do not show a consistent trend with depth. Groundwater with relatively low Eh has high As concentrations, indicating that the reducing environment is the major factor controlling As mobilization. Low As concentrations (<10 μg/L) are found in groundwater at depths less than 10 m. High groundwater As concentration is associated with aquifers that have thick overlying clay layers. The clay layers, mainly occurring at depths <10 m, have low permeability and high organic C content. These strata restrict diffusion of atmospheric O₂ into the aquifers, and lead to reducing conditions that favor As release. Sediment composition is an additional factor in determining dissolved As concentrations. In aquifers composed of yellowish-brown fine sands at depths around 10 m, groundwater generally has low As concentrations which is attributed to the high As adsorption capacity of the yellow–brown Fe oxyhydroxide coatings. Fluoride concentration is positively correlated with pH and negatively correlated with Ca²⁺ concentration. All groundwater samples are over-saturated with respect to calcite and under-saturated with respect to fluorite. Dissolution and precipitation of Ca minerals (such as fluorite and calcite), and F⁻ adsorption–desorption are likely controlling the concentration of F⁻ in groundwater.     

Considerations for conducting incubations to study the mechanisms of As release in reducing groundwater aquifers

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.     

Hydrological and geochemical control of metals and arsenic in a Mediterranean river contaminated by acid mine drainage (the Amous River,France); preliminary assessment of impacts on fish (Leuciscus cephalus)

Dissolved and particulate concentrations of metals (Fe, Al, Mn, Co, Ni, Cu, Zn, Cd, Tl, Pb) and As were monitored over a 5 year period in the Amous River downstream of its confluence with a creek severely affected by acid mine drainage (AMD) originating from a former Pb–Zn mine. Water pH ranged from 6.5 to 8.8. Metals were predominantly in dissolved form, except Fe and Pb, which were in particulate form. In the particulate phase, metals were generally associated with Al oxides, whereas As was linked to Fe oxides. Metal concentrations in the dissolved and/or particulate phase were generally higher during the wet season due to higher generation of AMD. Average dissolved (size < 0.22 μm) metal concentrations (μg/L) were 1 ± 4 (Fe), 69 ± 49 (Al), 140 ± 118 (Mn), 4 ± 3 Co, 6 ± 4 (Ni), 1.3 ± 0.8 (Cu), 126 ± 81 (Zn), 1.1 ± 0.7 (Cd), 0.9 ± 0.5 (Tl), 2 ± 3 (Pb). Dissolved As concentrations ranged from 5 to 134 μg/L (30 ± 23 μg/L). During the survey, the concentration of colloidal metals (5 kDa < size < 0.22 μm) was less than 25% of dissolved concentrations. Dissolved metal concentrations were generally higher than the maximum concentrations allowed in European surface waters for priority substances (Ni, Cd and Pb) and higher than the environmental quality standards for other compounds. Using Diffusion Gradient in Thin Film (DGT) probes, metals were shown to be in potentially bioavailable form. The concentrations in Leuciscus cephalus were below the maximum Pb and Cd concentrations allowed in fish muscle for human consumption by the European Water Directive. Amongst the elements studied, only As, Pb and Tl were shown to bioaccumulate in liver tissue (As, Pb) or otoliths (Tl). Bioaccumulation of metals or As was not detected in muscle.     

Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

Dynamics of arsenic adsorption in the targeted arsenic-safe aquifers in Matlab, south-eastern Bangladesh: Insight from experimental studies

Targeting shallow low-As aquifers based on sediment colour may be a viable solution for supplying As-safe drinking water to rural communities in some regions of Bangladesh and West Bengal in India. The sustainability of this solution with regard to the long-term risk of As-safe oxidized aquifers becoming enriched with As needs to be assessed. This study focuses on the adsorption behaviour of shallow oxidized sediments from Matlab Region, Bangladesh, and their capacity to attenuate As if cross-contamination of the oxidized aquifers occurs. Water quality analyses of samples collected from 20 tube-wells in the region indicate that while there may be some seasonal variability, the groundwater chemistry in the reduced and oxidized aquifers was relatively stable from 2004 to 2009. Although sediment extractions indicate a relatively low amount of As in the oxidized sediments, below 2.5 mg kg⁻¹, batch isotherm experiments show that the sediments have a high capacity to adsorb As. Simulations using a surface complexation model that considers adsorption to amorphous Fe(III) oxide minerals only, under-predict the experimental isotherms. This suggests that a large proportion of the adsorption sites in the oxidized sediments may be associated with crystalline Fe(III) oxides, Mn(IV) and Al(III) oxides, and clay minerals. Replicate breakthrough column experiments conducted with lactose added to the influent solution demonstrate that the high adsorption capacity of the oxidized sediments may be reduced if water drawn down into the oxidized aquifers contains high levels of electron donors such as reactive dissolved organic C.     

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.     

Organic carbon mobilization in a Bangladesh aquifer explained by seasonal monsoon-driven storativity changes

Currently, the most widely accepted hypothesis to explain high As concentrations in Bangladesh groundwaters is that dissolved organic C (DOC) reduces solid Fe (hydr)oxides and mobilizes sorbed arsenate. The nature of the DOC and its release mechanism are still controversial. Based on weekly to biweekly sampling over the course of one monsoon cycle at six monitoring wells of different depths, it is proposed that storativity changes drive natural DOC release from clay–peat layers to the adjacent aquifers. With a decrease in hydraulic heads during the dry season, total mineralization and DOC concentrations increased. With the onset of the rainy season and an increase in hydraulic heads, release of clay–peat derived components stopped and vertical water displacement due to groundwater recharge from rainwater occurred, causing aquifer flushing and a decrease in total mineralization and DOC concentrations. Total As and DOC concentrations correlated over depth. However, at the depth of maximum concentrations, the As peak was observed during the rainy season. At present, the reason for this inverse seasonal trend between As and DOC is unclear. Higher mineralization or DOC concentrations could lead to increased As sorption or the increased arsenite release is a time-lag abiotic or microbial response to the DOC peak. The vulnerability of the Pleistocene aquifer towards increased As concentrations was found to be much higher than previously assumed. Though sorption capacities were determined to be higher than in the Holocene aquifer, probably due to intact Fe (hydr)oxides, long-term continuous As input from overlying clay and peat layers by the proposed seasonal storativity changes has led to increased aqueous As concentrations of 85 μg/L, considerably higher than drinking water standards. Until now, aquifer and especially aquitard and aquiclude hydraulics have not been considered sufficiently when attempting to explain As mobilization in Bangladesh.     

Mobility of arsenic in a Bangladesh aquifer: Inferences from geochemical profiles, leaching data, and mineralogical characterization

Aquifer geochemistry was characterized at a field site in the Munshiganj district of Bangladesh where the groundwater is severely contaminated by As. Vertical profiles of aqueous and solid phase parameters were measured in a sandy deep aquifer (depth >150 m) below a thick confining clay (119 to 150 m), a sandy upper aquifer (3.5 to 119 m) above this confining layer, and a surficial clay layer (<3.5 m). In the deep aquifer and near the top of the upper aquifer, aqueous As levels are low (<10 μg/L), but aqueous As approaches a maximum of 640 μg/L at a depth of 30 to 40 m and falls to 58 μg/L near the base (107 m) of the upper aquifer. In contrast, solid phase As concentrations are uniformly low, rarely exceeding 2 μg/g in the two sandy aquifers and never exceeding 10 μg/g in the clay layers. Solid phase As is also similarly distributed among a variety of reservoirs in the deep and upper aquifer, including adsorbed As, As coprecipitated in solids leachable by mild acids and reductants, and As incorporated in silicates and other more recalcitrant phases. One notable difference among depths is that sorbed As loads, considered with respect to solid phase Fe extractable with 1 N HCl, 0.2 M oxalic acid, and a 0.5 M Ti(III)-citrate-EDTA solution, appear to be at capacity at depths where aqueous As is highest; this suggests that sorption limitations may, in part, explain the aqueous As depth profile at this site. Competition for sorption sites by silicate, phosphate, and carbonate oxyanions appear to sustain elevated aqueous As levels in the upper aquifer. Furthermore, geochemical profiles are consistent with the hypothesis that past or ongoing reductive dissolution of Fe(III) oxyhydroxides acts synergistically with competitive sorption to maintain elevated dissolved As levels in the upper aquifer. Microprobe data indicate substantial spatial comapping between As and Fe in both the upper and deep aquifer sediments, and microscopic observations reveal ubiquitous Fe coatings on most solid phases, including quartz, feldspars, and aluminosilicates. Extraction results and XRD analysis of density/magnetic separates suggest that these coatings may comprise predominantly Fe(II) and mixed valence Fe solids, although the presence of Fe(III) oxyhydroxides can not be ruled out. These data suggest As release may continue to be linked to dissolution processes targeting Fe, or Fe-rich, phases in these aquifers.     

The occurrence and geochemistry of arsenic in groundwaters of the Newark basin of Pennsylvania

Elevated As concentrations in groundwater in the eastern United States have been recognized predominantly in the accretionary geologic terranes of northern New England. A retrospective examination of more than 18,000 existing groundwater samples from the Pennsylvania Department of Environmental Protection (PA DEP) Drinking Water and Sampling Information System database indicates that elevated groundwater As concentrations occur throughout the northern half of the Piedmont Province of Pennsylvania. Chemical analyses of 53 samples collected in 2005 from drinking water wells in this area all had detectable As, and 23% of these samples contained elevated (>133 nmol/L or >10 μg/L) concentrations of As. Elevated concentrations of As in the groundwater samples were most common in the Mesozoic sedimentary strata composed of sandstone and red mudstone with interbedded gray shale, and gray to black siltstone and shale. Arsenic was typically not elevated in groundwater of diabase intrusions of the Newark Basin or in crystalline and calcareous aquifers to the north of the Newark Basin. Geochemical parameters such as pH and oxidation–reduction potential can indicate mobility mechanisms of As in some regions. In this area, measured groundwater conditions were predominantly oxidizing (Eh > +50 mV), and more than 85% of samples contained arsenate as the dominant As species. Variations in pH were strongly correlated to the As concentration, with highest As concentrations observed at pH values greater than 6.4. The original source of As is most likely the black and gray shales that contain some arsenian pyrite with groundwater concentrations likely to be controlled by adsorption/desorption reactions with Fe oxides in the red mudstone aquifer materials.     

Arsenic enrichment in groundwater in the middle Gangetic Plain of Ghazipur District in Uttar Pradesh,India

Groundwater with high geogenic arsenic (As) is extensively present in the Holocene alluvial aquifers of Ghazipur District in the middle Gangetic Plain, India. A shift in the climatic conditions, weathering of carbonate and silicate minerals, surface water interactions, ion exchange, redox processes, and anthropogenic activities are responsible for high concentrations of cations, anions and As in the groundwater. The spatial and temporal variations for As concentrations were greater in the pre-monsoon (6.4–259.5 μg/L) when compared to the post-monsoon period (5.1–205.5 µg/L). The As enrichment was encountered in the sampling sites that were close to the Ganges River (i.e. south and southeast part of Ghazipur district). The depth profile of As revealed that low concentrations of NO₃⁻ are associated with high concentration of As and that As depleted with increasing depth. The poor relationship between As and Fe indicates the As release into the groundwater, depends on several processes such as mineral weathering, O₂ consumption, and NO₃⁻ reduction and is de-coupled from Fe cycling. Correlation matrix and factor analysis were used to identify various factors influencing the gradual As enrichment in the middle Gangetic Plain. Groundwater is generally supersaturated with respect to calcite and dolomite in post-monsoon period, but not in pre-monsoon period. Saturation in both periods is reached for crystalline Fe phases such as goethite, but not with respect to poorly crystalline Fe phases and any As-bearing phase. The results indicate release of arsenic in redox processes in dry period and dilution of arsenic concentration by recharge during monsoon. Increased concentrations of bicarbonate after monsoon are caused by intense flushing of unsaturated zone, where CO₂ is formed by decomposition of organic matter and reactions with carbonate minerals in solid phase. The present study is vital considering the fact that groundwater is an exclusive source of drinking water in the region which not only makes situation alarming but also calls for the immediate attention.     

The arsenic source term for an in-pit uranium mine tailings facility and its long-term impact on the regional groundwater

Detailed field sampling and analyses and laboratory-based diffusion-cell experiments were used in conjunction with 3-D reactive transport modeling (MODFLOW and MT3D99) to quantify the fate and long-term (10 ka) transport of As in the Rabbit Lake In-pit Tailings Management Facility (RLITMF), northern Saskatchewan, Canada. The RLITMF (300 m × 425 m × 90 m thick) was engineered to ensure solute transport within the RLITMF is dominated by diffusion. Concentrations of As in the tailings pore fluids ranged from 0.24 to 140 mg/L (n = 43). Arsenic speciation analyses indicate 90% of this arsenic exists as As⁵⁺. This observation is supported by pH–Eh measurements of pore fluids (n = 135). Geochemical analyses yielded a strong inverse correlation between the Fe/As molar ratio in the tailings solids and the corresponding concentration of dissolved As, which is attributed to the adsorption of As to secondary 2-line ferrihydrite present in the tailings. Diffusion-cell testing yielded values for the effective diffusion coefficient, sorption coefficient, and effective porosity of As in the tailings of 4.5 × 10⁻¹⁰ m²/s, 2–4 cm³/g and 0.36, respectively. Reactive transport simulations using the field and laboratory data show adsorption of As to the tailings and diffusive transport of dissolved As in the tailings should reduce the source term concentration of As to between 40% and 70% of the initial concentrations over the 10 ka simulation period. Based on these simulations, the As concentrations in the regional groundwater, 50 m down gradient of the tailings facility, should be maintained at background concentrations of 0.001 mg/L over the 10 ka period. These findings suggest the engineered in-pit disposal of U mine tailings can provide long-term protection for the local groundwater regime from As contamination.     

A survey of the inorganic chemistry of bottled mineral waters from the British Isles

The inorganic chemistry of 85 samples of bottled natural mineral waters and spring waters has been investigated from 67 sources across the British Isles (England, Wales, Scotland, Northern Ireland, Republic of Ireland). Sources include boreholes, springs and wells. Waters are from a diverse range of aquifer lithologies and are disproportionately derived from comparatively minor aquifers, the most represented being Lower Palaeozoic (10 sources), Devonian Sandstone (10 sources) and Carboniferous Limestone (9 sources). The waters show correspondingly variable major-ion compositions, ranging from Ca–HCO₃, through mixed-cation–mixed-anion to Na–HCO₃ types. Concentrations of total dissolved solids are mostly low to very low (range 58–800 mg/L). All samples analysed in the study had concentrations of inorganic constituents well within the limits for compliance with European and national standards for bottled waters. Concentrations of NO₃–N reached up to half the limit of 11.3 mg/L, although 62% of samples had concentrations <1 mg/L. Concentrations of Ba were high (up to 1010 μg/L) in two spring water samples. Such concentrations would have been non-compliant had they been classed as natural mineral waters, although no limit exists for Ba in European bottled spring water. In addition, though no European limit exists for U in bottled water, should a limit commensurate with the current WHO provisional guideline value for U in drinking water (15 μg/L) be introduced in the future, a small number of groundwater sources would have concentrations close to this value. Two sources had groundwater U concentrations > 10 μg/L, both being from the Welsh Devonian Sandstone. The highest observed U concentration was 13.6 μg/L.