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

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

Arsenic distribution, concentration and speciation in groundwater of the Osijek area, eastern Croatia

Groundwater is the main source of drinking water for the population of nearly 200,000 people in eastern Croatia. The largest town in the region is Osijek whose citizens are supplied with drinking water obtained from groundwater from the “Vinogradi” well field. This study investigated and determined As occurrence in groundwater of the Osijek area. Groundwater samples were taken from 18 water wells and 12 piezometers with a depth ranging between 21 and 200 m. Over the 10-a period to 2007, a mean As concentration of 240 μg L⁻¹ was found. There was no statistically significant secular change in concentration over that period, however small but significant seasonal variations were noted, with the highest seasonal As concentrations over the period May 2006-February 2007 being observed in summer. The predominant As species observed was As(III), constituting 85% and 93% of total As in piezometers and water wells, respectively. Higher concentrations of As tended to be found in deeper wells with the mean As concentration in shallow groundwater (<50 m) and deep groundwater (>50 m) being 27 μg L⁻¹, and 205 μg L⁻¹, respectively. Geochemically, the groundwaters show similarities to those in other parts of the Pannonian Basin. Arsenic(tot) is weakly correlated with pH and Fe, negatively correlated with Mn and has no significant correlation with any of EC, COD-Mn or alkalinity.     

Mineral control of arsenic content in thermal waters from volcano-hosted hydrothermal systems: Insights from island of Ischia and Phlegrean Fields (Campanian Volcanic Province, Italy)

This paper documents arsenic concentrations in 157 groundwater samples from the island of Ischia and the Phlegrean Fields, two of the most active volcano-hosted hydrothermal systems from the Campanian Volcanic Province (Southern Italy), in an attempt to identify the environmental conditions and mineral-solution reactions governing arsenic aqueous cycling. On Ischia and in the Phlegrean Fields, groundwaters range in composition from NaCl brines, which we interpret as the surface discharge of deep reservoir fluids, to shallow-depth circulating fluids, the latter ranging from acid-sulphate steam-heated to hypothermal, cold, bicarbonate groundwaters. Arsenic concentrations range from 1.6 to 6900 μg·l^− 1 and from 2.6 to 3800 μg·l^− 1 in the Phlegrean Fields and on Ischia, respectively. They increase with increasing water temperature and chlorine contents, and in the sequence bicarbonate groundwaters < steam-heated groundwaters < NaCl brines. According to thermochemical modeling, we propose that high As concentrations in NaCl brines form after prolonged water-rock interactions at reservoir T, fO₂ and fH₂S conditions, and under the buffering action of an arsenopyrite + pyrite + pyrrhotite rock assemblage. On their ascent toward the surface, NaCl brines become diluted by As-depleted meteoric-derived bicarbonate groundwaters, giving rise to hybrid water types with intermediate to low As contents. Steam-heated groundwaters give their intermediate to high As concentrations to extensive rock leaching promoted by interaction with As-bearing hydrothermal steam.     

Irrigation produces elevated arsenic in the underlying groundwater of a semi-arid basin in Southwestern Idaho

The shallow aquifer beneath the Western Snake River Plain (Idaho, USA) exhibits widespread elevated arsenic concentrations (up to 120 μg L⁻¹). While semi-arid, crop irrigation has increased annual recharge to the aquifer from approximately 1 cm prior to a current rate of >50 cm year⁻¹. The highest aqueous arsenic concentrations are found in proximity to the water table (all values >50 μg L⁻¹ within 50 m) and concentrations decline with depth. Despite strong vertical redox stratification within the aquifer, spatial distribution of aqueous species indicates that redox processes are not primary drivers of arsenic mobilization. Arsenic release and transport occur under oxidizing conditions; groundwater wells containing dissolved arsenic at >50 μg L⁻¹ exhibit elevated concentrations of O₂ (average 4 mg L⁻¹) and NO₃ (average 8 mg L⁻¹) and low concentrations of dissolved Fe (<20 μg L⁻¹). Sequential extractions and spectroscopic analysis of surficial soils and sediments indicate solid phase arsenic is primarily arsenate and is present at elevated concentrations (4–45 mg kg⁻¹, average: 17 mg kg⁻¹) relative to global sedimentary abundances. The highest concentrations of easily mobilized arsenic (up to 7 mg kg⁻¹) are associated with surficial soils and sediments visibly stained with iron oxides. Batch leaching experiments on these materials using irrigation waters produce pore water arsenic concentrations approximating those observed in the shallow aquifer (up to 152 μg L⁻¹). While As:Cl aqueous phase relationships suggest minor evaporative enrichment, this appears to be a relic of the pre-irrigation environment. Collectively, these data indicate that infiltrating irrigation waters leach arsenic from surficial sediments to the underlying aquifer.     

Mobility of arsenic in West Bengal aquifers conducting low and high groundwater arsenic. Part I: Comparative hydrochemical and hydrogeological characteristics

The present study demonstrates the importance of hydrogeochemical characteristics (groundwater flow and recharge) of an aquifer in the release of As to groundwater. The study area (∼20 km²) is located in Chakdaha block, Nadia district, West Bengal, which hosts groundwaters of variable As content. The spatial distribution pattern of As is patchy with areas containing groundwater that is high in As (>200 μg L⁻¹) found in close vicinity to low As (<50 μg L⁻¹) groundwaters (within 100 m). The concentration of groundwater As is found to decrease with depth. In addition, the data shows that there is no conspicuous relationship between high groundwater As concentration and high groundwater abstraction, although the central cone of depression has enlarged over 2 a and is extending towards the SE of the study area. The river Hooghly, which forms the NW boundary of the study site, shows dual behaviour (effluent and influent during pre- and post-monsoon periods, respectively), complicating the site hydrogeology. The observed groundwater flow lines tend to be deflected away from the high As portion of the aquifer, indicating that groundwater movement is very sluggish in the As-rich area. This leads to a high residence time for this groundwater package, prolonging sediment–water interaction, and hence facilitating groundwater As release.     

Rhizosphere and flooding regime as key factors for the mobilisation of arsenic and potentially harmful metals in basic,mining-polluted salt marsh soils

The occurrence of mining areas in the vicinities of salt marshes may affect their ecological functions and facilitate the transfer of pollutants into the food chain. The mobilisation of metals in salt marsh soils is controlled by abiotic (pH, redox potential) and biotic (influence of rhizosphere) factors. The effect of the rhizosphere of two plant species (Sarcocornia fruticosa and Phragmites australis) and different flooding regimes on potentially harmful metals and As mobilisation from salt marsh soil polluted by mining activities were investigated (total concentrations: 536 mg kg⁻¹ As, 37 mg kg⁻¹ Cd, 6746 mg kg⁻¹ Pb, 15,320 mg kg⁻¹ Zn). The results show that the changes in redox conditions (from 300 mV to −100 mV) and pH after flooding and rewetting periods may mobilise the contaminant elements into soil solution (e.g., 100 μg L⁻¹ Cd, 30 μg L⁻¹ Pb, 7 mg L⁻¹ Zn), where they are available for plants or may be leached from the soil. Drying periods generated peaks of concentrations in the soil solution (up to 120 μg L⁻¹ Cd and 50 μg L⁻¹ Pb). The risk assessment of As and metal-polluted salt marshes should take into account flood dynamics in order to prevent metal(loid) mobilisation.     

Arsenic in rural groundwater in Ghana: Part special issue: Hydrogeochemical studies in sub-saharan Africa

Arsenic concentrations in groundwaters from two areas in Ghana, the Obuasi area in the Ashanti region and the Bolgatanga area of the Upper East region vary from <1–64 μg 1⁻¹ and <1–141 μg 1⁻¹, respectively. Sulphide minerals such as arsenopyrite and pyrite are present in the Birimian basement rocks of both areas and these form the dominant As sources. The basement aquifer is overlain by a variable thickness (ranging from <10 m to >40 m) of weathered regolith and lateritic soil. Arsenic concentrations are low in the shallowest groundwaters, but increase at greater depths (40–70 m below ground level in Obuasi and 20–40 m in Bolgatanga). At depths greater than this, total As concentrations are relatively low. The lateral and vertical variations in dissolved As concentrations are controlled by ambient pH and redox conditions and by the relative influences of sulphide oxidation and sorption. In the weathered regolith and lateritic soils, oxidation has been extensive. Shallow groundwaters are oxidizing and acidic. Under these conditions, As is readily oxidized to As(V) and may precipitate as ferric arsenate or be sorbed onto ferric hydroxide surfaces. At greater depth, groundwaters have longer contact times with the aquifer minerals and pH values are therefore higher (>6.0 in Obuasi and >6.5 in Bolgatanga). The oxidation of sulphide minerals may proceed, but dissolved O is consumed during the process and mildly reducing conditions (Eh 200–300 mV) result. Sorption of As onto ferric hydroxide minerals is less favoured under such pH and redox conditions and the element is relatively mobile. At the greatest abstraction depths, groundwaters are more reducing (Eh ≤200 mV; dissolved O <0.1 mg 1⁻¹) and few electron acceptors are available in the system to drive sulphide oxidation. Dissolved As concentrations therefore remain relatively low. The mildly reducing groundwaters in the sulphide-bearing basement aquifer are therefore of the poorest potable quality with respect to dissolved As concentrations.     

Arsenic levels in human hair,Kandal Province,Cambodia: The influences of groundwater arsenic,consumption period,age and gender

This study focused on the analysis of As levels in human hair samples collected from six villages in the Kandal Province of Cambodia. Of interest were the influence of, and interactions among, certain factors affecting As intake into the human body: As concentrations in groundwater, period of groundwater consumption, age and gender. The results revealed As levels in human hair ranging from 0.06 to 30 μg g⁻¹ with median and arithmetic mean values of 0.61 and 3.20 μg g⁻¹ (n = 68), respectively. Furthermore, a linear relationship was found between As concentrations in human hair and in the local groundwater. Arsenic (III) is the dominant species in Kandal groundwater, constituting in most cases at least 60% of the total As. Arsenic concentration ranged from 5 to 1543 μg L⁻¹, with the median value 348 μg L⁻¹ and arithmetic mean 454 μg L⁻¹. In large rural, poor areas holding most of Kandal’s 1.1 million people, up to 2 in 1000 people are believed to be at risk of cancer through the As-enriched water they drink. A toxicity risk assessment provides a hazard quotient (HQ) equaling 5.12, also a clear indication of non-carcinogenic exposure risk. On the authors’ visit to Kampong Kong commune, Kandal Province, cases of arsenicosis were diagnosed in patients as a result of drinking As-enriched groundwater.     

Geochemical comparison of waters and stream sediments close to abandoned Sb-Au and As-Au mining areas,northern Portugal

Waters from abandoned Sb-Au mining areas have higher Sb (up to 2138 μg L⁻¹), As (up to 1252 μg L⁻¹) and lower Al, Zn, Li, Ni and Co concentrations than those of waters from the As-Au mining area of Banjas, which only contain up to 64 μg L⁻¹ As. In general, Sb occurs mainly as SbO₃⁻ and As H₂AsO₄⁻. In general, waters from old Sb-Au mining areas are contaminated in Sb, As, Al, Fe, Cd, Mn, Ni and NO₂⁻, whereas those from the abandoned As-Au mining area are contaminated in Al, Fe, Mn, Ni, Cd and rarely in NO₂⁻. Waters from the latter area, immediately downstream of mine dumps are also contaminated in As. In stream sediments from Sb-Au and As-Au mining areas, Sb (up to 5488 mg kg⁻¹) and As (up to 235 mg kg⁻¹) show a similar behaviour and are mainly associated with the residual fraction. In most stream sediments, the As and Sb are not associated with the oxidizable fraction, while Fe is associated with organic matter, indicating that sulphides (mainly arsenopyrite and pyrite) and sulphosalts containing those metalloids and metal are weathered. Arsenic and Sb are mainly associated with clay minerals (chlorite and mica; vermiculite in stream sediments from old Sb-Au mining areas) and probably also with insoluble Sb phases of stream sediments. In the most contaminated stream sediments, metalloids are also associated with Fe phases (hematite and goethite, and also lepidocrocite in stream sediments from Banjas). Moreover, the most contaminated stream sediments correspond to the most contaminated waters, reflecting the limited capacity of stream sediments to retain metals and metalloids.     

Environmental geochemistry of an active Hg mine in Xunyang,Shaanxi Province,China

The Xunyang Hg mine (XMM) situated in Shaanxi Province is an active Hg mine in China. Gaseous elemental Hg (GEM) concentrations in ambient air were determined to evaluate its distribution pattern as a consequence of the active mining and retorting in the region. Total Hg (HgT) and methylmercury (MeHg) concentrations in riparian soil, sediment and rice grain samples (polished) as well as Hg speciation in surface water samples were measured to show local dispersion of Hg contamination. As expected, elevated concentrations of GEM were found, ranging from 7.4 to 410 ng m⁻³. High concentrations of HgT and MeHg were also obtained in riparian soils, ranged from 5.4 to 120 mg kg⁻¹ and 1.2 to 11 μg kg⁻¹, respectively. Concentrations of HgT and MeHg in sediment samples varied widely from 0.048 to 1600 mg kg⁻¹ and 1.0 to 39 μg kg⁻¹, respectively. Surface water samples showed elevated HgT concentrations, ranging from 6.2 to 23,500 ng L⁻¹, but low MeHg concentrations, ranging from 0.022 to 3.7 ng L⁻¹. Rice samples exhibited high concentrations of 50–200 μg kg⁻¹ in HgT and of 8.2–80 μg kg⁻¹ in MeHg. The spatial distribution patterns of Hg speciation in the local environmental compartments suggest that the XMM is the source of Hg contaminations in the study area.     

Chromium oxidation by manganese (hydr)oxides in a California aquifer

There are increasing concerns with elevated levels of Cr(VI) in the environment because it is a strong oxidant, corrosive, and carcinogenic. The concerns extend to the presence of Cr(VI) in many aquifers in California and elsewhere, where relatively high levels have been attributed to both industrial pollution and natural processes. The authors have, therefore, determined if natural redox processes contribute to the presence of high Cr(VI) concentrations (6–36 μg L⁻¹) in an aquifer in central California relative to non-detectable concentrations (<0.1 μg L⁻¹) in an adjacent aquifer. Specifically, the distribution and the redox speciation of dissolved (<0.45 μm) Cr have been compared with those of particulate Mn and Fe oxy-hydroxides in sediments, using X-ray absorption spectroscopy at the Mn and Fe L-edges. The analyses show a correlation between the presence of dissolved Cr(VI) and Mn (hydr)oxide minerals, which are the only common, naturally occurring minerals known to oxidize Cr(III) in laboratory experiments. This covariance substantiates the results of those experiments and previous field studies that indicate natural oxidation mechanisms might account for the relatively high levels of Cr(VI) in the study site, as well as for elevated concentrations in other aquifers with similar biogeochemical conditions.     

Uranium and arsenic dynamics in volcano-sedimentary basins – An exemplary study in North-Central Mexico

Uranium and As in deep groundwater of the volcano-sedimentary Villa de Reyes Graben around the city of San Luis Potosí in semi-arid North-Central Mexico (mean U: 7.6 μg L⁻¹, max. 138 μg L⁻¹; mean As: 11.4 μg L⁻¹, max. 25.8 μg L⁻¹) partly exhibit concentrations in excess of the WHO guideline values and thus endanger the quality of the most important drinking water source. To unravel the mechanisms for their enrichment in groundwater, the potential trace element sources, volcanic rocks and basin fill sediments, were characterized. A total of 131 solid and liquid samples were analyzed for major and trace element composition. The As/U hydrogeochemical signatures, their behavior during rock alteration and evidence from other major and trace element distributions, especially rare earth elements, strongly argue for dissolution of acid volcanic glass to be the dominating process of U and As release into groundwater. This natural baseline quality representing water–acid volcanic rock interaction is modified by additional trace element (preferentially As) mobilization from the sedimentary basin fill, representing a secondary source, in the course of decarbonatization of playa lake sediments and desorption from Fe-(hydr)oxide coated clastic material. The common behavior of both elements during magmatic differentiation and growing drift apart in sedimentary environments are important findings of this work. Comparison with recent findings in a similar environment suggests a common primary trace element source identification but significant differences in the evolution of As and U distribution. Geological and climatic similarity to numerous volcano-sedimentary basins makes the findings useful for water management purposes and transferable to other semi-arid regions facing challenges of geogenically impacted drinking water quality.     

Comparison of arsenic geochemical evolution in the Datong Basin (Shanxi) and Hetao Basin (Inner Mongolia), China

Insightful knowledge of geochemical processes controlling As mobility is fundamental to understanding the occurrence of elevated As in groundwater. A comparative study of As geochemistry was conducted in the Datong Basin (Shanxi) and Hetao Basin (Inner Mongolia), two strongly As-enriched areas in China. The results show that As concentrations ranged from <1–1160 μg L⁻¹ (n = 37) in the Datong Basin and <1–804 μg L⁻¹ (n = 62) in the Hetao Basin. The groundwater is of the Na-HCO₃ type in the Datong Basin and Na-Cl-HCO₃ type in the Hetao Basin. Silicate mineral weathering and cation exchange processes dominated the groundwater geochemistry in the two study areas. Principal component analysis of 99 groundwater samples using 12 geochemical parameters indicated positive correlations between concentrations of As and Fe/Mn in the Datong Basin, but no correlation of As and Fe/Mn in the Hetao Basin. Phosphate correlated well with As in the Datong Basin and Hetao Basin, suggesting phosphate competition might be another process affecting As concentrations in groundwater. High concentrations of As, Fe, and Mn occurred in the pe range −2 to −4. The results of this study further understanding of the similarities and differences of As occurrence and mobility at various locations in China.     

Dissolved metals and associated constituents in abandoned coal-mine discharges,Pennsylvania, USA. Part 1: Constituent quantities and correlations

Complete hydrochemical data are rarely reported for coal-mine discharges (CMD). This report summarizes major and trace-element concentrations and loadings for CMD at 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania. Clean-sampling and low-level analytical methods were used in 1999 to collect data that could be useful to determine potential environmental effects, remediation strategies, and quantities of valuable constituents. A subset of 10 sites was resampled in 2003 to analyze both the CMD and associated ochreous precipitates; the hydrochemical data were similar in 2003 and 1999. In 1999, the flow at the 140 CMD sites ranged from 0.028 to 2210 L s⁻¹, with a median of 18.4 L s⁻¹. The pH ranged from 2.7 to 7.3; concentrations (range in mg/L) of dissolved (0.45-μm pore-size filter) SO₄ (34–2000), Fe (0.046–512), Mn (0.019–74), and Al (0.007–108) varied widely. Predominant metalloid elements were Si (2.7–31.3 mg L⁻¹), B (<1–260 μg L⁻¹), Ge (<0.01–0.57 μg L⁻¹), and As (<0.03–64 μg L⁻¹). The most abundant trace metals, in order of median concentrations (range in μg/L), were Zn (0.6–10,000), Ni (2.6–3200), Co (0.27–3100), Ti (0.65–28), Cu (0.4–190), Cr (<0.5–72), Pb (<0.05–11) and Cd (<0.01–16). Gold was detected at concentrations greater than 0.0005 μg L⁻¹ in 97% of the samples, with a maximum of 0.0175 μg L⁻¹. No samples had detectable concentrations of Hg, Os or Pt, and less than half of the samples had detectable Pd, Ag, Ru, Ta, Nb, Re or Sn. Predominant rare-earth elements, in order of median concentrations (range in μg/L), were Y (0.11–530), Ce (0.01–370), Sc (1.0–36), Nd (0.006–260), La (0.005–140), Gd (0.005–110), Dy (0.002–99) and Sm (<0.005–79). Although dissolved Fe was not correlated with pH, concentrations of Al, Mn, most trace metals, and rare earths were negatively correlated with pH, consistent with solubility or sorption controls. In contrast, As was positively correlated with pH.     

On elevated fluoride and boron concentrations in groundwaters associated with the Lake Saint-Martin impact structure,Manitoba

Hydrogeological investigations conducted by the Geological Survey of Canada in the Lake Saint-Martin region of Manitoba have confirmed earlier reports of naturally elevated F⁻ and B concentrations in local groundwaters. Fluoride and B concentrations are highly correlated (r² = 0.905) and reach 15.1 mg/L and 8.5 mg/L, respectively. Virtually all groundwaters with F⁻ concentrations greater than the drinking water limit of 1.5 mg/L are from wells within the Lake Saint-Martin impact structure, a 208 Ma complex crater 23 km in diameter underlying a large part of the study area. The high-F⁻ groundwaters can be classified into two groups according to their anionic and isotopic compositions. Group I samples consist of Na-mixed anion groundwaters, with Cl greater than 100 mg/L and highly depleted ¹⁸O compositions indicative of recharge under much cooler climatic conditions than at present. Samples belonging to this group exhibit a striking relationship to crater morphology, and are found in an arcuate belt within the southern rim of the impact structure. Group II high-F⁻ samples consist of Na–HCO₃–SO₄ groundwaters, with little Cl, and less depleted ¹⁸O compositions. Samples belonging to this group are associated with groundwaters recharged locally, on a low ridge within the impact structure. This paper traces the probable source of high-F⁻ groundwaters to phosphatic pellets in shales of the Winnipeg Formation, a regional basal clastic unit which sub-crops at shallow depth beneath the crater rim as a result of more than 200 m of structural uplift associated with the impact event. This extensive aquifer is known elsewhere in southern Manitoba for its naturally-softened groundwaters and locally elevated F⁻ concentrations. Group I groundwaters are interpreted as discharge from the Winnipeg Formation where it abuts against crater-fill deposits. Group II high-F⁻ groundwaters are interpreted as modern recharge from within the impact structure, displacing Group I groundwaters. Thus, elevated F⁻ and B concentrations observed in groundwaters of the Lake Saint-Martin area represent the geochemical signature of upwelling from a deep regional aquifer. The previously unsuspected discharge zone occurs within an isolated sub-crop of the aquifer formed as a result of structural uplift caused by the impact event.     

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

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

Geochemistry of natural chromium occurrence in a sandstone aquifer in Bauru Basin, São Paulo State, Brazil

Anomalous concentrations of Cr(VI) occur in groundwaters of the Adamantina Aquifer, in a large region in the western state of São Paulo, sometimes exceeding the potability limit (0.05 mg L⁻¹). To identify the possible geochemical reactions responsible for the occurrence of Cr in groundwater in Urânia, borehole rock samples were collected in order to carry out mineralogical and chemical analyses. In addition, multilevel monitoring wells were installed and groundwater samples were analyzed. Analyses of the borehole rock samples show the occurrence of a geochemical anomaly of Cr in the quartzose sandstones (average concentrations of 221 ppm). Chrome-diopside is one of the main minerals contributing to this anomaly, having an average Cr content of 1505 ppm. Sequential extraction experiments indicated weakly adsorbed Cr in the order of 0.54 ppm, and this quantity is enough to provide the Cr concentrations observed in groundwater. Groundwaters from the monitoring wells proved to be stratified, with the highest concentrations of Cr(VI) (0.13 mg L⁻¹) being associated with high redox and pH values (over 10) and high concentrations of Na. Geochemical reactions that may explain the release of Cr from the solid phase to groundwater involve the release of Cr(III) from minerals (like chrome-diopside and Cr-Fe hydroxide), followed by oxidation of Cr(III) to Cr(VI), probably related to the reduction of Mn oxides present in the aquifer. Then cation exchange occurs and dissolution of carbonates which increases the pH of groundwater, resulting in the desorption and mobilization of Cr(VI) into groundwater.     

A hot spring in granite of the Western Tianshan,China

The western Tianshan range is a major Cenozoic orogenic belt in central Asia exposing predominantly Paleozoic rocks including granite. Ongoing deformation is reflected by very rugged topography with peaks over 7000 m high. Active tectonic deformation is tied to an E–W trending fracture and fault system that sections the mountain chain into geologically diverse blocks that extend parallel to the orogen. In the Muzhaerte valley upwelling hot water follows such a fault system in the Muza granite. About 20 L min⁻¹ Na–SO₄–Cl water with a temperature of 55 °C having a total mineralization of about 1 g L⁻¹ discharge from the hot spring. The water is used in a local spa that is frequented by the people of the upper Ili river area. Its waters are used for balneological purposes and the spa serves as a therapeutic institution. The major element composition of the hot water is dominated by Na and by SO₄ and Cl, Ca is a minor component. Dissolved silica (1.04 mmol L⁻¹) corresponds to a quartz-saturation temperature of 116 °C and a corresponding depth of the source of the water of about 4600 m. This temperature is consistent with Na/K and Na/Li geothermometry. The water is saturated with respect to fluorite and contains 7.5 mg L⁻¹ F⁻ as a consequence of the low Ca-concentration. The water is undersaturated with respect to the primary minerals of the reservoir granite at reservoir temperature causing continued irreversible dissolution of granite. The waters are oversaturated with respect to Ca–zeolite minerals (such as stilbite and mesolite), and it is expected that zeolites precipitate in the fracture pore space and in alteration zones replacing primary granite.     

Compositional characteristics of fluid inclusions as exploration tool for Au-mineralization at Larafella, Burkina Faso

The Larafella Au-prospect (Burkina Faso) lies within dacitic rocks of the Palaeoproterozoic Birimian greenstone belts. Gold mineralization is intimately associated with zones of cataclastic deformation. Whilst the lode-vein mineralization is closely associated with CO₂-rich fluid inclusions, the barren quartz veins are characterized by H₂O ± salt-bearing inclusions. Geochemical studies on the immediate wall-rock of the quartz veins have shown an increase of As in zones of gold enrichment, while alteration overprints such as carbonatization and chloritization cannot be correlated unequivocally with Au-mineralization. Consequently, fluid inclusion studies of quartz veins and As-anomalies constitute important exploration tools for mesothermal gold mineralization, since Au-rich zones can be distinguished from Au-depleted zones.     

Landscape scale controls on the vascular plant component of dissolved organic carbon across a freshwater delta

Lignin phenol concentrations and compositions were determined on dissolved organic carbon (DOC) extracts (XAD resins) within the Sacramento-San Joaquin River Delta (the Delta), the tidal freshwater portion of the San Francisco Bay Estuary, located in central California, USA. Fourteen stations were sampled, including the following habitats and land-use types: wetland, riverine, channelized waterway, open water, and island drains. Stations were sampled approximately seasonally from December, 1999 through May, 2001. DOC concentrations ranged from 1.3 mg L⁻¹ within the Sacramento River to 39.9 mg L⁻¹ at the outfall from an island drain (median 3.0 mg L⁻¹), while lignin concentrations ranged from 3.0 μg L⁻¹ within the Sacramento River to 111 μg L⁻¹ at the outfall from an island drain (median 11.6 μg L⁻¹). Both DOC and lignin concentrations varied significantly among habitat/land-use types and among sampling stations. Carbon-normalized lignin yields ranged from 0.07 mg (100 mg OC)⁻¹ at an island drain to 0.84 mg (100 mg OC)⁻¹ for a wetland (median 0.36 mg (100 mg OC)⁻¹), and also varied significantly among habitat/land-use types. A simple mass balance model indicated that the Delta acted as a source of lignin during late autumn through spring (10-83% increase) and a sink for lignin during summer and autumn (13-39% decrease). Endmember mixing models using S:V and C:V signatures of landscape scale features indicated strong temporal variation in sources of DOC export from the Delta, with riverine source signatures responsible for 50% of DOC in summer and winter, wetland signatures responsible for 40% of DOC in summer, winter, and late autumn, and island drains responsible for 40% of exported DOC in late autumn. A significant negative correlation was observed between carbon-normalized lignin yields and DOC bioavailability in two of the 14 sampling stations. This study is, to our knowledge, the first to describe organic vascular plant DOC sources at the level of localized landscape features, and is also the first to indicate a significant negative correlation between lignin and DOC bioavailability within environmental samples. Based upon observed trends: (1) Delta features exhibit significant spatial variability in organic chemical composition, and (2) localized Delta features appear to exert strong controls on terrigenous DOC as it passes through the Delta and is exported into the Pacific Ocean.