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.     

Redox chemistry of uranium and iron,radium geochemistry,and uranium isotopes in the groundwaters of the Lode`ve Basin,Massif Central,France

This paper discusses the geochemistry, origin and evolution of groundwaters in the Lode`ve Basin Massif Central, France, including major and trace elements (U, Ra, Ba and Fe) and the significance of the redox potential. These groundwaters originate from thermal waters by CO₂ outgassing and mixing with meteoric waters. The measured redox potential (Eh > −50 mV) is generally controlled by the ferric oxide-Fe²⁺ equilibrium; below this potential the groundwaters are saturated with respect to FeS.Redox systems other than Fe are not necessarily at equilibrium, and this is particularly true for U. In the relatively reduced waters (Eh< 100mV), U concentrations may be controlled by coffinite or uraninite. Above 100 mV, U concentrations range from 10 to 200 ppb; they correspond either to mineral dissolution, or could be controlled by an oxidized mineral.Radium mobility is strongly dependent on SO₄ concentration, and it coprecipitates with barite. Radium probably has its origin in calcium-sodium bicarbonate type waters and is not related to U mineralization.     

Hydrogeochemistry,groundwater ages and sources of salts in a granitic batholith on the Canadian Shield,southeastern Manitoba

The hydrogeochemistry of the Lac du Bonnet granitic batholith has been determined for the region of the Whiteshell Research Area (WRA) in southeastern Manitoba, Canada. This work forms part of the geosciences studies performed for the Canadian Nuclear Fuel Waste Management Program over the period 1980–1995 by Atomic Energy of Canada Limited (AECL). Knowledge of the variation of groundwater chemistry and its causes is useful in assessing the performance and safety of a nuclear fuel waste vault located at depths of up to 1000 m in a crystalline rock formation of the Canadian Shield. Groundwaters and matrix pore fluids have been obtained by standard sampling methods from shallow piezometers in clay-rich overburden, from packer-isolated borehole zones intersecting fractures or fault zones in the bedrock, and from boreholes in unfractured rock in AECL's Underground Research Laboratory (URL). Eighty-six individual fracture groundwaters have been sampled and analysed from permeable zones in 53 boreholes drilled to depths of up to 1000 m in the Lac du Bonnet batholith. In addition, 28 groundwaters from piezometers in a large wetland area near the URL have been sampled and analysed to determine the influence of clay-rich overburden on the bedrock hydrogeochemistry. Analyses have been made for major and minor ions, pH, Eh, trace metals, and stable and radioactive isotopes, to characterise these groundwaters and relate them to their hydrogeologic regimes. Shallow groundwaters in the fractured bedrock are generally dilute (TDS <0.3 g/l), Ca–Na–HCO₃ waters and show little indication of mixing with Ca–Mg–HCO₃–SO₄ groundwater from overburden sediments. The near-modern levels of ³H and ¹⁴C, and a warm-climate ²H/¹⁸O signature in these groundwaters, indicates that the upper ∼200 m of fractured bedrock contains an active groundwater circulation system with a residence time of tens to hundreds of years. Deeper fracture groundwaters (200–400 m depth) in recharge areas, are more alkaline, Na–Ca–HCO₃ waters and evolve to Na–Ca–HCO₃–Cl–SO₄ waters with increasing distance along the flow path. Isotopic data indicate the presence of a glacial melt-water component suggesting that the residence times of these waters are 10³–10⁵ a. These waters form a transition zone between the upper, advective flow regime and a deeper regime in sparsely fractured rock where groundwater in fractures and fracture zones is largely stagnant. At these depths (> 500 m), Na–Ca–Cl–SO₄ waters of increasing salinity (up to 50 g/l) with depth are found and in some fractures the waters have evolved to a Ca–Na–Cl composition. Isotopic data indicate that these waters are warm-climate and pre-glacial in origin, with residence times of over 1 Ma. Pore fluids observed to drain from the unfractured rock matrix in the URL facility are almost pure Ca–Cl in composition, ∼90 g/l salinity, and have a ²H/¹⁸O composition displaced well to the left of the global meteoric water line, about which all other WRA groundwaters lie. This information indicates that these pore fluids have undergone prolonged water-rock interaction and have residence times of 10¹–10³ Ma. Most of the deeper fracture groundwaters and pore fluids have low Br/Cl ratios and moderate to high δ³⁴S values of dissolved SO₄ which indicates that their salinity could be derived from a marine source such as the basinal sedimentary brines and evaporites to the west of the batholith. These fluids may have entered the batholith during early Paleozoic times when sedimentary rocks were deposited over the granite and were driven by a hydraulic gradient resulting from higher ground in western Canada. The hydrogeochemical data and interpretations show that below ∼500 m in the WRA, fracture-hosted groundwaters are very saline, reducing and old, and are, therefore, indicative of stagnant conditions over the period of concern for nuclear waste disposal (1 Ma). The intact rock matrix at these depths is extremely impermeable as indicated by the presence of pore fluids with unusual geochemical and isotopic characteristics. The pore fluids may represent basinal brines that have evolved geochemically and isotopically to their current composition over periods as long as 10³ Ma.     

Controls on the geochemistry of rare earth elements along a groundwater flow path in the Carrizo Sand aquifer,Texas, USA

Groundwater samples were collected along a groundwater flow path in the Carrizo Sand aquifer in south Texas, USA. Field measurements that included pH, specific conductivity, temperature, dissolved oxygen (DO), oxidation–reduction potentials (Eh in mV), alkalinity, iron speciation, and H₂S concentrations were also conducted on site. The geochemistry (i.e., concentrations, shale-normalized patterns, and speciation) of dissolved rare element elements (REEs) in the Carrizo groundwaters are described as a function of distance along a flow path. Eh and other redox indicators (i.e., DO, Fe speciation, H₂S, U, and Re) indicate that redox conditions change along the flow path in the Carrizo Sand aquifer. Within the region of the aquifer proximal to the recharge zone, groundwaters exhibit both highly oxidizing and localized mildly reducing conditions. However, from roughly 10 km to the discharge zone, groundwaters are reducing and exhibit a progressive decrease in redox conditions. Dissolved REE geochemical behavior exhibits regular variations along the groundwater flow path in the Carrizo Sand aquifer. The changes in REE concentrations, shale-normalized patterns, and speciation indicate that REEs are not conservative tracers. With flow down-gradient, redox conditions, pH and solution composite, and adsorption modify groundwater REE concentrations, fractionation patterns, and speciation.     

Detecting the near-surface redox front in crystalline bedrock using fracture mineral distribution,geochemistry and U-series disequilibrium

Oxidizing conditions normally prevail in surface waters and near-surface groundwaters, but there is usually a change to reducing conditions in groundwater at greater depth. Dissolved O₂ originally present is consumed through biogenic and inorganic reactions along the flow paths. Fracture minerals participate in these reactions and the fracture mineralogy and geochemistry can be used to trace the redox front. An important task in the safety assessment of a potential repository for the disposal of nuclear waste in crystalline bedrock, at an approximate depth of 500 m in Sweden, is to demonstrate that reducing conditions can be maintained for a long period of time. Oxygen may damage the Cu canisters that host nuclear waste; additionally, in the event of a canister failure, oxidizing conditions may increase the mobility of some radionuclides. The present study of the near-surface redox front is based on mineralogical (redox-sensitive minerals), geochemical (redox-sensitive elements) and U-series disequilibrium investigations of mineral coatings along open fractures. The fractures have been sampled along drill cores from closely spaced, 100 m deep boreholes, which were drilled during the site investigation work in the Laxemar area, south-eastern Sweden, carried out by the Swedish Nuclear Fuel and Waste Management Co. (SKB). The distribution of the redox-sensitive minerals pyrite and goethite in open fractures shows that the redox front (switch from mainly goethite to mainly pyrite in the fractures) generally occurs at about 15–20 m depth. Calcite leaching by recharging water is indicated in the upper 20–30 m and positive Ce-anomalies suggest oxidation of Ce down to 20 m depth. The U-series radionuclides show disequilibrium in most of the samples, indicating mobility of U during the last 1 Ma. In the upper 20 m, U is mainly removed (due to oxidation) or has experienced complex removal and/or deposition. At depths of 35–55 m, both deposition and removal of U are indicated. Below 55 m, recent deposition of U is generally indicated which suggests removal of U near surface (oxidation) and deposition of U below the redox front. Scattered goethite occurrences below the general redox front (down to ca 80 m) and signs of U removal at 35–55 m mostly correlate with sections of high transmissivity (and/or high fracture frequencies). This shows that highly transmissive fractures are generally required to allow oxygenated groundwaters at depth greater than ca 30 m. Removal of U (oxidation) below 55 m within the last 300 ka is not observed. Although penetration of glacial waters to great depths has been confirmed in the study area, their potential O₂ load seems to have been reduced near the surface.     

Groundwater Evolution and Mineral Alteration Reactions in the Basaltic Rock Sequence of Mt. Wasserkuppe, Germany: A Case Study

Groundwater sampling was accomplished in the basaltic sequence of the Rh?n mountain range, Germany, in order to investigate hydrochemical groundwater evolution and to delineate mineral alteration reactions involved in natural weathering. The hydrochemical compositions of near-surface groundwaters indicate a Ca/Mg–HCO₃ type with near-neutral pH and evolve to a Na–HCO₃ type with high pH at greater depth. Column experiments were performed with basaltic and phonolitic rock samples to determine individual mineral alteration reactions. The basic reactions could be related to the alteration of olivine, Ca-pyroxene, plagioclase, pyrrhotite, and feldspathoids under formation of secondary clay minerals (smectites, illite) and goethite. The mineral alteration reactions deduced from the leaching experiments by inverse modelling were found to be consistent with the mineral reactions associated with the natural groundwaters. The reactions calculated for groundwater evolution involve the alteration of primary and secondary minerals to produce low-T mineral phase. The conversion of secondary Na-beidellite to illite occurs at a later stage of groundwater evolution, reducing the concentrations of K⁺ and Mg²⁺. Near-surface groundwaters do not indicate significant cation exchange. Initial cation exchange requires elevated pH values, with Mg²⁺ removed from solution preferred to Ca²⁺. Na-alkalisation of the groundwaters at greater depth suggests the exchange of Na⁺ for Mg²⁺ and Ca²⁺ on Na-beidellite, supported by cation exchange on coatings of iron hydroxides as alteration products. Among the mature high-pH groundwater at greater depth, the dissolution of anorthite and albite has significant effect on groundwater composition.     

Redox Potential and Seasonal Porewater Biogeochemistry of Three Mountain Wetlands in Southeastern Kentucky, USA

Redox potentials (Eh) were monitored bimonthly and porewater chemistry was analyzed seasonally at three slightly-acidic, high-elevation Kentucky wetlands that differed in hydrology, parent materials, and vegetation. At all sites, Eh values were below 300 mV, which indicated that reducing conditions persisted within the upper 90 cm and fluctuated mainly within the range of iron and sulfate reduction. Significant relationships of Eh values with depth were observed only at the Martins Fork wetland, where precipitation was the primary water source. The strongest and most stable reducing conditions, observed at the Kentenia site, reflected consistently high water levels, which were sustained by ground water. The third wetland (Four Level) was distinguished by irregular Eh fluctuations coinciding with strong seasonal ground-water upwelling. Although Fe³⁺ and SO₄ ²⁻ were the primary terminal electron acceptors in all wetlands, porewater chemistry also varied significantly by season and soil depth in response to piezometric water level fluctuations. Additional factors that influenced porewater chemistry included: (1) the presence of limestone parent materials that affected porewater pH, Ca²⁺, and Mg²⁺; and (2) the prevalence of sphagnum moss or graminoid species that influenced dissolved organic carbon, CO₂, and CH₄. Results from this study indicated the diverse range and importance of multiple factors in controlling biogeochemical processes and properties in small, high-elevation Appalachian wetlands.     

Arsenic and Antimony in Groundwater Flow Systems: A Comparative Study

Arsenic (As) and antimony (Sb) concentrations and speciation were determined along flow paths in three groundwater flow systems, the Carrizo Sand aquifer in southeastern Texas, the Upper Floridan aquifer in south-central Florida, and the Aquia aquifer of coastal Maryland, and subsequently compared and contrasted. Previously reported hydrogeochemical parameters for all three aquifer were used to demonstrate how changes in oxidation–reduction conditions and solution chemistry along the flow paths in each of the aquifers affected the concentrations of As and Sb. Total Sb concentrations (Sb_T) of groundwaters from the Carrizo Sand aquifer range from 16 to 198 pmol kg⁻¹; in the Upper Floridan aquifer, Sb_T concentrations range from 8.1 to 1,462 pmol kg⁻¹; and for the Aquia aquifer, Sb_T concentrations range between 23 and 512 pmol kg⁻¹. In each aquifer, As and Sb (except for the Carrizo Sand aquifer) concentrations are highest in the regions where Fe(III) reduction predominates and lower where SO₄ reduction buffers redox conditions. Groundwater data and sequential analysis of the aquifer sediments indicate that reductive dissolution of Fe(III) oxides/oxyhydroxides and subsequent release of sorbed As and Sb are the principal mechanism by which these metalloids are mobilized. Increases in pH along the flow path in the Carrizo Sand and Aquia aquifer also likely promote desorption of As and Sb from mineral surfaces, whereas pyrite oxidation mobilizes As and Sb within oxic groundwaters from the recharge zone of the Upper Floridan aquifer. Both metalloids are subsequently removed from solution by readsorption and/or coprecipitation onto Fe(III) oxides/oxyhydroxides and mixed Fe(II)/Fe(III) oxides, clay minerals, and pyrite. Speciation modeling using measured and computed Eh values predicts that Sb(III) predominate in Carrizo Sand and Upper Floridan aquifer groundwaters, occurring as the Sb(OH)₃⁰ species in solution. In oxic groundwaters from the recharge zones of these aquifers, the speciation model suggests that Sb(V) occurs as the negatively charged Sb(OH)₆⁻ species, whereas in sufidic groundwaters from both aquifers, the thioantimonite species, HSb₂S₄ ⁻ and Sb₂S₄ ²⁻, are predicted to be important dissolved forms of Sb. The measured As and Sb speciation in the Aquia aquifer indicates that As(III) and Sb(III) predominate. Comparison of the speciation model results based on measured Eh values, and those computed with the Fe(II)/Fe(III), S(-II)/SO₄, As(III)/As(V), and Sb(III)/Sb(V) couples, to the analytically determined As and Sb speciation suggests that the Fe(II)/Fe(III), S(-II)/SO₄ couples exert more control on the in situ redox condition of these groundwaters than either metalloid redox couple.     

利用包裹体测温资料估算早子沟金矿成岩成矿压力及ｐＨ、Eh值

早子沟金矿位于秦岭造山带西段夏河—合作断裂带上,矿区成矿作用与岩浆热液及断裂构造关系密切,矿区岩浆岩内石英中含有大量熔体包裹体及流体包裹体,显微测温结果显示,熔体包裹体均一温度范围为700℃-790℃,流体包裹体分为H2O-NaCl包裹体、NaCl-H2O-CO2包裹体、H2O-CO2包裹体3种类型,包裹体均一温度范围为195℃-360℃,本文通过对熔体包裹体的研究,采用“熔体包裹体＋流体包裹体”的方法 ,估算矿区岩浆岩成岩压力为275MPa,依据断裂带流体垂直分带规律,计算得到早子沟金矿成岩深度为13.96km,成矿深度为2.10-6.02km,平均成矿深度为4.06km。表明矿区深部成矿找矿尚有很大潜力。应用刘斌及Ryzhenko and Bryzgalin推导的计算流体包裹体pH值及Eh值的公式,对矿区不同体系（类型）流体包裹体的pH值及Eh值进行了估算,其结果表明：早子沟金矿包裹体的pH值为2.25-5.88,成矿溶液为酸性,在成矿阶段pH呈升高的趋势;包裹体的Eh值为0.409-0.139V,成矿溶液体系从早期到晚期Eh呈逐渐降低的趋势。pH值及Eh值的这种变化趋势,均有利于矿区Au元素的沉淀富集。     

Investigation of groundwater mineralization in the Hammamet–Nabeul unconfined aquifer,north-eastern Tunisia: geochemical and isotopic approach

Detailed hydrogeochemical and isotopic data of groundwaters from the Hammamet–Nabeul unconfined aquifer are used to provide a better understanding of the natural and anthropogenic processes that control the groundwater mineralization as well as the sources of different groundwater bodies. It has been demonstrated that groundwaters, which show Na–Cl and Ca–SO₄–Cl water facies, are mainly influenced by the dissolution of evaporates, the dedolomitization and the cation-exchange process; and supplementary by anthropogenic process in relation with return flow of irrigation waters. The isotopic signatures permit to classify the studied groundwaters into two different groups. Non-evaporated groundwaters that are characterized by depleted δ ¹⁸O and δ ²H contents highlighting the importance of modern recharge at higher altitude. Evaporated groundwaters with enriched contents reflecting the significance infiltration of return flow irrigation waters. Tritium data in the studied groundwaters lend support to the existence of pre-1950 and post-1960 recharge. Carbon-14 activities in shallow wells that provide evidence to the large contamination by organic ¹⁴C corroborate the recent origin of the groundwaters in the study area.     

Fe and Mn levels regulated by agricultural activities in alluvial groundwaters underneath a flooded paddy field

Iron and Mn concentrations in fresh groundwaters of alluvial aquifers are generally high in reducing conditions reflecting low SO₄ concentrations. The mass balance and isotopic approaches of this study demonstrate that reduction of SO₄, supplied from agricultural activities such as fertilization and irrigation, is important in lowering Fe and Mn levels in alluvial groundwaters underneath a paddy field. This study was performed to investigate the processes regulating Fe and Mn levels in groundwaters of a point bar area, which has been intensively used for flood cultivation. Four multilevel-groundwater samplers were installed to examine the relationship between geology and the vertical changes in water chemistry. The results show that Fe and Mn levels are regulated by the presence of NO₃ at shallow depths and by SO₄ reduction at the greater depths. Isotopic and mass balance analyses revealed that NO₃ and SO₄ in groundwater are mostly supplied from the paddy field, suggesting that the Fe-and Mn-rich zone of the study area is confined by the agricultural activities. For this reason, the geologic conditions controlling the infiltration of agrochemicals are also important for the occurrence of Fe/Mn-rich groundwaters in the paddy field area.     

Dolomitization by hypersaline reflux into dense groundwaters as revealed by vertical trends in strontium and oxygen isotopes: Upper Muschelkalk,Switzerland

The Trigonodus Dolomit is the dolomitized portion of the homoclinal ramp sediments of the Middle Triassic Upper Muschelkalk in the south‐east Central European Basin. Various dolomitizing mechanisms, followed by recrystallization, have been previously invoked to explain the low δ¹⁸O, high ⁸⁷Sr/⁸⁶Sr, extensive spatial distribution and early nature of the replacive matrix dolomites. This study re‐evaluates the origin, timing and characteristics of the dolomitizing fluids by examining petrographic and isotopic trends in the Trigonodus Dolomit at 11 boreholes in northern Switzerland. In each borehole the ca 30 m thick unit displays the same vertical trends with increasing depth: crystal size increase, change from anhedral to euhedral textures, ultraviolet‐fluorescence decrease, δ¹⁸O_VPDB decrease from ?1·0‰ at the top to ?6·7‰ at the base and an ⁸⁷Sr/⁸⁶Sr increase from 0·7080 at the top to 0·7117 at the base. Thus, dolomites at the top of the unit record isotopic values similar to Middle Triassic seawater (δ¹⁸O_VSMOW = 0‰; ⁸⁷Sr/⁸⁶Sr = 0·70775) while dolomites at the base record values similar to meteoric groundwaters from the nearby Vindelician High (δ¹⁸O_VSMOW = ?4·0‰; ⁸⁷Sr/⁸⁶Sr = >0·712). According to water–rock interaction modelling, a single dolomitizing or recrystallizing fluid cannot have produced the observed isotopic trends. Instead, the combined isotopic, geochemical and petrographic data can be explained by dolomitization via seepage‐reflux of hypersaline brines into dense, horizontally‐advecting groundwaters that already had negative δ¹⁸O and high ⁸⁷Sr/⁸⁶Sr values. Evidence for the early groundwaters is found in meteoric calcite cements that preceded dolomitization and in fully recrystallized dolomites with isotopic characteristics identical to the groundwaters following matrix dolomitization. This study demonstrates that early groundwaters can play a decisive role in the formation and recrystallization of massive dolomites and that the isotopic and textural signatures of pre‐existing groundwaters can be preserved during seepage‐reflux dolomitization in low‐angle carbonate ramps.     

Volcanic degassing at Somma–Vesuvio (Italy) inferred by chemical and isotopic signatures of groundwater

A geochemical model is proposed for water evolution at Somma–Vesuvio, based on the chemical and isotopic composition of groundwaters, submarine gas emission and chemical composition of the dissolved gases. The active degassing processes, present in the highest part of the volcano edifice, strongly influence the groundwater evolution. The geological–volcanological setting of the volcano forces the waters infiltrating at Somma–Vesuvio caldera, enriched in volcanic gases, to flow towards the southern sector to an area of high pCO₂ groundwaters. Reaction path modelling applied to this conceptual model, involving gas–water–rock interaction, highlights an intense degassing process in the aquifer controlling the chemical and isotopic composition of dissolved gases, total dissolved inorganic C (TDIC) and submarine gas emission. Mapping of TDIC shows a unique area of high values situated SSE of Vesuvio volcano with an average TDIC value of 0.039 mol/L, i.e., one order of magnitude higher than groundwaters from other sectors of the volcano. On the basis of TDIC values, the amount of CO₂ transported by Vesuvio groundwaters was estimated at about 150 t/d. This estimate does not take into account the fraction of gas loss by degassing, however, it represents a relevant part of the CO₂ emitted in this quiescent period by the Vesuvio volcanic system, being of the same order of magnitude as the CO₂ diffusely degassed from the crater area.     

Development of an apparatus to measure groundwater qualities in situ and to sample groundwater using boreholes

 To accurately measure the pH, Eh, EC and temperature of groundwater retrieved from boreholes, a deep groundwater sampling apparatus was developed which provided sensory measurements both in situ and in a flow-through cell at ground level. Under a pressure of 1×10⁶ Pa the in situ accuracy of the apparatus sensor was within the following limits: pH ±0.2, temperature ±0.1°C, Eh ±10 mV, and EC ±2.4%. The measuring and sampling of deep groundwater from a borehole of more than 1000 m in depth was performed continuously for 30 days. Values of pH were the same for the in situ sensor, the flow-through cell sensor and the laboratory measurements of the sampled water. At the beginning of the sampling period, Eh values of the in situ sensor indicated deep groundwater conditions. The apparatus is particularly useful for Eh measurement. Chemical composition and stable isotope ratios indicated that the groundwater sampled from more than 1000 m depth was a connate water with a chemical composition slightly different from seawater of the present time, and the groundwater retrieved from 800 m depth was a meteoric water. Natural radioactive elements are thought to be the origin of the tritium in the groundwater retrieved from the 1000 m depth. Received: 6 August 1996 / Accepted: 22 October 1996     

Isotopic and morphological features of fracture calcite from granitic rocks of the Tono area,Japan: a promising palaeohydrogeological tool

This study aimed to develop a methodology for assessing the hydrochemical evolution of a groundwater system, using fracture-filling and fracture-lining calcite. Fracture calcite in deep (to ca. 1000 m) granitic rocks of the Tono area, central Japan, was investigated by optical and electron microscopy, and chemical and isotopic analysis. Coupled with geological evidence, these new data imply 3 main origins for the waters that precipitated calcite: (1) relatively high-temperature hydrothermal solutions, precipitating calcite distinguished by δ¹⁸O_SMOW from −3 to ca. 10‰, and with δ¹³C_PDB from ca. −18 to −7‰; (2) seawater, probably partly of Miocene age, which precipitated calcite distinguished by δ¹³C_PDB of ca. 0‰ and δ¹⁸O_SMOW > ca. 20‰; (3) fresh water, with a variable δ¹³C_PDB composition, but which precipitated calcite distinguished by δ¹³C_PDB that was significantly < 0‰ and as low as ca. −29‰ and δ¹⁸O_SMOW > ca. 17‰. Data for ¹⁴C suggest that at least some of the fresh-water calcite formed within the last 50 ka. The present day hydrogeological regime in the Tono area is also dominated by fresh groundwater. However, the marine calcite of probable Miocene age found at depth has shown no evidence for dissolution and many different calcite crystal forms have been preserved. Studies of other groundwater systems have correlated similar crystallographic variations with variations in the salinity of coexisting groundwaters. When this correlation is applied to the Tono observations, the calcite crystal forms imply a similar range of groundwater salinity to that inferred from the isotopic data. Thus, the present study suggests that even in presently low-salinity groundwater systems, calcite morphological variations may record the changing salinity of coexisting groundwaters. It is suggested that calcite morphological data, coupled with isotopic data, could provide a powerful palaeohydrogeological tool in such circumstances.     

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.     

Corrosion of brass in a marine environment: mineral products and their relationship to variable oxidation and reduction conditions

Minerals coating brass ammunition shells that rested at the bottom of Halifax Harbour, Nova Scotia, for 52 a have been identified by X-ray diffraction and analytical scanning electron microscopy. The admiralty brass shells, partially buried in anoxic muds, straddle a strong Eh gradient ranging from 0 mV to values characteristic of oxygenated seawater. Whereas the brass surface in contact with the sediment has been preserved, parts of the shells exposed to seawater have corroded throughout their thickness. The corrosion products identified include metallic Cu, djurleite (Cu_1.96S), cuprite (Cu₂O), atacamite (Cu₂Cl(OH)₃), spertiniite (Cu(OH)₂) and hydrozincite (Zn₅(CO₃)₂(OH)₆). These products are those predicted thermodynamically on the basis of ambient Eh and pH. However, this study also revealed the presence of a mineral not previously known to exist and tentatively identified as Cu₁₄Zn₁₄Cl₅(SO₄)₅(OH)₄₁.H₂O. This “new” mineral seems to have a stability field in Eh–pH diagrams similar to that of connellite (Cu₁₉Cl₄SO₄(OH)₃₂.2H₂O).     

Source,transport, and fate of rhenium,selenium, molybdenum,arsenic, and copper in groundwater associated with porphyry–Cu deposits,Atacama Desert,Chile

We collected groundwaters in and around a large (313 Mt at 1.08% Cu and 0.3% cutoff) undisturbed porphyry copper deposit (Spence) in the hyperarid Atacama Desert of northern Chile, which is buried beneath 30–180 m of Miocene piedmont gravels. Groundwaters within and down-flow of the Spence deposit have elevated Se (up to 800 μg/l), Re (up to 31 μg/l), Mo (up to 475 μg/l) and As (up to 278 μg/l) concentrations compared to up-flow waters (interpreted to represent regional groundwater flow). In contrast, Cu is only elevated (up to 2036 μg/l) in groundwaters recovered from within the deposit; Cu concentrations are low down gradient of the deposit. The differential behavior of the metals/metalloids occurs because the former group dissolves as anions, enhancing their mobility, whereas the base metals dissolve as cations and are lost from solution most likely through adsorption to clay surface exchange sites and through formation of secondary copper chlorides, carbonates, and oxides. Most groundwaters within and down-flow of the deposit have Eh–pH values around the Fe^II/Fe^III phase boundary, limiting the impact of Fe-oxyhydroxides on oxyanions mobility. Se, Re, Mo, and As are all mobile (with filtered/unfiltered samples ～ 1) to the limit of sampling 2 km down gradient from the deposit. The increase in ore-related metals, metalloids, and sulfate and decrease in sulfate–S isotope ratios (from values similar to regional salars, + 4 to + 8‰ δ³⁴S_CDT to lower values closer to hypogene sulfides, + 1 to + 4‰ δ³⁴S_CDT) is consistent with active water–rock reactions between saline groundwaters and the Spence deposit. It is likely that hypogene and/or supergene sulfides are being oxidized under the present groundwater conditions and mineral saturation calculations suggest that secondary copper minerals (antlerite, atacamite, malachite) may also be actively forming, suggesting that supergene and exotic copper mineralization is possible even under the present hyperarid climate of the Atacama Desert.     

Evaluation of groundwater quality in coastal areas: implications for sustainable agriculture

Seawater intrusion is a problem in the coastal areas of Korea. Most productive agricultural fields are in the western and southern coastal areas of the country where irrigation predominantly relies on groundwater. Seawater intrusion has affected agricultural productivity. To evaluate progressive encroachment of saline water, the Korean government established a seawater intrusion monitoring well network, especially in the western and southern part of the peninsula. Automatic water levels and EC monitoring and periodic chemical analysis of groundwater help track salinization. Salinization of fresh groundwater is highly associated with groundwater withdrawal. A large proportion of the groundwaters are classified as Na–Cl and Ca–Cl types. The Na–Cl types represent effects of seawater intrusion. The highest EC level was over 1.6 km inland and high Cl values were observed up to 1.2 km inland. Lower ratios of Na/Cl and SO₄/Cl than seawater values indicate the seawater encroachment. A linear relation between Na and Cl represents simple mixing of the fresh groundwater with the seawater. The saline Na–Cl typed groundwaters showed Br/Cl ratios similar to or less than seawater values. The Ca–HCO₃ type groundwaters had the highest Br/Cl ratios. Substantial proportions of the groundwaters showed potential for salinity and should be better managed for sustainable agriculture.