Laser oxygen isotope analysis of weathering goethite from the lateritic profile of Yaou,French Guiana: paleoweathering and paleoclimatic implications

Oxygen isotopic compositions of weathering goethite pseudomorphs after pyrite in the lateritic profile of Yaou, French Guiana, were measured by laser fluorination. The laterite at Yaou is composed of a 25 m thick saprolite overlain by a 3 m thick latosol. Petrographic observations indicate that the pseudomorphic replacement of pyrite by goethite occurs at or near the weathering front and is complete. The goethite pseudomorphs are essentially devoid of Al and are progressively dissolved and partially replaced by a microcrystalline plasma of kaolinite and goethite in the upper horizons (latosol) of the profile.The laser technique used in this study permitted the determination of the δ¹⁸O value of individual grains of goethite and the investigation of grain-to-grain variation within a single sample (horizon) as well as vertical variation with depth. In the latosol, the goethite δ¹⁸O values range from 0.8 to 3.2%‰ and exhibit significant grain-to-grain and vertical variation. This most likely reflects undetected intragrain contamination with microcrystalline kaolinite. In the saprolite, the goethite δ¹⁸O values are consistent, ranging from 1.0 to 1.8%‰ between 3 and 18 m depth, and from 2.5 to 3.3‰ between 23 m depth and the weathering front at 28 m. Oxygen isotope compositions of present groundwater, “soil water” and rainfall at Yaou were also measured, and compared with calculated isotopic compositions for goethite-forming waters. Goethite pseudomorphs in the lower part of the saprolite are in isotopic equilibrium with present groundwater, indicating that they may be forming today or that they formed in the recent past under climatic conditions similar to present conditions. In contrast, goethite pseudomorphs found higher in the profile are not in isotopic equilibrium with present water but with a water depleted in¹⁸O by ≈ 1.50% relative to present groundwater. It is suggested that these low-δ¹⁸O pseudomorphs are probably older and formed under different paleoclimatic conditions, at a time when climatic regimes were possibly more monsoonal than today. This is in agreement with models of climatic evolution derived from pedological considerations.The results of this study suggest that goethite pseudomorphs in ancient saprolites may preserve their original O isotopic composition acquired at the weathering front, and may, therefore, be used as indicators of changes in weathering-climatic conditions during the evolution of a profile.     

Behavior of stable isotopes of dissolved oxygen,dissolved inorganic carbon and nitrate in groundwater at a former wood treatment facility containing hydrocarbon contamination

The speciation and mobility of a variety of chemical species in groundwater are strongly influenced by redox and pH conditions. Dissolved O₂ (DO) and dissolved inorganic C (DIC) concentrations are significant controls of these conditions, respectively. It is not always clear what the major processes are that influence changes in the concentration of DO and DIC across a groundwater flowpath. The combined use of the stable isotope compositions of DO (δ¹⁸O–DO) and DIC (δ¹³C–DIC) has the potential to help investigators discriminate between sources and sinks of DO and DIC in groundwater systems.     

The fate of nitrogen and sulfur in hard-rock aquifers as shown by sulfate-isotope tracing

Stable SO₄ isotopes (δ³⁴S_-SO4 and δ¹⁸O_-SO4), and more occasionally δ¹⁵N_-NO3 were studied in groundwater from seven hard-rock aquifer catchments. The sites are located in Brittany (France) and all are characterized by intensive agricultural activity. The purpose of the study was to investigate the potential use of these isotopes for highlighting the fate of both SO₄ and NO₃ in the different aquifer compartments. Nitrate-contaminated groundwater occurs in the regolith; δ³⁴S fingerprints the origin of SO₄, such as atmospheric deposition and fertilizers, and δ¹⁸O_-SO4 provides evidence of the cycling of S within soil. The correlation between the δ¹⁸O_-SO4 of sulfates and the δ¹⁵N_-NO3 of nitrates suggests that S and N were both cycled in soil before being leached to groundwater. Autotrophic and heterotrophic denitrification was noted in fissured aquifers and in wetlands, respectively, the two processes being distinguished on the basis of stable SO₄ isotopes. During autotrophic denitrification, both δ³⁴S_-SO4 and δ¹⁸O_-SO4 decrease due to the oxidation of pyrite and the incorporation of O from the NO₃ molecule in the newly formed SO₄. Within wetlands, fractionation occurs of O isotopes on SO₄ in favour of lighter isotopes, probably through reductive assimilation processes. Fractionation of S isotopes is negligible as the redox conditions are not sufficiently reductive for dissimilatory reduction. δ³⁴S_-SO4 and δ¹⁸O_-SO4 data fingerprint the presence of a NO₃-free brackish groundwater in the deepest parts of the aquifer. Through mixing with present-day denitrified groundwater, this brackish groundwater can contribute to significantly increase the salinity of pumped water from the fissured aquifer.     

Hydrogeochemistry and stable isotopes of thermal springs: earthquake-related chemical changes along Belice Fault (Western Sicily)

Three geothermal systems, Montevago, Castellammare-Alcamo and Sciacca, are located along the main seismogenetic structures in Western Sicily. Concentrations of dissolved species including the gases CO₂, N₂, He and the results of stable isotope measurements δ¹⁸O, δD and δ¹³C_TDIC in water samples collected from six thermal springs and 28 cold discharges were used to characterise their feeder aquifers and to reveal the relationships between water chemistry and regional seismicity. The Sciacca thermal springs differ chemically and isotopically from those of Montevago and the Castellammare-Alcamo areas. The inferred deep end-members of the thermal waters of Montevago and Castellammare-Alcamo are almost similar, suggesting that both systems are fed by carbonate waters and selenite waters. A slight contribution (1–3%) of seawater, during groundwater ascent it is also present. The Sciacca thermal springs are fed by a deep reservoir comprising a mixture of 50% carbonate water and 50% seawater. During ascent towards the surface, these waters interact with NaCl-rich evaporite layers. By combination of published and present data significant temporal variations of temperature and some chemical parameters in the thermal waters of Western Sicily have been recorded. These variations were mostly between 1966 and 1969. Although the data are discontinuous it is still possible to reveal a direct link between physico–chemical changes in the Acqua Pia and Terme Selinuntine springs and the 1968 Belice Valley earthquake. Within the studied springs, two kinds of geochemical behaviour have been recognised. The chemistry of the Montevago thermal springs was permanently changed in response to changes in the groundwater system. Water temperature and dissolved SO₄, Cl, Na, and TDS showed minimum values before the earthquake and maximum values after the event. Almost constant values substantially higher than before, were recorded after the seismic event. Conversely, the temporal variations observed in the waters of the Terme Selinuntine spring, from 1965 to 1991, exhibit a transient increase most probably caused by a temporary contribution of deep CO₂-rich fluids caused by the strain release during the 1968 earthquake.     

Hydrochemical and isotopic characterisation of the Bathonian and Bajocian coastal aquifer of the Caen area (northern France)

This paper describes the geochemical evolution of groundwater in the Bathonian and Bajocian aquifer along its flowpath. Since this aquifer represents one of the main sources of fresh water supply in the Caen area and has been subjected to a Holocene marine intrusion, its management requires a sound knowledge of (1) the primary conditions and (2) the potential influence of either natural or anthropogenic pressures. Groundwater vertical sampling validity is discussed with the contribution of high resolution temperature logging. The main processes of geochemical evolution along a groundwater flow line and the sea-water intrusion characteristics are discussed using ionic concentrations (Br⁻, F⁻ and major elements) and isotopes (water δ²H and δ¹⁸O, TDIC δ¹³C and A¹⁴C, sulphate δ¹⁸O and δ³⁴S). As the ¹³C content of TDIC is used as a tracer of water-rock interaction, it shows evidence of specific chemical and isotopic evolutions of groundwater within the aquifer, both related to water-rock interaction and mineral equilibria in groundwater. All the above-mentioned tracers evolve downflow: cation concentrations are modified by exchange with clay minerals allowing a high F⁻ concentration in groundwater, whereas Br⁻ and SO²⁻₄ concentrations appear to be redox condition dependant. Superimposed on these geochemical patterns, δ¹⁸O and δ²H compositions indicate that aquifer recharge has varied significantly through time. The chemical evolution of groundwater is locally affected by a salty water intrusion that is characterised by mixing between Flandrian fresh water and sea-water which has interacted with peat as evidenced by a high Br⁻/Cl⁻ ratio and SO²⁻₄ reduction.     

Interaction between shallow and deep aquifers in the Tivoli Plain (Central Italy) enhanced by groundwater extraction: A multi-isotope approach and geochemical modeling

In the Tivoli Plain (Rome, Central Italy) the interaction between shallow and deep groundwater flow systems enhanced by groundwater extraction has been investigated using isotopic and chemical tracers. A conceptual model of the groundwater flowpaths has been developed and verified by geochemical modeling. A combined hydrogeochemical and isotopic investigation using ion relationships such as DIC/Cl⁻, Ca/(Ca + Mg)/SO₄/(SO₄ + HCO₃), and environmental isotopes (δ¹⁸O, δ²H, ⁸⁷Sr/⁸⁶Sr, δ³⁴S and δ¹³C) was carried out in order to determine the sources of recharge of the aquifer, the origin of solutes and the mixing processes in groundwater of Tivoli Plain. Multivariate statistical methods such as principal component analysis and Cluster analyses have confirmed the existence of different geochemical facies and the role of mixing in the chemical composition of the groundwater.     

Stable-isotope and solute-chemistry approaches to flow characterization in a forested tropical watershed,Luquillo Mountains,Puerto Rico

The prospect of changing climate has led to uncertainty about the resilience of forested mountain watersheds in the tropics. In watersheds where frequent, high rainfall provides ample runoff, we often lack understanding of how the system will respond under conditions of decreased rainfall or drought. Factors that govern water supply, such as recharge rates and groundwater storage capacity, may be poorly quantified. This paper describes 8-year data sets of water stable isotope composition (δ²H and δ¹⁸O) of precipitation (4 sites) and a stream (1 site), and four contemporaneous stream sample sets of solute chemistry and isotopes, used to investigate watershed response to precipitation inputs in the 1780-ha Río Mameyes basin in the Luquillo Mountains of northeastern Puerto Rico. Extreme δ²H and δ¹⁸O values from low-pressure storm systems and the deuterium excess (d-excess) were useful tracers of watershed response in this tropical system. A hydrograph separation experiment performed in June 2011 yielded different but complementary information from stable isotope and solute chemistry data. The hydrograph separation results indicated that 36% of the storm rain that reached the soil surface left the watershed in a very short time as runoff. Weathering-derived solutes indicated near-stream groundwater was displaced into the stream at the beginning of the event, followed by significant dilution. The more biologically active solutes exhibited a net flushing behavior. The d-excess analysis suggested that streamflow typically has a recent rainfall component (∼25%) with transit time less than the sampling resolution of 7 days, and a more well-mixed groundwater component (∼75%). The contemporaneous stream sample sets showed an overall increase in dissolved solute concentrations with decreasing elevation that may be related to groundwater inputs, different geology, and slope position. A considerable amount of water from rain events runs off as quickflow and bypasses subsurface watershed flowpaths, and better understanding of shallow hillslope and deeper groundwater processes in the watershed will require sub-weekly data and detailed transit time modeling. A combined isotopic and solute chemistry approach can guide further studies to a more comprehensive model of the hydrology, and inform decisions for managing water supply with future changes in climate and land use.     

Geochemistry of the mineral waters and gases of the Mukhen deposit,Far East

This work reports new hydrochemical data on the two types of cold high p CO₂ groundwaters from the Mukhen deposit (Khabarovsk district). The first type is classed with HCO₃-Ca-Mg waters with a relatively low TDS (up to 1.7 g/l) and high concentrations of Fe²⁺, Mn²⁺, Ba²⁺, and SiO₂. The second type is of HCO₃-Na composition with high TDS (up to 14 g/l) and elevated Li⁺, B, Sr²⁺, Br^?, and I^?. New oxygen (δ¹⁸O) and hydrogen (δD) isotopic data on the waters and carbon (δ¹³C) isotopic data on the gas phase, together with a detailed geological and hydrogeological analysis of the study area, allowed us to decipher the origin of both the mineral waters. Based on the tritium content (³H) in the ground and surface waters of the area, the duration of the mineral water circulation was estimated. It was established that the both types of groundwaters were formed during interaction of meteoric water with bedrock under active influence of CO₂, however HCO₃-Na groundwaters have longer residence time than HCO₃-Ca-Mg groundwaters.     

Groundwater in the Broken Hill region,Australia: recognising interaction with bedrock and mineralisation using S,Sr and Pb isotopes

The supergiant Pb–Zn–Ag Broken Hill orebody and numerous other minor mineral deposits occur within the limited outcrop of the Proterozoic Curnamona Province of Australia. The vast majority of this Province is concealed by up to 200 m of transported regolith, hampering conventional exploration strategies. Approximately 300 groundwater samples were collected over the southern Curnamona Province to test whether this medium could be helpful in the search for hidden mineral deposits. Sulphur, Sr and Pb isotope composition of the groundwaters were determined and S excess (S_XS), i.e., the amount of S that can be ascribed neither to evaporation nor to mixing, was calculated. Many samples were recognised to have undergone an addition of ³⁴S-depleted S, which can be attributed to oxidation of sulfides with a Broken Hill type δ³⁴S signature (average ∼0‰ V-CDT). Furthermore, Sr isotopes identify the broad types of bedrock that the groundwater has been interacting with, from the less radiogenic Adelaidean rocks (and minerals) in the west (groundwater ⁸⁷Sr/⁸⁶Sr ratio as low as 0.708) to the highly radiogenic Willyama Supergroup in the east (⁸⁷Sr/⁸⁶Sr ratio up to 0.737). The groundwaters have ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb ratios comparable to, or intermediate between, various mineralisation types recognised in the area (Broken Hill, Rupee, Thackaringa, etc., types). The few samples taken in the vicinity of known mineralisation yield positive indicators (positive S_XS, low δ³⁴S, ⁸⁷Sr/⁸⁶Sr signature of bedrock type and Pb isotope fingerprinting of mineralisation type). This study also highlights several new locations under sedimentary cover where these indicators suggest interaction with mineralisation.     

The sources and budget for dissolved sulfate in a fractured carbonate aquifer,southern Sacramento Mountains,New Mexico,USA

Climate change in the SW USA is likely to involve drier conditions and higher surface temperatures. In order to better understand the evolution of water chemistry and the sources of aqueous SO₄ in these semi-arid settings, chemical and S isotope compositions were determined of springs, groundwater, and bedrock associated with a Permian fractured carbonate aquifer located in the southern Sacramento Mountains, New Mexico, USA. The results suggest that the evolution of water chemistry in the semi-arid carbonate aquifer is mainly controlled by dedolomitization of bedrock, which was magnified by increasing temperature and increasing dissolution of gypsum/anhydrite along the groundwater flow path. The δ³⁴S of dissolved SO₄ in spring and groundwater samples varied from +9.0‰ to +12.8‰, reflecting the mixing of SO₄ from the dissolution of Permian gypsum/anhydrite (+12.3‰ to +13.4‰) and oxidation of sulfide minerals (−24.5‰ to −4.2‰). According to S isotope mass balance constraints, the contribution of sulfide-derived SO₄ was considerable in the High Mountain recharge areas, accounting for up to ∼10% of the total SO₄ load. However, sulfide weathering decreased in importance in the lower reaches of the watershed. A smaller SO₄ input of ∼2–4% was contributed by atmospheric wet deposition. This study implies that the δ³⁴S variation of SO₄ in semi-arid environments can be complex, but that S isotopes can be used to distinguish among the different sources of weathering. Here it was found that H₂SO₄ dissolution due to sulfide oxidation contributes up to 5% of the total carbonate weathering budget, while most of the SO₄ is released from bedrock sources during dedolomitization.     

Carbon, sulfur, and oxygen isotope evidence for a strong depth gradient and oceanic oxidation after the Ediacaran Hankalchough glaciation

In order to understand spatial variations of stable isotope geochemistry in the Quruqtagh basin (northwestern China) in the aftermath of an Ediacaran glaciation, we analyzed carbonate carbon isotopes (δ¹³C_carb), carbonate oxygen isotopes (δ¹⁸O_carb), carbonate associated sulfate sulfur (δ³⁴S_CAS) and oxygen isotopes (δ¹⁸O_CAS), and pyrite sulfur isotopes (δ³⁴S_py) of a cap dolostone atop the Ediacaran Hankalchough glacial diamictite at four sections. The four studied sections (YKG, MK, H and ZBS) represent an onshore-offshore transect in the Quruqtagh basin. Our data show a strong paleobathymetry-dependent isotopic gradient. From the onshore to offshore sections, δ¹³C_carb values decrease from −2‰ to −16‰ (VPDB), whereas δ¹⁸O_carb values increase from −4‰ to −1‰ (VPDB). Both δ³⁴S_CAS and δ³⁴S_py show stratigraphic variations in the two onshore sections (MK and YKG), but are more stable in the two offshore sections (H and ZBS). δ¹⁸O_CAS values of onshore samples are consistent with terrestrial oxidative weathering of pyrite. We propose that following the Hankalchough glaciation seawater in the Quruqtagh basin was characterized by a strong isotopic gradient. The isotopic data may be interpreted using a three-component mixing model that involves three reservoirs: deep-basin water, surface water, and terrestrial weathering input. In this model, the negative δ¹³C_carb values in the offshore sections are related to the upwelling of deep-basin water (where anaerobic oxidation of dissolved organic carbon resulted in ¹³C-depleted DIC), whereas sulfur isotope variations are strongly controlled by surface water sulfate and terrestrial weathering input derived from oxidative weathering of pyrite. The new data provide evidence for the oceanic oxidation following the Hankalchough glaciation.     

Controls of δS and δO in dissolved sulphate: Learning from a detailed survey in the Llobregat River (Spain)

The S and O isotopic composition of dissolved SO₄, used as a tracer for SO₄ sources, was applied to the water of the Llobregat River system (NE Spain). The survey was carried out at 30 sites where surface water was sampled on a monthly basis over a period of 2a. The concentration of dissolved SO₄ varied from 20 to 1575 mg L⁻¹. Sulphur isotopic compositions clustered in two populations: one – 93% of the samples – had positive values with a mode of +9‰; the other had negative values and a mode of −5‰. Data for δ¹⁸O_SO4 showed a mean value of +11‰, with no bi-modal distribution, though lower values of δ¹⁸O corresponded to samples with negative δ³⁴S. These values can not be explained solely by the contribution of bedrock SO₄ sources: that is, sulphide oxidation and the weathering of outcrops of sulphates, though numerous chemical sediments exist in the basin. Even in a river with a high concentration of natural sources of dissolved SO₄, such as the Llobregat River, the δ³⁴S values suggest that dissolved SO₄ is controlled by a complex mix of both natural and anthropogenic sources. The main anthropogenic sources in this basin are fertilizers, sewage, potash mine effluent and power plant emissions. Detailed river water sampling, together with the chemical and isotopic characterisation of the main anthropogenic inputs, allowed determination of the influence of redox processes, as well as identification of the contribution of natural and anthropogenic SO₄ sources and detection of spatial variations and seasonal changes among these sources. For instance, in the Llobregat River the input of fertilisers is well marked seasonally. Minimum values of δ³⁴S are reported during fertilization periods – from January to March – indicating a higher contribution of this source. The dual isotope approach, δ³⁴S and δ¹⁸O, is useful to better constrain the sources of SO₄. Moreover, in small-scale studies, where the inputs are well known and limited, the mixing models can be enhanced and the contribution of the different sources can be quantified to some extent.     

Groundwater recharge,circulation and geochemical evolution in the source region of the Blue Nile River,Ethiopia

Geochemical and environmental isotope data were used to gain the first regional picture of groundwater recharge, circulation and its hydrochemical evolution in the upper Blue Nile River basin of Ethiopia. Q-mode statistical cluster analysis (HCA) was used to classify water into objective groups and to conduct inverse geochemical modeling among the groups. Two major structurally deformed regions with distinct groundwater circulation and evolution history were identified. These are the Lake Tana Graben (LTG) and the Yerer Tullu Wellel Volcanic Lineament Zone (YTVL). Silicate hydrolysis accompanied by CO₂ influx from deeper sources plays a major role in groundwater chemical evolution of the high TDS Na–HCO₃ type thermal groundwaters of these two regions. In the basaltic plateau outside these two zones, groundwater recharge takes place rapidly through fractured basalts, groundwater flow paths are short and they are characterized by low TDS and are Ca–Mg–HCO₃ type waters. Despite the high altitude (mean altitude ∼2500 masl) and the relatively low mean annual air temperature (18 °C) of the region compared to Sahelian Africa, there is no commensurate depletion in δ¹⁸O compositions of groundwaters of the Ethiopian Plateau. Generally the highland areas north and east of the basin are characterized by relatively depleted δ¹⁸O groundwaters. Altitudinal depletion of δ¹⁸O is 0.1‰/100 m. The meteoric waters of the Blue Nile River basin have higher d-excess compared to the meteoric waters of the Ethiopian Rift and that of its White Nile sister basin which emerges from the equatorial lakes region. The geochemically evolved groundwaters of the YTVL and LTG are relatively isotopically depleted when compared to the present day meteoric waters reflecting recharge under colder climate and their high altitude.     

Tracing the decomposition of dissolved organic carbon in artificial groundwater recharge using carbon isotope ratios

Reducing the concentration of dissolved organic C (DOC) in water is one of the main challenges in the process of artificial groundwater recharge. At the Tuusula waterworks in southern Finland, surface water is artificially recharged into an esker by pond infiltration and an equal amount of groundwater is daily pumped from the aquifer. This groundwater study was conducted to consider the role of redox processes in the decomposition of DOC. The isotopic composition of dissolved inorganic C (δ¹³C_DIC) in the recharged water was used as a tracer for redox reactions. The isotopic composition of O and H in water was determined in order to calculate mixing ratios between the local groundwater and the infiltrated surface water. Three distinct processes in the reduction of the DOC content were traced using isotopic methods and concentration analyses of DIC and DOC: (1) the decomposition of DOC, (2) adsorption of DOC on mineral matter, and (3) the dilution of artificially recharged water by mixing with local groundwater. The largest decrease (44%) in the DOC content occurred during the early stage of subsurface flow, within 350 m of the infiltration ponds. The reduction of DOC was accompanied by an equal increase in DIC and a significant drop in δ¹³C_DIC. This change is attributed to the oxidative decomposition of DOC. A further 23% decrease in DOC is attributed to adsorption and a final drop of 14% to dilution with local groundwater.     

Rocks control the chemical composition of surface water from the high Alpine Zermatt area (Swiss Alps)

The study presents composition data of 87 surface water samples from high alpine catchments of the Zermatt area (Swiss Alps). The investigated area covers 170 km². It was found that the surface runoff acquires the dissolved solids mostly by reaction of precipitation water with the minerals of the bedrock. Total dissolved solids (TDS) vary from 6 to 268 mg L^?1. All collected water shows a clear chemical signature of the bedrock mineralogy. The contribution of atmospheric input is restricted to small amounts of ammonium nitrate and sodium chloride. NH₄ is a transient component and has not been detected in the runoff. Evaporation is not a significant mechanism for TDS increase in the Zermatt area. The chemical composition of the three main types of water can be related to the mineralogy of the dominant bedrock in the catchments. Specifically, Ca-HCO₃ (CC) waters develop from metamorphic mafic rocks and from carbonate-bearing schists. Mg-HCO₃ water originates from serpentinites and peridotites. Ca-SO₄ (CS) waters derive from continental basement rocks such as pyrite-rich granite and gneiss containing oligoclase or andesine. The collected data suggest that, together with reaction time, modal sulfide primarily controls and limits TDS of the waters by providing sulfuric acid for calcite (CC waters) and silicate (CS waters) dissolution. If calcite is present in the bedrock, its dissolution neutralizes the acid produced by sulphide weathering and buffers pH to near neutral to weakly alkaline conditions. If calcite is absent, the process produces low-pH waters in gneiss and granite catchments. The type of bedrock and its mineral assemblage can be recognized in water leaving very small catchments of some km² area. The large variety of water with a characteristic chemical signature is an impressive consequence of the richly diverse geology and the different rock inventory of the local catchments in the Zermatt area.     

Hydrochemical and isotopic characteristics of groundwater in the northeastern Tennger Desert,northern China

Groundwater is typically the only water source in arid regions, and its circulation processes should be better understood for rational resource exploitation. Stable isotopes and major ions were investigated in the northeastern Tengger Desert, northern China, to gain insights into groundwater recharge and evolution. In the northern mountains, Quaternary unconsolidated sediments, exposed only in valleys between hills, form the main aquifer, which is mainly made of aeolian sand and gravel. Most of the mountain groundwater samples plot along the local meteoric water line (LMWL), with a more depleted signature compared to summer precipitation, suggesting that mountain groundwater was recharged by local precipitation during winter. Most of the groundwater was fresh, with total dissolved solids less than 1 g/L; dominant ions are Na⁺, SO₄ ^2? and Cl^?, and all mineral saturation indices are less than zero. Evaporation, dissolution and cation exchange are the major hydrogeochemical processes. In the southern plains, however, the main aquifers are sandstone. The linear regression line of δD and δ ¹⁸O of groundwater parallels the LMWL but the intercept is lower, indicating that groundwater in the plains has been recharged by ancient precipitation rather than modern. Both calcite and dolomite phases in the plains groundwater are close to saturation, while gypsum and halite can still be dissolved into the groundwater. Different recharge mechanisms occur in the northern mountains and the southern plains, and the hydraulic connection between them is weak. Because of the limited recharge, groundwater exploitation should be limited as much as possible.     

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ¹⁸O_H2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O₂ and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε¹⁸O_SO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent ε_SO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O₂ into sulfate. δ³⁴S_SO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ³⁴S_SO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.     

Rare earth elements,neodymium and strontium isotopic systematics in mineral waters: evidence from the Massif Central,France

Rare Earth Elements (REEs), and Sr and Nd isotope distributions, have been studied in mineralized waters from the Massif Central (France). The CO₂-rich springs are characterized by a neutral pH (6–7) associated with total dissolved solids (TDS) from 1 to 7 g l⁻¹. The waters result from the mixing of very mineralized water pools, thought to have equilibrated at a temperature of around 200°C with superficial waters. These two mineral water pools evidenced by Sr isotopes and dissolved REEs could reflect 2 different stages of water–rock interaction and an equilibrium with different mineral assemblages.The concentrations of individual dissolved REEs and total dissolved REEs (ΣREE), in the mineral waters examined, vary over several orders of magnitude but are not dependent on the main parameters of the waters (TDS, T°C, pH, Total Organic C). The dissolved REE concentrations presented as upper continental crust normalized patterns show HREE enrichment in most of the samples. The time evolution of REE patterns does not show significant fluctuations except in 1 borehole, located in the Limagne d’Allier area, which was sampled on 16 occasions over an 18 month period. Ten samples are HREE-enriched, whereas 6 samples show flat patterns.The aqueous speciation of REEs shows that CO²⁻₃ complexes dominate (>80%) over the free metal, F⁻, SO²⁻₄ and HCO⁻₃ complexes. The detailed speciation demonstrates that the fractionation of REEs (i.e. the HREE enrichment) in CO₂-rich and pH neutral fluids is due essentially to the predominance of the CO²⁻₃ complexes.The Sr isotopic composition of the mineral waters in the Massif Central shows different mixing processes; in the Cézallier area at least 3 end-member water types exist. The most dilute end-member is likely to originate as poorly mineralized waters with minimal groundwater circulation. Two other mineralized end-members are identified, although the link between the geographical location of spring outflow and the mixing proportion between the 2 end-members is not systematic. The range in ϵ_Nd(0) for mineralized waters in the Massif Central correlates well with that of the known parent rocks except for 4 springs. One way to explain the ϵ_Nd(0) in these instances is a contribution from drainage of volcanic rocks. The isotopic systematics help to constrain the hydrogeological models for this area.     

Relationships between radium and radon occurrence and hydrochemistry in fresh groundwater from fractured crystalline rocks, North Carolina (USA)

Naturally-occurring radionuclides (uranium, radium, and radon), major dissolved constituents, and trace elements were investigated in fresh groundwater in 117 wells in fractured crystalline rocks from the Piedmont region (North Carolina, USA). Chemical variations show a general transition between two water types: (1) slightly acidic (pH 5.0–6.0), oxic, low-total dissolved solids (TDS) waters, and (2) near neutral, oxic to anoxic, higher-TDS waters. The uranium, radium, and radon levels in groundwater associated with granite (Rolesville Granite) are systematically higher than other rock types (gneiss, metasedimentary, and metavolcanic rocks). Water chemistry plays a secondary role on radium and radon distributions as the ²²²Rn/²²⁶Ra activity ratio is correlated with redox-sensitive solutes such as dissolved oxygen and Mn concentrations, as well as overall dissolved solids content including major divalent cations and Ba. Since ²²⁴Ra/²²⁸Ra activity ratios in groundwater are close to 1, we suggest that mobilization of Ra and Rn is controlled by alpha recoil processes from parent nuclides on fracture surfaces, ruling out Ra sources from mineral dissolution or significant long-distance Ra transport. Alpha recoil is balanced by Ra adsorption that is influenced by redox conditions and/or ion concentrations, resulting in an approximately one order of magnitude decrease (~ 20,000 to ~ 2000) in the apparent Ra distribution coefficient between oxygen-saturated and anoxic conditions and also across the range of dissolved ion concentrations (up to ~ 7 mM). Thus, the U and Th content of rocks is the primary control on observed Ra and Rn activities in groundwater in fractured crystalline rocks, and in addition, linked dissolved solids concentrations and redox conditions impart a secondary control.