Use of hydrogeochemistry and environmental isotopes for evaluation of groundwater in Qingshuihe Basin,northwestern China

Hydrogeochemistry and environmental isotope data were utilized to understand origin, geochemical evolution, hydraulic interconnection, and renewability of groundwater in Qingshuihe Basin, northwestern China. There are four types of groundwater: (1) shallow groundwater in the mountain front pluvial fans, originating from recent recharge by precipitation, (2) deep paleo-groundwater of the lower alluvial plains, which was formed long ago, (3) shallow groundwater in the lower alluvial plains, which has undergone evaporation during the recharge process, and (4) mixed groundwater (shallow and deep groundwater in the plain). The main water types are Na–HCO₃, which dominates type (1), and Na–SO₄, which dominates types (2) and (3). Geochemical evolution in the upper pluvial fans is mainly the result of CO₂ gas dissolution, silicates weathering and cation exchange; in the lower alluvial plains, it is related to mineral dissolution. The evaporative enrichment only produces significant salinity increases in the shallow groundwater of the lower alluvial plains. Shallow groundwater age in the upper plain is 10 years or so, showing a strong renewability. Deep groundwater ages in the lower plain are more than 200 years, showing poor renewability. In the exploitation areas, the renewability of groundwater evidently increases and the circulation period is 70–100 years.     

Vertical geochemical variations and arsenic mobilization in the shallow alluvial aquifers of the Chapai-Nawabganj District, northwestern Bangladesh: implication of siderite precipitation

Core sediments from three disturbed boreholes (JOR, GHAT, and RAJ) and two undisturbed boreholes (DW1 and DW2) were collected in the study area of the Chapai-Nawabganj district of northwestern Bangladesh for geochemical analyses. In the study area, groundwater samples from fourteen As-contained private wells and five nested piezometers at both the DW1 and DW2 boreholes were also collected and analyzed. The groundwater arsenic concentrations in the uppermost aquifer (10–40 m of depth) range from 3 to 315 μg/L (mean 47.73 ± 73.41 μg/L), while the arsenic content in sediments range from 2 to 14 mg/kg (mean 4.36 ± 3.34 mg/kg). An environmental scanning electron microscope (ESEM) with an energy dispersive X-ray spectrometer was used to investigate the presence of major and trace elements in the sediments. Groundwaters in the study area are generally the Ca–HCO₃ type with high concentrations of As, but low levels of Fe, Mn, NO₃ ^? and SO ₄ ^?2 . The concentrations of As, Fe, Mn decrease with depth in the groundwater, showing vertical geochemical variations in the study area. Statistical analysis clearly shows that As is closely associated with Fe and Mn in the sediments of the JOR core (r = 0.87, p < 0.05 for Fe and r = 0.78, p < 0.05 for Mn) and GHAT core (r = 0.95, p < 0.05 for Fe and r = 0.93, p < 0.05 for Mn), while As is not correlated with Fe and Mn in groundwater. The comparatively low Fe and Mn concentrations in some groundwater and the ESEM image revealed that siderite precipitated as a secondary mineral on the surface of the sediment particles. The correlations along with results of sequential extraction experiments indicated that reductive dissolution of FeOOH and MnOOH represents a mechanism for releasing arsenic into the groundwater.     

Reassessing the management of groundwater use from sandy aquifers: acidification and base cation depletion exacerbated by drought and groundwater withdrawal on the Gnangara Mound, Western Australia

The combined effects of low rainfall, groundwater withdrawal in excess of 300 GL/year and reduced recharge in areas covered by pine plantations has caused the water table in a sandy unconfined aquifer on the Gnangara Mound in Western Australia to drop by up to 5 m and aquifer storage to decline by about 500 GL over the last 20 years. Groundwater has become acidic in areas of high drawdown, with pH values typically being less than 5.0 at the water table, and elevated concentrations of SO₄ ^2?, Al, Fe, Zn, Cu, Ni and Pb. Trends of increasing acidity and base cation concentrations in deep water supply wells in the Mirrabooka wellfield indicate that about 0.7 keq/ha/year of base cations are being leached from soil within cones of depression of pumping wells. These results indicate that the assessment of the sustainable yields of aquifers under conditions of low rainfall needs to consider geochemical interactions between groundwater, aquifer sediments, soils and vegetation, and not be just based on aquifer hydraulics and water-balance changes.     

Characterization of groundwater chemistry under the influence of lithologic and anthropogenic factors along a climatic gradient in Upper Cauvery basin, South India

Hydrogeological and climatic effect on chemical behavior of groundwater along a climatic gradient is studied along a river basin. ‘Semi-arid’ (500–800 mm of mean annual rainfall), ‘sub-humid’ (800–1,200 mm/year) and ‘humid’ (1,200–1,500 mm/year) are the climatic zones chosen along the granito-gneissic plains of Kabini basin in South India for the present analysis. Data on groundwater chemistry is initially checked for its quality using NICB ratio (<±5 %), EC versus TZ+ (~0.85 correlation), EC versus TDS and EC versus TH analysis. Groundwater in the three climatic zones is ‘hard’ to ‘very hard’ in terms of Ca–Mg hardness. Polluted wells are identified (>40 % of pollution) and eliminated for the characterization. Piper’s diagram with mean concentrations indicates the evolution of CaNaHCO₃ (semi-arid) from CaHCO₃ (humid zone) along the climatic gradient. Carbonates dominate other anions and strong acids exceeded weak acids in the region. Mule Hole SEW, an experimental watershed in sub-humid zone, is characterized initially using hydrogeochemistry and is observed to be a replica of entire sub-humid zone (with 25 wells). Extension of the studies for the entire basin (120 wells) showed a chemical gradient along the climatic gradient with sub-humid zone bridging semi-arid and humid zones. Ca/Na molar ratio varies by more than 100 times from semi-arid to humid zones. Semi-arid zone is more silicaceous than sub-humid while humid zone is more carbonaceous (Ca/Cl ~14). Along the climatic gradient, groundwater is undersaturated (humid), saturated (sub-humid) and slightly supersaturated (semi-arid) with calcite and dolomite. Concentration–depth profiles are in support of the geological stratification i.e., ~18 m of saprolite and ~25 m of fracture rock with parent gneiss beneath. All the wells are classified into four groups based on groundwater fluctuations and further into ‘deep’ and ‘shallow’ based on the depth to groundwater. Higher the fluctuations, larger is its impact on groundwater chemistry. Actual seasonal patterns are identified using ‘recharge–discharge’ concept based on rainfall intensity instead of traditional monsoon–non-monsoon concept. Non-pumped wells have low Na/Cl and Ca/Cl ratios in recharge period than in discharge period (Dilution). Few other wells, which are subjected to pumping, still exhibit dilution chemistry though water level fluctuations are high due to annual recharge. Other wells which do not receive sufficient rainfall and are constantly pumped showed high concentrations in recharge period rather than in discharge period (Anti-dilution). In summary, recharge–discharge concept demarcates the pumped wells from natural deep wells thus, characterizing the basin.     

Exploring the effects of data quality,data worth,and redundancy of CO2 gas pressure and saturation data on reservoir characterization through PEST inversion

This study examined the impacts of reservoir properties on carbon dioxide (CO₂) migration after subsurface injection and evaluated the possibility of characterizing reservoir properties using CO₂ monitoring data such as spatial–temporal distributions of gas pressure, which can be reasonably monitored in practice. The injection reservoir was assumed to be located 1,400–1,500 m below the ground surface such that CO₂ remained in the supercritical state. The reservoir was assumed to contain layers with alternating conductive and resistive properties, which is analogous to actual geological formations such as the Mount Simon Sandstone unit. The CO₂ injection simulation used a cylindrical grid setting in which the injection well was situated at the center of the domain, which extended out 8,000 m from the injection well. The CO₂ migration was simulated using the latest version of the simulator, subsurface transport over multiple phases (the water–salt–CO₂–energy module), developed by Pacific Northwest National Laboratory. A nonlinear parameter estimation and optimization modeling software package, Parameter ESTimation (PEST), is adopted for automated reservoir parameter estimation. The effects of data quality, data worth, and data redundancy were explored regarding the detectability of reservoir parameters using gas pressure monitoring data, by comparing PEST inversion results using data with different levels of noises, various numbers of monitoring wells and locations, and different data collection spacing and temporal sampling intervals. This study yielded insight into the use of CO₂ monitoring data for reservoir characterization and how to design the monitoring system to optimize data worth and reduce data redundancy. The feasibility of using CO₂ saturation data for improving reservoir characterization was also discussed.     

Hydrogeochemical evaluation of fractured Limestone aquifer by applying a geochemical model in eastern Nile Valley,Egypt

Rock water interactions play an important role in the flow of groundwater. Groundwater samples were collected from deep production wells with depths ranging from 120 to 230 m. Complete chemical analysis of 40 groundwater samples was collected from the fractured limestone aquifer including major cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and major anions (Cl^?, SO₄ ^2?, HCO₃ ^?, CO₃ ^2?). A geochemical modeling (NETPATH Software) was applied for environmental simulate net geochemical mass-balance reactions between initial and final waters along a hydrologic flow path. This program simulates selected evolutionary waters for every possible combination of the plausible phases that account for the composition of a selected set of chemical constraints in the system. The groundwater of the Eocene aquifer mainly belongs to fairly fresh water with salinity contents ranging from 228 to 3595 ppm. The measured groundwater levels range between 8 and 25 m near the river Nile to the limestone plateau (eastwards). Consequently, groundwater flows from east to westward toward the river Nile. Groundwater aquifer in the study area is mainly composed of fractured limestone; the saturated states of the PCO₂, calcite, aragonite, dolomite, siderite, gypsum, anhydrite, hematite, and goethite in addition to H₂ gas were estimated. The undersaturated state of carbon dioxide reflects closed conditions and very low probability of recent recharge, and it reveals also the high tendency of water to precipitates carbonate species. Undersaturation by carbonate minerals is only restricted to some pockets distributed on the different places of the aquifer in the study area. The majority of groundwater samples of Eocene aquifer in the study area indicated that groundwater is not suitable for irrigation with treatment and requires good drainage.     

Assessing the potential consequences of CO2 leakage to freshwater resources: A batch-reaction experiment towards an isotopic tracing tool

The assessment of the environmental impacts of CO₂ geological storage requires the investigation of potential CO₂ leakages into fresh groundwater, particularly with respect to protected groundwater resources. The geochemical processes and perturbations associated with a CO₂ leak into fresh groundwater could alter groundwater quality: indeed, some of the reacting minerals may contain hazardous constituents, which might be released into groundwater. Since the geochemical reactions may occult direct evidence of intruding CO₂, it is necessary to characterize these processes and identify possible indirect indicators for monitoring CO₂ intrusion. The present study focuses on open questions: Can changes in water quality provide evidence of CO₂ leakage? Which parameters can be used to assess impact on freshwater aquifers? What is the time scale of water chemistry degradation in the presence of CO₂? The results of an experimental approach allow selecting pertinent isotope tracers as possible indirect indicators of CO₂ presence, opening the way to devise an isotopic tracing tool.The study area is located in the Paris Basin (France), which contains deep saline formations identified as targets by French national programs for CO₂ geological storage. The study focuses on the multi-layered Albian fresh water aquifer, confined in the central part of the Paris Basin a major strategic potable groundwater overlying the potential CO₂ storage formations. An experimental approach (batch reactors) was carried out in order to better understand the rock–water–CO₂ interactions with two main objectives. The first was to assess the evolution of the formation water chemistry and mineralogy of the solid phase over time during the interaction. The second concerned the design of an isotopic monitoring program for freshwater resources potentially affected by CO₂ leakage. The main focus was to select suitable environmental isotope tracers to track water rock interaction associated with small quantities of CO₂ leaking into freshwater aquifers.In order to improve knowledge on the Albian aquifer, and to provide representative samples for the experiments, solid and fluid sampling campaigns were performed throughout the Paris Basin. Albian groundwater is anoxic with high concentrations of Fe, a pH around 7 and a mineral content of 0.3 g L⁻¹. Macroscopic and microscopic solid analyses showed a quartz-rich sand with the presence of illite/smectite, microcline, apatite and glauconite. A water–mineral–CO₂ interaction batch experiment was used to investigate the geochemical evolution of the groundwater and the potential release of hazardous trace elements. It was complemented by a multi-isotope approach including δ¹³C_DIC and ⁸⁷Sr/⁸⁶Sr. Here the evolution of the concentrations of major and trace elements and isotopic ratios over batch durations from 1 day to 1 month are discussed. Three types of ion behavior are observed: Type I features Ca, SiO₂, HCO₃, F, PO₄, Na, Al, B, Co, K, Li, Mg, Mn, Ni, Pb, Sr, Zn which increased after initial CO₂ influx. Type II comprises Be and Fe declining at the start of CO₂ injection. Then, type III groups element with no variation during the experiments like Cl and SO₄. The results of the multi-isotope approach show significant changes in isotopic ratios with time. The contribution of isotope and chemical data helps in understanding geochemical processes involved in the system. The isotopic systems used in this study are potential indirect indicators of CO₂–water–rock interaction and could serve as monitoring tools of CO₂ leakage into an aquifer overlying deep saline formations used for C sequestration and storage.     

Investigation of the geochemical impact of CO2 on shallow groundwater: design and implementation of a CO2 injection test in Northeast Germany

A small scale and temporally limited CO₂ injection test was performed in a shallow aquifer to investigate the geochemical impact of CO₂ upon such aquifers and to apply and verify different monitoring methods. Detailed site investigation coupled with multiphase simulations were necessary to design the injection experiment and to set up the monitoring network, before CO₂ was injected over a ten-day period at three injection wells, at a depth of 18?m below surface level into a quaternary sand aquifer located close to the town of Wittstock in Northeast Germany. Monitoring methods comprised groundwater sampling and standard analyses, as well as trace element analyses and isotope analyses; geoelectrical borehole monitoring; passive samplers to analyse temporally integrated for cations and multi-parameter probes that can measure continuously for dissolved CO₂, pH and electrical conductivity. Due to CO₂ injection, total inorganic carbon concentrations increased and pH decreased down to a level of 5.1. Associated reactions comprised the release of major cations and trace elements. Geoelectrical monitoring, as well as isotope analyses and multi-parameter probes proved to be suitable methods for monitoring injected CO₂ and/or the alteration of groundwater.     

Geochemistry of groundwater from a rhyolite aquifer,Northwest Iran

Chemical data on groundwater composition in rhyolitic hard rock aquifers with limited global occurrence are rarely found. In this research geochemistry of Mahabad Rhyolite Aquifer, NW Iran, was studied considering major ions, silica and trace elements measured in wet and dry seasons. Based on the results, the mean silica content was 18 mg l^?1, less than the average of the rhyolitic waters. However, the relatively higher electrical conductivity (EC) of 418 µS cm^?1 was measured. Based on a PHREEQCI model, the weathering of the silicate minerals and dissolution of carbonated intercalations turns groundwater dominantly into Ca–HCO₃ type, enhancing EC, pH and silica concentration along the flow path. Trace elements of Sr, Ba and Pb were measured at highest concentrations, the later with an average value of 83 ppb exceeds the drinking guidelines. Cluster analysis confirms biotite weathering and barite dissolution as the main sources of the trace elements in the groundwater. The results signify geochemical features of rhyolitic groundwater which can be a useful tracer of mixing in flow systems containing variety of aquifers including rhyolites.     

Hydrogeochemical assessment of groundwater quality along the coastal aquifers of southern Tamil Nadu,India

Hydrogeochemical investigation of groundwater has been carried out in the coastal aquifers of southern Tamil Nadu, India. Seventy-nine dug well samples were collected and analyzed for various physicochemical parameters. The result of the geochemical analysis indicates the groundwater in the study area is slightly alkaline with moderate saline water. The cation and anion concentrations confirm most of the groundwater samples belong to the order of Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ and Cl^? > SO₄ ^2? > HCO₃ ^?. Thereby three major hydrochemical facies (Ca–Cl, mixed Ca–Mg–Cl and Na–Cl) were identified. Based on the US Salinity diagram, majority of the samples fall under medium to very high salinity with low to high sodium hazard. The cross plot of Ca²⁺ + Mg²⁺ versus chloride shows 61 % of the samples fall under saline water category. Higher EC, TDS and Cl concentrations were observed from Tiruchendur to Koodankulam coastal zone. It indicates that these regions are significantly affected by saltwater contamination due to seawater intrusion, saltpan deposits, and beach placer mining activities.     

Groundwater composition,hydrochemical evolution and mass transfer in a regional detrital aquifer (Baza basin,southern Spain)

The physical–chemical characteristics of the groundwater in the Baza–Caniles detrital aquifer system indicate that a wide diversity of hydrochemical conditions exists in this semiarid region, defining geochemical zones with distinct groundwater types. The least mineralized water is found closest to the main recharge zones, and the salinity of the water increases significantly with depth towards the center of the basin. Geochemical reaction models have been constructed using water chemistry data along flow paths that characterize the different sectors of the aquifer system, namely: Quaternary aquifer, unconfined sector and shallow and deep confined sectors of the Mio–Pliocene aquifer. Geochemical mass–balance calculations indicate that the dominant groundwater reaction throughout the detrital system is dedolomitisation (dolomite dissolution and calcite precipitation driven by gypsum dissolution); this process is highly developed in the central part of the basin due to the abundance of evaporites. Apart from this process, there are others which influence the geochemical zoning of the system. In the Quaternary aquifer, which behaves as a system open to gases and which receives inputs of CO₂ gas derived from the intensive farming in the area, the interaction of the CO₂ with the carbonate matrix of the aquifer produces an increase in the alkalinity of the water. In the shallow confined sector of the Mio–Pliocene aquifer, the process of dedolomitisation evolves in a system closed to CO₂ gas. Ca²⁺/Na⁺ cation exchange and halite dissolution processes are locally important, which gives rise to a relatively saline water. Finally, in the deep confined sector, a strongly reducing environment exists, in which the presence of H₂S and NH⁺₄ in the highly mineralized groundwater can be detected. In this geochemical zone, the groundwater system is considered to be closed to CO₂ gas proceeding from external sources, but open to CO₂ from oxidation of organic matter. The geochemical modeling indicates that the chemical characteristics of this saline water are mainly due to SO₄ dissolution, dedolomitisation and SO₄ reduction, coupled with microbial degradation of lignite.     

Mechanism of fluoride enrichment in groundwater of hard rock aquifers in Medak,Telangana State,South India

A total of 194 groundwater samples were collected from wells in hard rock aquifers of the Medak district, South India, to assess the distribution of fluoride in groundwater and to determine whether this chemical constituent was likely to be causing adverse health effects on groundwater user in the region. The study revealed that the fluoride concentration in groundwater ranged between 0.2 and 7.4 mg/L with an average concentration of 2.7 mg/L. About 57% of groundwater tested has fluoride concentrations more than the maximum permissible limit of 1.5 mg/L. The highest concentrations of fluoride were measured in groundwater in the north-eastern part of the Medak region especially in the Siddipeta, Chinnakodur, Nanganoor and Dubhaka regions. The areas are underlain by granites which contain fluoride-bearing minerals like apatite and biotite. Due to water–rock interactions, the fluoride has become enriched in groundwater due to the weathering and leaching of fluoride-bearing minerals. The pH and bicarbonate concentrations of the groundwater are varied from 6.6 to 8.8 and 18 to 527 mg/L, respectively. High fluoride concentration in the groundwater of the study area is observed when pH and the bicarbonate concentration are high. Data plotted in Gibbs diagram show that all groundwater samples fall under rock weathering dominance group with a trend towards the evaporation dominance category. An assessment of the chemical composition of groundwater reveals that most of the groundwater samples have compositions of Ca²⁺–Mg²⁺–Cl^? > Ca²⁺–Na⁺–HCO₃ ^? > Ca²⁺–HCO₃ ^? > Na⁺–HCO₃ ^?. This suggests that the characteristics of the groundwater flow regime, long residence time and the extent of groundwater interaction with rocks are the major factors that influence the concentration of fluoride. It is advised not to utilize the groundwater for drinking purpose in the areas delineated, and they should depend on alternate safe source.     

OpenGeoSys-ChemApp: a coupled simulator for reactive transport in multiphase systems and application to CO2 storage formation in Northern Germany

Sequestration of CO₂ into a deep geological reservoir causes a complex interaction of different processes such as multiphase flow, phase transition, multicomponent transport, and geochemical reactions between dissolved CO₂ and the mineral matrix of the porous medium. A prognosis of the reservoir behaviour and the feedback from large-scale geochemical alterations require efficient process-based numerical models. For this purpose, the multiphase flow and multicomponent transport code OpenGeoSys-Eclipse have been coupled to the geochemical model ChemApp. The newly developed coupled simulator was successfully verified for correctness and accuracy of the implemented reaction module by benchmarking tests. The code was then applied to assess the impact of geochemical reactions during CO₂ sequestration at a hypothetical but typical Bunter sandstone formation in the Northern German Basin. Injection and spreading of 1.48 × 10⁷ t of CO₂ in an anticline structure of the reservoir were simulated over a period of 20 years of injection plus 80 years of post-injection time. Equilibrium geochemical calculations performed by ChemApp show only a low reactivity to the geochemical system. The increased acidity of the aqueous solution results in dissolution of small amounts of calcite, anhydrite, and quartz. Geochemical alterations of the mineral phase composition result in slight increases in porosity and permeability, which locally may reach up to +0.02 and 0.1 %, respectively.     

Impact of CO<Subscript>2</Subscript> injection rate on heat extraction at the HDR geothermal field of Zhacanggou,China

CO₂ is now considered as a novel heat transmission fluid to extract geothermal energy. It can achieve the goal of energy exploitation and CO₂ geological sequestration. Taking Zhacanggou as research area, a “Three-spot” well pattern (one injection with two production), “wellbore–reservoir” coupled model is built, and a constant injection rate is set up. A fully coupled wellbore–reservoir simulator—T2Well—is introduced to study the flow mechanism of CO₂ working as heat transmission fluid, the variance pattern of each physical field, the influence of CO₂ injection rate on heat extraction and the potential and sustainability of heat resource in Guide region. The density profile variance resulting from temperature differences of two wells can help the system achieve “self-circulation” by siphon phenomenon, which is more significant in higher injection rate cases. The density of CO₂ is under the effect of both pressure and temperature; moreover, it has a counter effect on temperature and pressure. The feedback makes the flow process in wellbore more complex. In low injection rate scenarios, the temperature has a dominating impact on the fluid density, while in high rate scenario, pressure plays a more important role. In most scenarios, it basically keeps stable during 30-year operation. The decline of production temperature is <5 °C. However, for some high injection rate cases (75 and 100 kg/s), due to the heat depletion in reservoir, there is a dramatic decline for production temperature and heat extraction rate. Therefore, a 50-kg/s CO₂ injection rate is more suitable for “Three-spot” well pattern in Guide region.     

Climate controls on nitrate concentration variability in the Abbotsford-Sumas aquifer,British Columbia,Canada

Understanding the linkage between temporal climate variability and groundwater nitrate concentration variability in monitoring well records is key to interpreting the impacts of changes in land-use practices and assessing groundwater quality trends. This study explores the coupling of climate variability and groundwater nitrate concentration variability in the Abbotsford-Sumas aquifer. Over the period of 1992–2009, the average groundwater nitrate concentration in the aquifer remained fairly steady at approximately 15 mg/L nitrate-N. Normalized nitrate data for 19 individual monitoring wells were assessed for a range of intrinsic factors including precipitation, depth to water table, depth below water table, and apparent groundwater age. At a broad scale, there is a negative correlation between nitrate concentration and apparent groundwater age. Each dedicated monitoring well shows unique, non-uniform cyclical variability in nitrate concentrations that appears to correspond with seasonal (1 year) cycles in precipitation as well as longer-period cycles (~5 years), possibly due to ENSO (El Niño Southern Oscillation) or the Pacific North American (PNA) pattern. These precipitation cycles appear to influence nitrate concentrations by approximately ±30 % of the critical concentration (10 mg/L NO₃–N). Not all wells show direct correlation due to many complex local-scale factors that influence nitrate leaching including spatially and temporally variable nutrient management practices and soil/crop nitrogen dynamics (anthropogenic and agronomic factors).     

Effects of rainwater-harvesting-induced artificial recharge on the groundwater of wells in Rajasthan, India

In light of the increasing deterioration of groundwater supplies in Rajasthan, India, rainwater harvesting practices in southern Rajasthan were studied to determine the effects of artificially recharged groundwater on the supply and quality of local groundwater. A physical and geochemical investigation utilizing environmental tracers (δ¹⁸O and Cl^–), groundwater level and groundwater quality measurements, and geological surveys was conducted with two objectives: (1) to quantify the proportion of artificially recharged groundwater in wells located near rainwater harvesting structures and (2) to examine potential effects of artificial recharge on the quality of groundwater in these wells. A geochemical mixing model revealed that the proportion of artificial recharge in these wells ranged from 0 to 75%. Groundwater tracer, water table, and geological data provided evidence of complex groundwater flow and were used to explain the spatial distribution of artificial recharge. Furthermore, wells receiving artificial recharge had improved groundwater quality. Statistical analysis revealed a significant difference between the water quality in these wells and wells determined not to receive artificial recharge, for electrical conductivity and SO ₄ ^– . The findings from this study provide quantitative evidence that rainwater harvesting structures in southern Rajasthan influence the groundwater supply and quality of nearby wells by artificially recharging local groundwater.     

Groundwater flow dynamics in the complex aquifer system of Gidabo River Basin (Ethiopian Rift): a multi-proxy approach

Hydrochemical and isotope data in conjunction with hydraulic head and spring discharge observations were used to characterize the regional groundwater flow dynamics and the role of the tectonic setting in the Gidabo River Basin, Ethiopian Rift. Both groundwater levels and hydrochemical and isotopic data indicate groundwater flow from the major recharge area in the highland and escarpment into deep rift floor aquifers, suggesting a deep regional flow system can be distinguished from the shallow local aquifers. The δ¹⁸O and δ²H values of deep thermal (≥30 °C) groundwater are depleted relative to the shallow (<60 m below ground level) groundwater in the rift floor. Based on the δ¹⁸O values, the thermal groundwater is found to be recharged in the highland around 2,600 m a.s.l. and on average mixed with a proportion of 30 % shallow groundwater. While most groundwater samples display diluted solutions, δ¹³C data of dissolved inorganic carbon reveal that locally the thermal groundwater near fault zones is loaded with mantle CO₂, which enhances silicate weathering and leads to anomalously high total dissolved solids (2,000–2,320 mg/l) and fluoride concentrations (6–15 mg/l) exceeding the recommended guideline value. The faults are generally found to act as complex conduit leaky barrier systems favoring vertical mixing processes. Normal faults dipping to the west appear to facilitate movement of groundwater into deeper aquifers and towards the rift floor, whereas those dipping to the east tend to act as leaky barriers perpendicular to the fault but enable preferential flow parallel to the fault plane.     

Geochemistry and assessment of hydrogeochemical processes in groundwater in the southern part of Bathinda district of Punjab, northwest India

Hydrogeochemistry of groundwater is important for sustainable development and effective management of the groundwater resource. Fifty-six groundwater samples were collected from shallow tube wells of the intensively cultivated southern part of district Bathinda of Punjab, India, during pre- and post-monsoon seasons. Conventional graphical plots were used to define the geochemical evaluation of aquifer system based on the ionic constituents, water types, hydrochemical facies and factors controlling groundwater quality. Negative values of chloroalkaline indices suggest the prevalence of reverse ion exchange process irrespective of the seasons. A significant effect of monsoon is observed in terms chemical facies as a considerable amount of area with temporary hardness of Ca²⁺–Mg²⁺–HCO₃ ^? type in the pre-monsoon switched to Ca²⁺–Mg²⁺–Cl^? type (18%) followed by Na⁺–HCO₃ ^? type (14%) in the post-monsoon. Evaporation is the major geochemical process controlling the chemistry of groundwater process in pre-monsoon; however, in post-monsoon ion exchange reaction dominates over evaporation. Carbonate weathering is the major hydrogeochemical process operating in this part of the district, irrespective of the season. The abundance of Ca²⁺ + Mg²⁺ in groundwater of Bathinda can be attributed mainly to gypsum and carbonate weathering. Silicate weathering also occurs in a few samples in the post-monsoon in addition to the carbonate dissolution. Water chemistry is deteriorated by land-use activities, especially irrigation return flow and synthetic fertilisers (urea, gypsum, etc.) as indicted by concentrations of nitrate, sulphate and chlorides. Overall, results indicate that different natural hydrogeochemical processes such as simple dissolution, mixing, weathering of carbonate minerals locally known as ‘‘kankar’’ and silicate weathering are the key factors in both seasons.     

Hydrogeochemical characterization and evolution of a regional karst aquifer in the Cuatrociénegas area,Mexico

The Cuatrociénegas area is useful for the investigation of the effect of groundwater extraction in the Chihuahuan freshwater xeric ecoregion. It has been investigated at this time using a selection of geochemical indicators (major, minor and trace elements) and δ³⁴S data, to characterize the origin of groundwater, the main geochemical processes and the mineral/groundwater interactions controlling the baseline geochemistry. The area is composed of limestones of Mesozoic age, with a composite thickness of about 500 m, overlaid by basin fill (poorly consolidated young sediments). Substantial water extraction and modification of natural discharges from the area along the last century have produced a detrimental impact on ecosystem structure and function. Water–rock interactions, mixing and evaporative processes dominate the baseline groundwater quality. Natural recharge is HCO₃–Ca type in equilibrium with calcite, low salinity (TDS?<?500 mg/L), Cl^? lower than 11 mg/L and average Li⁺ concentration of 0.005 mg/L. Along the groundwater flow systems, δ³⁴S evidence and mass transfer calculations indicate that Cretaceous gypsum dissolution and dedolomitization reactions adjust water composition to the SO₄–Ca type. The increase of water–rock interaction is reflected by Cl^? values increase (average 68 mg/L), TDS up to about 1500 mg/L and an average Li⁺ concentration of 0.063 mg/L. Calculations with chemical geothermometers indicate that temperature at depth could be at maximum of 15–20 °C higher than field-measured temperature for pozas. After groundwater is discharged to the surface, chemical evolution continues; water evaporation, CO₂ degassing and precipitation of minerals such as gypsum, calcite and kaolinite represent the final processes and reactions controlling water chemical composition.     

Carbon isotopes and geochemical processes in CO2-rich cold mineral water,N-Portugal

This paper summarizes a new outlook on the conceptual model of Melgaço–Messegães CO₂-rich cold (≈18 °C) mineral water systems, issuing in N of Portugal, based on their isotopic (²H, ³H, ¹³C, ¹⁴C and ¹⁸O) and geochemical features. Stable isotopes indicate the meteoric origin of these CO₂-rich mineral waters. Based on the isotopic fractionation with the altitude, a recharge altitude between 513 up to 740 m a.s.l. was estimated, corroborating the tritium results. The lowest ³H content (0 TU) is found in the groundwater samples with the highest mineralization. The mineral waters circulation are mainly related to a granitic and granodioritic environment inducing two different groundwater types (Ca/Na–HCO₃ and Na/Ca–HCO₃), indicating different underground flow paths. Calcium dissolution is controlled by hydrolysis of rock-matrix silicate minerals (e.g. Ca-plagioclases) and not associated to anthropogenic sources. The shallow dilute groundwaters exhibit signatures of anthropogenic origins (e.g. NO₃) and higher Na/Ca ratios. The stable isotopes together with the geochemistry provided no indication of mixing between the regional shallow cold dilute groundwater and mineral water systems. The heavy isotopic signatures identified in the δ¹³C data (δ¹³C = 4.7 ‰, performed on the total dissolved inorganic carbon (TDIC) of CO₂-rich mineral waters) could be derived from a deep-seated (upper mantle) source or associated to methanogenesis (CH₄ source). The negligible ¹⁴C content (≈2 pmC) determined in the TDIC of the mineral waters, corroborates the hypothesis of a mantle-derived carbon source to the mineral groundwater systems or dissolution of carbonate layers at depth.