Water-rock Interaction Processes Research Articles

Geochemistry and sources of boron and strontium of geothermal waters from the Pearl River Delta region, South China: Implications for water-rock interactions

Pearl River Delta (PRD) region of South China is abundant of geothermal water resources. However, the development and utilization level of geothermal resources in this region is relatively low, due in part to the lack of fundamental geochemical research. To access water-rock interaction processes of the PRD geothermal system, we analyzed the geochemistry of geothermal waters by combining trace elements (B, Sr, and Br) and isotopes (δ11B and 87Sr/86Sr) with conventional tracers (major elements) that had been reported. The Cl/Br ratios (from 31 to 639) confirm the multi-source salinity of marine origin, precipitation, and a minor dissolution of halite. Major ions chemistry highlights the influence of ions exchange, the dissolution of carbonate, silicate, and sulphate minerals as well as the contribution of seawater. The Cl/B ratios (61 to 22,583) suggest interactions with carbonate rock and felsic rock, input of seawater, and groundwater mixing. Boron isotopic compositions (δ11B) range between −9.22 and +39.78 ‰. Sr contents and 87Sr/86Sr ratios are more homogeneous, falling between 0.06 and 32.26 mg/L and between 0.71239 and 0.72121, respectively. The B and Sr isotopic signatures show that three processes contribute to geochemistry of geothermal waters: 1) water/rock interaction involving marine carbonate rock, evaporite, and granitoid or/and gneiss, 2) seawater intrusion, and 3) shallow groundwater mixing. Major-trace element chemistry and these isotope systematics on their own indicates essential information on the aspects of fluid origin or water-rock interaction processes, and however provide a more comprehensive understanding of the geothermal system in the PRD region, South China.

A Highly Resolved Speleothem δ13C Record from Central China and Its Manifestation on Multiple Time Scales during the Last Glacial

Speleothem δ13C in monsoonal China differs from speleothem δ18O, which is widely used as a climatic proxy for several complex control reasons. Nevertheless, δ13C records have the potential to reveal the implications of hydroclimatic changes. This study reports a speleothem δ13C record from Didonghe (DDH) Cave in central China spanning 34 to 13 kyr BP. After we investigated the factors that influence speleothem δ13C, we found that the δ13C record showed that DDH Cave can prompt directional shifts via local hydroclimatic changes, such as in vegetation types, biomass, and rock–water interaction processes, suggesting that δ13C is mainly controlled by the local hydroclimate. Ensemble empirical mode decomposition (EEMD) results revealed a coupling relationship between δ18O and δ13C on multiple timescales, which suggested that changes in precipitation caused by large-scale monsoonal circulation are controlled by regional hydrological conditions to a great extent. However, the hydrological conditions of the cave were relatively mild and humid during the last glacial maximum (LGM), which revealed the impact of evaporation on changes in the region’s hydrological conditions. We also found that the δ18O and δ13C profiles decoupled when δ13C changed with a shift in the location of the westerly during HS1. The δ13C record correlates well with other paleoclimate records, suggesting that regional hydrological conditions are also modulated by the Earth’s internal and external driving factors.

Water–Rock Interaction Processes in Tíscar and Larva Active Faults (Betic Cordillera, SE Spain)

A hydrochemical and mineral study of groundwaters and damaged rocks from the Tíscar and Larva fault zones (Betic Cordillera, Iberian Peninsula) was carried out in order to (a) describe the physical and chemical properties of the groundwaters; (b) recognize significant locations with deep-origin fluids related to active tectonics; (c) and to describe the water–rock interaction and the neoformation of clay mineral processes and their importance in the seismicity of the faults. A sampling campaign was completed between November 2012 and November 2013, during which data were obtained from 23 different groundwater sites in the fault areas. Two main groups of waters were distinguished: (a) Ca2+-Mg2+-HCO3− facies characterized by poor conductivity and salinity; and (b) saline waters (up to 30 meq/L) rich in Ca2+-Mg2+-SO4-Cl− and with an elevated conductivity (frequently > 1000 μS/cm). In addition, a minor group of saline and warm waters (T > 16.5 °C) was found to be Na+-rich and show moderately high B values (>0.33 ppm), and which mig ht be hosted in aquifers deeper than the two main groups. This group of deep-origin waters is oversaturated in clay minerals and is in equilibrium for Ca-Mg carbonate minerals. X-ray diffraction and scanning and transmission electron microscopy data corroborate the crystallization forecast of authigenic smectite, which appears as thin films coating carbonate fragments. The origin of smectite is related to the fragile strain and thermal–fluid–mineral interactions in fault rocks. Smectite could lubricate carbonate rocks, which favor creep deformation versus seismic slip. This work provides locations where groundwater physico-chemical properties and composition suggest tectonic fault activity.

Hydrogeochemical evolution and water–rock interaction processes in the multilayer volcanic aquifer of Yogyakarta-Sleman Groundwater Basin, Indonesia

Volcanic aquifers have become valuable resources for providing water to approximately 2.5 million people in the Yogyakarta-Sleman Groundwater Basin, Indonesia. Nevertheless, hydrogeochemical characteristics at the basin scale remain poorly understood due to the complexity of multilayered aquifer systems. This study collected sixty-six groundwater samples during the rainy and dry seasons for physicochemical analysis and geochemical modeling to reveal the hydrogeochemical characteristics and evolution in the Yogyakarta-Sleman Groundwater Basin. The results showed that groundwater in the unconfined and confined aquifers exhibited different hydrogeochemical signatures. The Ca–Mg–HCO3 facies dominated groundwater from the unconfined aquifer. The groundwater facies evolved into a mixed Ca–Mg–Cl type along the flow direction towards the discharge zone. Meanwhile, groundwater from the confined aquifer showed mixed Ca–Na–HCO3, Na–HCO3, and Na–Cl–SO4 facies. The presence of Mg in the confined aquifer was replaced by Na, which was absorbed in the aquifer medium, thus showing the ion exchange process. The main geochemical processes can be inferred from the Gibbs diagram, where most groundwater samples show an intensive water–rock interaction process mainly influenced by the weathering of silicate minerals. Additionally, only groundwater samples from the confined aquifer were saturated with certain minerals (aragonite, calcite, and dolomite), confirming that the groundwater followed the regional flow system until it had sufficient time to reach equilibrium and saturation conditions. This study successfully explained the hydrogeochemical characteristics and evolution of a multilayer volcanic aquifer system that can serve as a basis for groundwater basin conservation.

Water–Rock Interaction Processes in Groundwater and Flows in a Maar Lake in Central Mexico

Tropical maar lakes are distinct ecosystems with unique ecological features. To comprehend, manage, and conserve these lakes, it is essential to understand their water sources, particularly groundwater, and the hydrogeochemical processes shaping their water chemistry. This research focuses on the maar lake Alchichica in central Mexico, known for harboring 18 new and endemic species and a ring of stromatolites. With groundwater discharge as the primary source, concerns arise over anthropic extraction impacts on water levels and stromatolite survival. Sampling six wells and one piezometer revealed major ion (Ca2+, Mg2+, K+, Na+, Cl−, HCO3−, SO42−) and trace element (Fe, Al3+, SiO2) concentrations. Geochemical evolution was explored through diagrams, geological sections, and inverse geochemical models using the PHREEQC code. Findings indicate groundwater evolving along controlled flow paths, and influencing chemical composition through water–rock interactions. The lake’s unique conditions, resulting from the mixing of two flows, enable stromatolite formation. Water level reduction appears unrelated to evaporation at the sampled sites, suggesting a need for a broader study in a larger area. Analyzing the maar lake’s hydrochemistry provides valuable insights into unique characteristics supporting high endemism in this ecosystem. This research enhances our understanding of groundwater’s geochemical processes and hydrogeochemical evolution in maar lakes, with potential applications worldwide.

Oxygen Isotope Fractionation between Carbonate Minerals and Carbonic Acid Systems and Constraints for Environmental Science and Geological Processes

The equilibrium oxygen isotope fractionation factor is widely used in geological thermometry. However, under most natural conditions, the oxygen isotope exchange is rare to reach equilibrium. Especially for the complex water–rock interaction process, the contribution of the H2CO3 solution, CO32− solution, Ca(HCO3)2 solution, and CaCO3 solution to the equilibrium oxygen isotope fractionation factor of this process is poorly understood. In view of this predicament, these key parameters are obtained by ab initio calculations. The results showed that the contributions of different carbonate minerals and different aqueous solutions to the equilibrium oxygen isotope fractionation factor were different. Among all nine carbonate minerals (dolomite, calcite, aragonite, magnesite, siderite, otavite, smithsonite, ankerite, and strontianite), the minerals with the highest and lowest reduced partition function ratios (RPFR) were siderite and strontianite, respectively. At the same time, the RPFR of nitratine, which has the same structure as carbonate, was studied. The RPFRs of the three most widely distributed carbonates in nature (dolomite, calcite, and aragonite) were dolomite > calcite > aragonite. Among the H2CO3 solution, CO32− solution, Ca(HCO3)2 solution, and CaCO3 solution, the H2CO3 solution had the strongest ability to enrich 18O. In addition, the equilibrium oxygen isotope fractionation factors between aqueous solutions and gas phase species (CO2(g), H2O(g), and O2(g), etc.) were calculated systematically. The results showed that the oxygen isotope fractionation factors between solutions and gas phases were often inconsistent with the temperature change direction and that the kinetic effects played a key role. These theoretical parameters obtained in this study will provide key equilibrium oxygen isotope constraints for water-rock interaction processes.

Experimental study on the influence of water-rock interaction on the time-varying characteristics of coal rock mass.

In order to study the influence of water-rock interaction on the mass time-varying characteristics of coal rocks, coal was selected as the research object and subjected to chemical immersion tests with different pH aqueous solutions for 12days. By experiment, the time-varying patterns of mass change fraction in coal samples, pH value in solution, and ions concentration of calcium and magnesium were obtained. Based on the gray correlation theory, the correlation degree between the mass change fraction and four influencing factors was analyzed. The gray prediction models for the mass time-varying characteristics of coal rocks have been established. The research shows that: (1) the influence waysanddegree of different pH aqueous solutions on the mass changes of coal rocks are different, (2) during the process of water-rock interaction, the change law of pH value, ions concentration of calcium and magnesium in solution are obvious, (3) the multiple regression modelscan be used to predict the mass change of coal rocks accurately under water-rock interaction.

Controlling Factors of Groundwater Salinization and Pollution in the Oasis Zone of the Cherchen River Basin of Xinjiang

Groundwater is a vital resource for local human life and production in the oasis zone of the Cherchen River Basin of Xinjiang. Understanding the controlling factors of groundwater salinization and pollution is of great significance for the sustainable utilization of groundwater resources and protection of the ecological environment in desert oasis areas. In light of this, a total of 36 single structure unconfined groundwater samples and 54 multi-layered structure unconfined and confined groundwater samples were collected from the oasis zone of the Cherchen River Basin and evaluated for the distribution characteristics and pollution status of major ions. Hydrogeochemical methods (e.g., Piper diagram, multivariate statistics, Gibbs model, and relationships among ions) were used to determine the main controlling factors of groundwater salinization and pollution. Differences in hydrogeochemical zonation were found from the single structure unconfined aquifers in sloping plains of piedmont areas to the multi-layered structure unconfined and confined aquifers in alluvial-proluvial plain areas, and Cl-Na (87.8%) was the main hydrochemical type in the groundwater of the study area. The quality of single structure unconfined groundwater was starkly better than that of the multi-layered unconfined and confined groundwater, which was mainly caused by Na+ (mean value of 9 969 mg·L-1), Cl- (13 687 mg·L-1), and SO42- (5 840 mg·L-1). Moreover, the natural hydrogeochemical process was the main reason for the deterioration of groundwater quality. The hydrochemistry was mainly controlled by the water-rock interaction and evaporation processes. The mineral dissolution of silicates and evaporites was an important source of chemical ions in the groundwater. Furthermore, the chemical weathering of evaporites combined with the processes of evaporation and cation exchange had a significant influence on the salinization of multi-layered unconfined and confined groundwater in alluvial-proluvial plain areas. In addition, synthetic fertilizers were the main pollution sources of NO3- in groundwater in the intensive agricultural zones.

The world-class carbonate-hosted Fankou Zn-Pb deposit in China. Part II. Alterations: C-O isotopic halos footprint the nature and transfer pathway of ore-fluids, and quantitative water-rock interaction process

The giant Fankou Zn-Pb deposit (more than 10 Mt Zn + Pb metals, grading at 15 %), situated in northern margin of the Quren Basin, is one of the largest Zn-Pb deposits in China. The stratiform orebodies are jointly bounded by both the strata (in the specific layers of Middle to Upper Devonian Donggangling and Tianziling carbonate sequences) and the fault system (a three-order thrusting fault system). Ore textures of carbonate dissolution, replacement-infilling and cementation are widespread in Fankou, analogous to a MVT (Mississippi Valley-type) deposit. Owing to the poorly developed fluid inclusions, the nature of the Fankou ore fluids remains indeterminate. To address this problem, we herein utilize micro-petrography, carbon-oxygen (C-O) isotopes and quantitative isotopic exchange modelling to trace the ore-fluids and water-rock interaction process. A total of ninety-three (93) carbonate samples, covering the majorities of stratigraphic horizons, planar locations, and various alteration intensities, were systematically collected. Micro-petrography reveals the primitively sedimentary bioclastic limestone suffer from heterogeneous dolomitization and carbonatization followed by massive Zn-Pb precipitation. These carbonate samples display a widely-ranged, δ18O- and δ13C-depleted isotope signature (δ18O = 12.57 to 23.82 ‰, δ13C = −7.79 to −0.46 ‰), relative to normal marine carbonates (δ18O = 25 ‰, δ13C = 0 ‰). Further modelling of isotopic exchange indicates a low-temperature (100 to 250 °C), δ18O-depleted (−3 to 7 ‰) and δ13C-depleted (−10 to −7‰) ore fluid equilibrated with the host rock by a relatively low water-rock ratio (W/R = 1 to 10). In terms of space, we identified a relatively decreasing trend of δ18O and δ13C isotopic compositions of carbonates, from southeast to northwest, and from bottom to up. Based upon the previous structural analysis, we interpret that the δ18O and δ13C isotopic distribution patterns are caused by a northwestwards transfer pathway of ore-fluids along the thrusting fault system, and the metalliferous, δ18O- and δ13C-depleted fluids are sourced from the interior of the Quren Basin. Collectively, we clarify the deep southeastern part of the Fankou Zn-Pb deposit and the interiors of the Quren Basin is the favorable exploration target in future.

In-situ experiment reveals CO2 enriched fluid migration in faulted caprock

The sealing characteristics of the geological formation located above a CO2 storage reservoir, the so-called caprock, are essential to ensure efficient geological carbon storage. If CO2 were to leak through the caprock, temporal changes in fluid geochemistry can reveal fundamental information on migration mechanisms and induced fluid–rock interactions. Here, we present the results from a unique in-situ injection experiment, where CO2-enriched fluid was continuously injected in a faulted caprock analogue. Our results show that the CO2 migration follows complex pathways within the fault structure. The joint analysis of noble gases, ion concentrations and carbon isotopes allow us to quantify mixing between injected CO2-enriched fluid and resident formation water and to describe the temporal evolution of water–rock interaction processes. The results presented here are a crucial complement to the geophysical monitoring at the fracture scale highlighting a unique migration of CO2 in fault zones.

Fluid-mineral dynamics at the Rincón de la Vieja volcano—hydrothermal system (Costa Rica) inferred by the study of major, minor and rare earth elements in the hyperacid crater lake

Volcanic lakes are complex natural systems and their chemical composition is related to a myriad of processes. The chemical composition of major, minor, Rare Earth Elements (REE) and physico-chemical parameters at the hyperacid crater lake of Rincón de la Vieja volcano (Costa Rica) are here investigated during February 2013–August 2014. The study of the lake chemical composition allows to identify the main geochemical processes occurring in the lake and to track the changes in the volcanic activity, both important for active volcanoes monitoring. The total REE concentration (∑REE) dissolved in the crater lake varies from 2.7 to 3.6 mg kg−1 during the period of observation. REE in the water lake samples normalized to the average volcanic local rock (REEN-local rock) are depleted in light REE (LREE). On the contrary REEN-local rock in the solids precipitated (mainly gypsum/anhydrite), from lake water samples in laboratory at 22°C, are enriched in LREE. The low variability of (La/Pr)N-local rock and (LREE/HREE)N-local rock ratios (0.92–1.07 and 0.66–0.81, respectively) in crater lake waters is consistent with the low phreatic activity (less than 10 phreatic eruptions in 2 years) observed during the period of observation. This period of low activity precedes the unrest started in 2015, thus, it could be considered as a pre-unrest, characterized by infrequent phreatic eruptions. No clear changes in the REE chemistry are associated with the phreatic eruption occurred at mid-2013. The results obtained investigating water-rock interaction processes at the Rincón de la Vieja crater lake show that rock dissolution and mineral precipitation/dissolution are the main processes that control the variability of cations composition over time. In particular, precipitation and dissolution of gypsum and alunite are responsible for the variations of REE in the waters. Despite the low variations of (La/Pr)N-local rock and (LREE/HREE)N-local rock ratios, this study allows to suggest that REE can be used, together with major elements, as practical tracers of water-rock interaction processes and mineral precipitation/dissolution at active hyperacid crater lakes over time, also during periods of quiescence and low phreatic activity.

Hydrochemistry and strontium isotope fingerprints of solute sources and CO2 consumption in Changbai Mountain area, Northeast China.

As one of the most representative forms of groundwater, mineral water provides a critical understanding of regional hydrogeochemical features and rock weathering processes. However, current studies have mostly focused on the quality of mineral water and have rarely addressed the weathering process during its formation. Therefore, a multi-tracer approach combines chemical parameters, major ions, selected trace elements, and 87Sr/86Sr ratios for mineral water samples in Changbai Mountain during 2020-2021. First, we determined the hydrogeochemical characteristics of different types of mineral water. Secondly, the water-rock interaction processes governing the water mineralization were described to fix the hydrogeochemical background. Thirdly, the chemical weathering rate was calculated. The total dissolved load generated by rock weathering was around 6.76 tons/km2/year in the mineral water catchment area; 44.6% and 36.9% of the dissolved load were derived from silicate and carbonate weathering, respectively. The trace carbonates also played an important role in the overall rock weathering. Finally, after fully considering various influencing factors, we concluded that lithological characteristics and the soil environment rich in organic acids were the most important factors affecting rock weathering in the Changbai Mountain area. Overall, this study highlights the mineral water's role in the fluxes of CO2 in local area and reveals possible influence of the unique ecological and geological environment on rock weathering in Changbai Mountain. It can provide a reference for the subsequent assessment of environmental stability for basalt areas and the possibility of sustainable water resources development.

A multidisciplinary geochemical approach to geothermal resource exploration: The Spezzano Albanese thermal system, southern Italy

This work aims to define the geothermal conceptual model of the Spezzano Albanese thermal system located in the northern sector of the Calabria Region, along the western edge of the Sibari Plain. The study confirms that the deep thermal reservoir of Spezzano Albanese is mainly hosted within the permeable levels of the evaporite deposits of the Messinian succession including siltstones with manganese mineralisation, halite, and gypsum-arenites. The thermal waters show discharging temperature between 20.2 and 26.6 °C and a high compositional variability, from Na–Cl to Na–Ca–HCO3. The compositional evolution (from Na–Cl to Na–HCO3) is accompanied by a decrease in both salinity and the concentrations of most dissolved constituents, including Cl, Br, B, Li, Na, K, Mg, Ca, and Ba. These variations are due to mixing between the thermal endmember, rich in Cl and related components, and low-salinity, cold shallow waters (temperature between 17.5 and 22.7 °C). The study points out that the thermal endmember derives by halite dissolution and more complex water-rock interaction processes involving (1) the dissolution of other solid phases of the Messinian deposits, as also confirmed by δ34S values of dissolved sulphate and sulphide, and (2) the precipitation of secondary solid phases (e.g., barite). The geothermometric modelling suggests that the thermal groundwaters in the deep reservoir are probably in equilibrium with either (i) quartz, calcite, disordered dolomite, low-albite, and K-feldspar, as well as with pyrophyllite and poorly crystalline kaolinite (as proxies of clay minerals) at temperatures of 65.5 ± 4.5 °C or (ii) quartz, calcite, disordered dolomite, low-albite, disordered adularia, laumontite and saponites at temperatures of 56.1 ± 4.3 °C, based on the first and second geothermometric model, respectively.The δ18O and δ2H values of water confirm a meteoric origin for the thermal waters with average recharge altitudes between 745 and 857 m a.s.l. These elevations are compatible with the recharge from the western side of the Esaro valley where evaporite successions are found close to the surface.The isotopic value of the dissolved CO2 associated to the Spezzano Terme water highlights its likely microbial origin, as recognised for other thermal circuits hosted in sedimentary rocks of the southern Apennines. Furthermore, the thermal endmember shows a noteworthy enrichment in CH4 with respect to air due to the interaction of groundwater with sediments rich in organic matter. Although methane could have a biogenic origin, the presence of a minor component of thermogenic methane in the gas phase dissolved in the Spezzano Terme waters cannot be completely excluded.The data obtained in this study allow to assume that the recharge meteoric waters descend to a maximum depth of about 1.1–1.4 km below the main emergence area and then the regional NE-SW fault systems probably act as a preferential pathway for the ascent of the thermal waters towards the surface. These waters discharge at Spezzano Albanese, where the crystalline-metamorphic units cropping out immediately upstream of the emergence area act as cap-rock favouring the final ascent towards the surface of the thermal waters.

Reservoir Temperature Calculation and Modeling for Convective Geothermal Systems: Case Study of Five Major Hot Springs in Lushan, Henan, China

The thermal storage temperature and water-rock interaction process of the Lushan convective geothermal system (Qinling stratigraphic zonation fracture zone in China) are clarified by using surface cold water and geothermal fluid as the research objects. In this study, a conceptual model of the temperature profile of the geothermal system in the study area was developed using surface temperature inversion, the cation temperature scale, the SiO2 temperature scale method, the mineral equilibrium phase method, the silicon-enthalpy model, the FixAl method, and the Cl-enthalpy model. The inversion temperature at the surface is in the range of 33-39°C, and the temperature difference indicates the direction of the Checun-Lushan fracture. The study area is recharged from atmospheric precipitation, and the temperature of the recharge area is approximately 5.8–7.7°C (the temperature of the alkali field is approximately 10°C), and the recharge elevation is approximately 1200 m. The thermal storage pattern in the study area is near-surface hydrothermal thermal storage transferred to shallow thermal storage and then to deep thermal storage. The near-surface hydrothermal thermal storage temperature is at a constant temperature of 60°C, and the shallow thermal storage temperature is calculated by K-Mg and Li-Mg geothermometers to be between 99 and 112°C. The thermal storage temperature is simulated using the FixAl method, with deviation values ranging from 2.9% to 15.0%. The silicon-enthalpy model calculates the deep thermal storage temperature to be between 181 and 230°C. The mixing ratio of geothermal water in the study area is extremely high, with a cold water mixing ratio of 85.4–94.8%. The home ground fluid temperature was estimated to be approximately 282°C using the Cl-enthalpy model. The main thermally controlled conductivity channel in the study area is the Checun-Lushan fracture zone. The water vapor formed by convection at depth moves upward to approximately 5 km to form a deep thermal reservoir, and this convection and upward movement cause it to mix with cold water from the fracture zone to form a shallow thermal reservoir, which moves to the near-surface, forming a hydrothermal-type reservoir, which is later discharged in the form of a spring. The conceptual model of geothermal system temperature established in this study provides a basis for further development and utilization of Lushan hot springs and provides guidance for future thermal storage temperature calculations of convection-type geothermal systems in uplifted mountains.

Research on Temporal Patterns of Water-Rock Interaction in the Coal Mine Underground Reservoir Based on the Dynamic Simulation Test.

The temporal pattern of water-rock interaction is significant in predicting the ion concentration of the effluent in coal mine underground reservoirs. This study used the roof-caved rock samples and main incoming water (mine water and fissure water) of the Daliuta coal underground reservoir as the research object and designed four groups of dynamic simulation experiments of the water-rock interaction. Based on the main ion concentrations in the water sample at different reaction times, Q-type hierarchical cluster analysis (HCA) was used to classify the stages of water-rock interaction. The types and intensities of water-rock interaction in each stage were identified by combining the ion ratio and principal component analysis (PCA). Q-type HCA shows that the dynamic simulation experimental water samples can be divided into three categories according to the reaction time, representing the early, middle, and late stages of the water-rock interaction process. The influence of water quality on the division of the water-rock interaction stage is greater than that of rock characteristics. The ion ratio and PCA show that the dissolution of pyrite minerals, cation exchange reaction, and mineral adsorption mainly occur in the early stage of water-rock interaction, in which the cation exchange reaction plays a leading role in the change of ions in water. In the middle stage, the cation exchange reaction and the dissolution of carbonate minerals, such as calcite and dolomite, mainly occur, in which mineral dissolution is the main. In the late stage, the water-rock interaction is relatively weak, and the change of ion concentration in water is not obvious. This study proves the temporal patterns of water-rock interaction between caved rock and mine water (or fissure water) and differences in the types and intensities of water-rock interaction in each stage. The results can provide a theoretical basis for the optimization of the operation cycle of coal mine underground reservoirs and the prediction of effluent ion concentration.

Interdisciplinary Approach and Geodynamic Implications of the Goutitir Geothermal System (Eastern Meseta, Morocco)

Morocco has an important geothermal potential materialized by its several thermal springs which constitute an essential surface geothermal indicator. These springs are dispersed throughout the country and present in every major structural domain. However, a significant amount is concentrated in the northern and northeastern areas. Associated with the great hydrothermal system of eastern Morocco, the thermal spring of Goutitir emerges in the Meso-Cenozoic sedimentary formations located east of the Guercif Basin, composed of a mixture of clays, carbonates, and marls, covered in unconformity by Quaternary tabular molasses. The upflow of the thermal water is dependent of Alpine faults systems with N30 and N100 directions, which are probable reactivated Hercynian structures that facilitate its circulation to the surface. The Goutitir spring has been studied by an interdisciplinary approach to identify the origin of the thermal water, the rock–water interactions, and the reservoir temperatures, contributing to the establishment of the conceptual model of the associated hydrothermal system. This thermal water is of chloride-sodium type with a hyperthermal character (43–47 °C). The isotopic composition (δ18O = −8.7 to −8.35‰; δ2H = −58.6 to −54.3‰) indicates a meteoric origin and a recharging zone located at around 2000 m of altitude. The chemical composition allows to classify the water as chloride-sodium hydrochemical facies, stabilized at ~100 °C in crystalline basement rocks, which, according to seismic data, are located at ~3 km depth. The concentrations, patterns, and correlations of trace elements point out water–rock interaction processes between the deep water and basic magmatic rocks. The integration of the chemical and isotopic data and the surface geological context shows that the Goutitir water flows within a hydrothermal zone were basic to ultrabasic lamprophyres rich in gabbroic xenoliths outcrop, witnessing the existence, at depth, of basic plutons. Moreover, near the source, these veins are strongly altered and hydrothermalized, showing late recrystallization of centimetric-sized biotites. The chloride-sodium composition of this water may also be a testimony to the presence and reaction with the overlying Triassic saline and gypsiferous and Meso-Cenozoic mainly carbonated formations.

The use of copper isotopes for understanding metal transfer mechanisms within the continuum mine-river-dam (Huelva Region, Spain).

Mining areas and in particular those containing massive sulfides have left a heavy environmental legacy with soils and hydrographic networks highly contaminated with metals and metalloids as for example in the Iberian Pyrite Belt (Huelva, Spain). Here, we present new data on copper (Cu) isotopic composition of waters and solids collected along a continuum Mine (Tharsis)-River (Meca)-Lake (Sancho) in the Iberian Pyrite Belt. Our results show that the isotopic signature of pit lakes is spatially variable, but remains stable over the seasons; this signature seems to be controlled by water-rock interaction processes. The data obtained on the Meca River imply a number of attenuation processes such as decrease in the metal concentration by precipitation of secondary minerals. This is accompanied by preferential retention of the heavy isotope (65Cu) with a possibility of living organisms (e.g., algae) participation. The terminal Sancho lake demonstrated constant isotopic signature over the entire depth of the water column despite sizable variations in Cu concentrations, which can be tentatively explained by a superposition of counter-interacting biotic and abiotic processes of Cu fractionation. Overall, the understanding of the isotopic variations along the hydrological continuum is useful for a better understanding of metal element transfer within mining environments and surrounding surface waters.

Environmental Stable and Radioactive Isotopes in the Assessment of Thermomineral Waters in Lisbon Region (Portugal): Contributions for a Conceptual Model

The existence of thermomineral waters in the Lisbon region (western Portugal), has been known for centuries. Several authors have investigated the characteristics of these thermomineral waters, but their conceptual model (recharge zone, processes controlling the origin and chemical evolution, depth of circulation, etc.) remains unknown. This work highlights the advantages of assessing the conceptual model in urban coastal areas, where different saline sources coexist, combining chemical analyses with environmental isotopes and geochemical modeling. The final physicochemical composition of thermomineral waters seems to be mainly controlled by water–rock interaction processes and different mixing degrees between HCO3-Ca regional groundwaters, cold dilute shallow groundwaters and highly salinized fluid (brackish or brine or non-recent seawater) probably trapped at depth. Based on these results, neither the contribution of polluted water nor the leaching of evaporite rocks seems to be the main salinization factor of the warmer and saline waters. A positive correlation exists between the lowest radiocarbon activities (average apparent ages ~6 ka BP) and highest water temperature and salinity (up to 39 °C and 6.3 g/L), suggesting progressive salinization and deeper circulation (up to 1200 m depth) into the hosting formations, where mixing with trapped salinized fluids probably took place, as confirmed by geochemical modeling. Finally, very favorable geological conditions in the Estoril region allow for fast rising and the occurrence of these thermomineral waters at relatively shallow depths.

Hydrogeochemical characterization of groundwater in a coastal area, central western Senegal

One of the most serious problems affecting coastal aquifers is seawater intrusion. Senegal is currently facing an increased demand for freshwater resources due to population growth and economic development in coastal areas. In areas affected by saltwater contamination, chloride concentrations as high as 8880 mg/L were measured in groundwater samples taken from wells near the coastal zone, indicating deterioration in water quality. Our study aims to identify the zones of degradation of the water quality by determining the chemical composition of groundwater and the geochemical processes controlling the chemical patterns. Hydrogeochemical (Piper and Chadha diagrams, chloroalkaline indices, normalized bivariate plots) and multivariate statistical (Hierarchical cluster analyses) techniques were used. Forty-two groundwater samples were collected and analyzed for concentrations of major and some minor ions, electrical conductivity (EC), total dissolved solids (TDS), temperature, and pH. From samples we were able to establish a diagnosis of the very heterogeneous quality of the groundwater in this area. The average pH of the groundwater is 7.6 and about 80% of the groundwater samples have a TDS below 1000 mg/L. On the other hand, the EC values are very heterogeneous with very high conductivities in coastal areas. Approximately, 80% of the groundwater samples have a TDS less than 1000 mg/L and EC values are very heterogeneous. The dominant water types in the study area are Na-Cl water type (less than 10% of the samples) characteristic of the spatial evolution of groundwater salinization from west to east, mixed Ca-Mg-Cl due to fresh water/salt water contact and Ca-Mg-HCO3 water-type (nearly 56% of the samples) to the east. A hydrogeochemical zonation of the aquifer, based on the presence of different water families allows us to visualize the highly degraded (west), mixed (center) and healthy (east) zones. Chloroalkaline indices and normalized bivariate plots show that the chemistry of groundwater is controlled mainly by water-rock interaction and evaporation processes. As water-rock interaction processes, dissolution of carbonate and evaporite, weathering of silicate, ions exchange regulates major ion chemistry.

Understanding regional groundwater flow using water-rock interaction processes and anthropic signatures in a fractured volcanic aquifer

This research evaluated the hydrochemistry of a fractured volcanic aquifer at Paraná 3 Basin, in the western region of the state of Paraná, southern Brazil. Geochemical rock data from the literature were used to describe the distinctive characteristics of the principal geological units in the area, Pitanga and Paranapanema Formations, both belonging to the Serra Geral Group. Data from x-ray diffraction were obtained to deepen the study of hydrogeochemical processes. Previous studies did not consider the differences in the lithogeochemistry of the group, in the terms contemplated in this research. In addition, the research also approaches the evaluation of the flow depth contribution in the groundwater chemistry and the analysis of hydrogeochemistry processes. For this analysis, a set of chemical data was utilized on 35 groundwater samples from water supply boreholes at Paraná 3 Basin. From shallow to deep flow, there was an increase in pH, electrical conductivity, total dissolved solids, total alkalinity and a decrease in CO2. These parameters exert the main physical-chemical groundwater controls, which are identified by changes in the major ions along the flow lines, as well as by variations in trace elements. The water-rock interaction becomes increasingly evident in the intermediate and deep flows, standing the higher alkalinity, pH, electrical conductivity, total dissolved solids (TDS) and most of the trace elements at Pitanga Formation. Pitanga Formation presents higher medians of alkalinity (95.5 mg.L-1), electrical conductivity (225 μS.cm-1) and TDS (140.0 mg.L-1) than Paranapanema Formation (57.0 mg.L-1; 130 μS.cm-1 and 90.0 mg.L-1, respectively). Furthermore, the pH distribution shows greater values starting at the 60% percentile in Pitanga Formation (8.24), compared to Paranapanema (8.10). Despite such differences, it was not possible to distinguish the geological units with the hydrochemical characterization, probably because both units are mainly represented by rocks of basic composition, with a similar mineralogical basis. The shallow hydrogeochemical processes are characterized by the weathering of Fe–Mg silicates and plagioclase, changing to a predominance of ion exchange in deeper flows. Calcite precipitation is a secondary process, associated with calcium consumption towards deeper flows. Anthropic influences are mainly observed with more elevated concentrations of NO3-, PO43-, Cl- and K+, occurring in the entire basin, and they are strongly evidenced by the correlation between Cl- and NO3- in most samples.