Water-rock Interaction Processes Research Articles

Understanding water–rock interaction in crystalline shield fluids using calcium isotopes

Calcium isotopes provide a potentially robust tool for understanding the evolution of crystalline shield fluids, but previous applications have focused on near surface groundwaters. The tendency of Ca isotopes to be affected by mass-dependent fractionation during processes such as water–rock interaction provides a powerful tool for studying the evolution and origin of groundwaters hosted in crystalline rocks. We report Ca isotope ratios (δ44/40Ca) of deep fluids (>300 m) from across the Canadian Shield and integrate these with Sr and Br isotope values to understand long-term fluid–rock interactions in crystalline shield environments. Ca isotope ratios have a wide range of values from 0.07‰ to 0.86‰. At individual sites, δ44/40Ca values are variable whereas 87Sr/86Sr ratios are relatively constant. Sr isotope ratios (87Sr/86Sr) have a negative relationship with the Ca vs. Na content of the fluid indicating different host-minerals contributing Sr to the fluid. Ca isotope fractionation was caused by metamorphic reactions and by the growth and dissolution of Ca-rich fracture-filling minerals. The δ44/40Ca signatures of these processes are overprinted by radiogenic ingrowth of 40Ca by decay of 40K, which is expected to affect older and more K-rich rocks. At one site, δ44/40Ca and δ81Br variability reflects gas-generating reactions in the fluid and/or water–rock interaction processes. These new results demonstrate the strength of combining multiple isotope analysis to elucidate the sources of groundwater salinity and decipher the complex long-term processes that occur in crystalline shield environments.

Groundwater quality assessment for drinking and irrigation purposes in arid to semiarid region of Indus Basin of South Punjab, Pakistan

<p><a name="_Hlk173243332"><span style="background-color:white;color:black;font-family:"Times New Roman",serif;font-size:12.0pt;line-height:150%;">As the groundwater pollution is increasing, it is crucial to assess groundwater quality and characterize hydrogeochemistry accurately for long term water supply. </span></a><span style="background-color:white;color:black;font-family:"Times New Roman",serif;font-size:12.0pt;line-height:150%;">In this study groundwater samples were collected from 120 locations from Bahawalpur district and analyzed for electrical conductivity (EC), pH, total dissolved solids (TDS), sodium (Na<sup>+</sup>), potassium (K<sup>+</sup>), calcium (Ca<sup>2+</sup>), magnesium (Mg<sup>2+</sup>), carbonate (CO<sub>3</sub><sup>-</sup>), bicarbonate (HCO<sub>3</sub><sup>-</sup>), sulfate (SO<sub>4</sub><sup>2-</sup>), chloride (Cl<sup>-</sup>), nitrate (NO<sub>3</sub><sup>-</sup>), fluoride (F<sup>-</sup>) and heavy metals. The results obtained from the analysis of samples showed that the SAR of nearly 65% of samples collected from Bahawalpur district were in acceptable limit (<6 meq L<sup>-1</sup>), while 12% found to be unfit for irrigation (>10 meq L<sup>-1</sup>). Similarly, the RSC values depicted that 8% samples were unfit while 64% samples were falling in the category of fit irrigation water. Most of the water samples were predominantly Ca<sup>2+</sup>-HCO<sub>3</sub><sup>-</sup> and Na<sup>+</sup>-HCO<sub>3</sub><sup>-</sup> type, that were controlled by various processes of cation exchange, water-rock interaction, dissolution and evaporation. Some samples fall in the middle of diamond and lower triangles of Piper diagram are showing no dominant type of water (mixed water type) due to the complex influence of rock-water interactions as well as anthropogenic activities. The Water Quality Index (WQI) showed that out of total 120 sampling sites in Bahawalpur the number of excellent water samples were only 2% while 18% water samples were characterized as hazardous. Moreover, the number of samples falling in the categories of good, poor and very poor quality water were 36%, 29% and 13% respectively.</span></p>

Performance evaluation of a community-based water management organisation using integrated water quality monitoring

ABSTRACT Community-based water management organisations (CBWMOs) play an important role in providing water services worldwide. However, there is some debate as to their capacity to sustain a safe drinking water supply considering the current socioeconomic and climate scenarios. Here, we present an integrated water quality assessment of the supply system of a CBWMO in Concepción of San Ramon, Costa Rica. Major ions, trace metals, and coliforms were analysed in the households and water sources over a 1-year period. The spring risk assessments and the water quality of the main river in the catchment were also carried out. We found that although the supplied water meets adequate standards, spatial and temporal changes in the water quality of the sources exist. Springwater composition is mainly driven by rock–water interaction processes, but early signs of potential anthropogenic pollution were found. The springs showed concentrations of NO3- above natural levels and microbial contamination in 37 and 18% of the cases, respectively. River water quality showed a distinct composition, which is consistent with the anthropogenic pressures in the catchment. This study provides useful information on how water quality assessments can be used beyond regulatory processes to improve planning by CBWMOs to ensure water security.

Understanding zinc isotopic signatures in volcanic lakes

Magmatic activity can be monitored through the chemical variations of volcanic lakes. While those lakes can be influenced by direct magmatic input, water-rock interaction processes in hydrothermal system also have a large influence. Disentangling those effects is critical to use crater lakes for volcanic activity monitoring purposes. Zinc is a volatile metal that is easily degassed and can be incorporated into fluid circulation. During degassing, Zn isotopes can be fractionated and can thus be a potential tracer of magmatic input. Here we present a novel approach using stable Zn isotopic systems to understand how dissolution/precipitation processes affect isotopic compositions of volcanic lakes and if they can be used as tracers of magmatic activity. We investigate Zn isotopes expressed as δ66Zn for four volcanic lakes ranging from hyperacidic to neutral waters. Two of them, Kawah Ijen (Indonesia) and Santa Ana (El Salvador) volcanic lakes have been sampled from 2010 to 2012 and 2000–2002, respectively, and show a clear magmatic input with extremely low pH [0.1–1]. Taal (Philippines, pH ≈ 3) and Kelud (Indonesia, pH ≈ 6.5) volcanic lakes were sampled from 2017 to 2019 and 2003–2007 respectively, and are dominated by hydrothermal rather than magmatic inputs. Hyper-acidic lakes show minimal isotopic variation over the investigated time ranges, with δ66Zn values similar to their basalt-andesitic host rocks (0.26 ± 0.08 ‰). In contrast, we observe large δ66Zn fractionation for the Taal waters (0.4 ± 0.01 ‰) compared to their basalt-andesitic host rocks but no δ66Zn temporal variations. Kelud waters show significant δ66Zn (−0.08 ± 0.06 ‰ to 0.43 ± 0.06 ‰) temporal variation. This could be related to an evolution of the lake water chemistry as the sampling period occurred between two increases in lake temperature culminating into a lava dome eruption in 2007. For Taal and Kelud volcanic lakes, enrichment factors (EF) and PHREEQc modelling indicate that Zn is depleted and suggest that Zn could precipitate in the hydrothermal system, hence fractionating Zn isotopes during these precipitation processes. This contrasts to Zn elemental and isotope values from Kawah Ijen and Santa Ana with an EF ≈ 1 suggesting that Zn is derived from host rock dissolution, in agreement with their δ66Zn. These data are still limited and a longer observation is needed in the future to highlight significant geochemical changes in volcanic lakes and their relation to volcanic activity.

Origin of Groundwater in Kawung Carang Cold Spring, Sumbang District, Banyumas Regency, Central Java

Abstract The occurrence of several springs around Slamet Volcano raised questions regarding their origin. Many studies have been conducted to understand the origin of hot spring water around Slamet Volcano. Meanwhile, there has not been any research on the origin and hydrogeological system of cold spring water around Slamet Volcano. Kawung Carang Spring is one of cold spring water that occurs on the southern flank of Slamet Volcano. It is situated in a quaternary volcanic deposit of Mt. Slamet formation. Field observation was conducted to identify local geological conditions and hydrogeological systems in the research area. Isotopic analysis was performed to help understand how to delineate the recharge area. This study used a physical-chemical analysis of Kawung Carang cold spring water and the ratio of deuterium (2H) and 18O stable isotopes to interpret its groundwater origin. The results of the analysis informed that the origin of Kawung Carang spring water was local meteoric water. The hydrogeological system was an unconfined aquifer that consisted of a lahar deposit on the top of a volcanic breccia layer. The physical-chemical characteristic of groundwater around the Kawung Carang cold spring shows low electric conductivity (EC) and total dissolved solids (TDS) values. EC and TDS values of groundwater vary from 92 to 253 µS/cm and 46 to 126 mg/L indicating that groundwater has a short time in water-rock interaction process and comes from shallow depth aquifer. Furthermore, the signature of stable isotopes of δ18O and δ2H shows the elevation of the Kawung Carang cold spring recharge area ranges from 386.08 to 441.37 meters above sea level in the northwestern part of the research area.

Hydrogeochemistry of geothermal water in Huangshadong and adjacent areas of Guangdong province: Implications for water-rock interaction

Hydrogeochemical characteristics can reflect important information on the circulation processes of geothermal fluids, reservoir temperatures, etc., which are essential for exploring geothermal field evolution and the rational development of geothermal resources. 23 sets of water samples were collected from Huangshadong and adjacent geothermal fields. Major cations and anions, hydrogen and oxygen isotopes, and 14C activities were analyzed to investigate the hydrogeochemical characteristics of geothermal fluids and their formation mechanisms. Hydrogen and oxygen isotope analysis and major element chemistry indicate that the geothermal waters in the study area are mainly recharged by meteoric water. The chemical facies of the geothermal waters are mainly Na−HCO3 and Ca−HCO3, and most of the geothermal waters have high Na+ contents, which are attributed to the involvement of albite in water-rock interaction and the replacement of Na+ in rocks by Ca2+ or Mg2+ in water. Geothermometry of geothermal waters suggests that the reservoir temperatures are between 140-150 ℃, and the geothermal water circulation depths range from 2.0 to 4.3 km. The residence time of up to 17.3ka for geothermal water likely suggests the earliest precipitation recharge during the Late Pleistocene. Major element chemistry and hydrogen and oxygen isotope systematics indicate essential information on the origins of geothermal waters and water-rock interaction processes and provide a more comprehensive understanding of the geothermal system in Huangshadong and adjacent areas of Guangdong province.

A comprehensive monitoring approach for a naturally anoxic aquifer beneath a controlled landfill

The processes leading to high levels of arsenic (As), iron (Fe), and manganese (Mn) in groundwater, in a naturally reducing aquifer at a controlled municipal landfill site, are investigated. The challenge is to distinguish the natural water-rock interaction processes, that allow these substances to dissolve in groundwater, from direct pollution or enhanced dissolution of hydroxides as undesired consequences of the anthropic activities above. Ordinary groundwater monitoring of physical-chemical parameters and inorganic compounds (major and trace elements) was complemented by environmental isotopes of groundwater (tritium, deuterium, oxygen-18 and carbon-13) and dissolved gases (carbon-13 of methane and carbon dioxide and carbon-14 of methane). Pearson/Spearman correlation indices, as well as Principal Component Analysis (PCA), were used to determine the main correlations among variables. The concurrent presence of As, Fe and CH4, as reported in similar anoxic environments, suggests that anaerobic oxidation of methane could drive the reductive dissolution of As-rich Fe(III)(hydro)oxides. Manganese is more sensitive to carbon dioxide, possibly due to a decrease in pH which accelerates the dissolution of Mn-oxides. Finally, we found that tritium and deuterium, which have been used for decades as leachate tracer in groundwater, may be subject to false positives due to the reuse of water recovered from leachate treatment (which has the same isotopic signature of leachate) within the plants, to comply with the requirements of the circular economy. The integration of the environmental isotope analysis into the traditional monitoring approach can effectively support the comprehension of processes. However, this strategy needs to be complemented by a good conceptual hydrogeological model and expert evaluation to avoid misinterpretations.

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.