Fluid Geochemistry as Indicator of Tectonically-Related,Deep Water Circulations in the Sardinian Rift-Campidano Graben (Italy): New Insights from Environmental Isotopes

The EC funded Geochemical Seismic Zonation program (EEC GSZ Project 1996–1998) chose Sardinia as a low-seismicity site, in which the relationships between fluid geochemistry and seismo-tectonics had to be investigated and results compared with outcomes from other selected high-seismicity sites. A first article, examining the role of fault segmentation and seismic quiescence on the geochemical composition of groundwaters and gases, has already been presented (Angelone et al. 2005). This article deals with environmental isotopes which, together with selected hydrochemical data, give hints on tectonically-related fluid circulations. Four water-dominated hydrothermal systems were considered, all located along regional fault systems and discharging groundwaters belonging to the Na–HCO₃ and Na–Cl facies. In the considered systems, groundwater circulation takes place, principally, in the Palaeozoic Crystalline Basement (PCB), with the exception of the Logudoro system, where hydrological circuits develop in the Mesozoic Carbonate Platform (MCP). The high CO₂ contents, the non-attainment of fluid-rock equilibrium and the large lithological variability prevent the construction of a unique hydrogeological–geochemical conceptual model. In this case, stable isotopes provide a useful tool to describe the origin of fluids and their subterranean movements. Stable isotopes of water, integrated with hydrochemical data, indicate that fluids are derived from three main end members. The dominant component is a relatively recent local meteoric water; the second one is marine water; and the third one is a fossil freshwater, depleted in heavy isotopes with respect to modern rains. The latter end member entered the aquifer system in the past, when climatic conditions were greatly different from today. At least two circulation systems can be recognised, namely a shallow cold system and a deep hydrothermal system, as well as two distinct hydrological processes: (1) gravity-controlled descent of cold water towards greater depths and (2) convection linked to a thermal gradient, causing deep fluids to rise up from the hydrothermal reservoir towards the surface. The highly variable δ¹³C_TDIC values suggest the presence of two distinct CO₂ sources, namely, a biogenic one and a thermogenic one. The relation between the isotopic compositions of CO₂ and He indicates an increased mantle signature in uprising CO₂-rich fluids.     

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.     

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO₃ (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO₃ spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (³H), helium-3 (³He_trit), sulfur hexafluoride (SF₆)—for four Ca–HCO₃ spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.The online version of the original article can be found at     

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO₃ (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO₃ spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (³H), helium-3 (³He_trit), sulfur hexafluoride (SF₆)—for four Ca–HCO₃ spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.An erratum to this article can be found at     

The origin of thermal waters in the northeastern part of the Eger Rift,Czech Republic

An investigation of the thermal waters in the Ústí nad Labem area in the northeastern part of the Eger Rift has been carried out, with the principal objective of determining their origin. Waters from geothermal reservoirs in the aquifers of the Bohemian Cretaceous Basin (BCB) from depths of 240 to 616 m are exploited here. For comparison, thermal waters of the adjacent Teplice Spa area were also incorporated into the study. Results based on water chemistry and isotopes indicate mixing of groundwater from aquifers of the BCB with groundwater derived from underlying crystalline rocks of the Erzgebirge Mts. Unlike thermal waters in Dě?ín, which are of Ca–HCO₃ type, there are two types of thermal waters in Ústí nad Labem, Na–HCO₃–Cl–SO₄ type with high TDS values and Na–Ca–HCO₃–SO₄ type with low TDS values. Carbon isotope data, speciation calculations, and inverse geochemical modeling suggest a significant input of endogenous CO₂ at Ústí nad Labem in the case of high TDS groundwaters. Besides CO₂ input, both silicate dissolution and cation exchange coupled with dissolution of carbonates may explain the origin of high TDS thermal waters equally well. This is a consequence of similar δ¹³C and ¹⁴C values in endogenous CO₂ and carbonates (both sources have ¹⁴C of 0 pmc, endogenous CO₂ δ¹³C around −3‰, carbonates in the range from −5‰ to +3‰ V-PDB). The source of Cl⁻ seems to be relict brine formed in Tertiary lakes, which infiltrated into the deep rift zone and is being flushed out. The difference between high and low TDS groundwaters in Ústí nad Labem is caused by location of the high mineralization groundwater wells in CO₂ emanation centers linked to channel-like conduits. This results in high dissolution rates of minerals and in different δ¹³C(DIC) and ¹⁴C(DIC) fingerprints. A combined δ³⁴S and δ¹⁸O study of dissolved SO₄ indicates multiple SO₄ sources, involving SO₄ from relict brines and oxidation of H₂S. The study clearly demonstrates potential problems encountered at sites with multiple sources of C, where several evolutionary groundwater scenarios are possible.     

Integrated hydrochemical assessment of the Quaternary alluvial aquifer of the Guadalquivir River, southern Spain

The alluvial aquifer of the Guadalquivir River comprises shallow Quaternary deposits located in the central-eastern part of the Province of Jaén in southern Spain, where groundwater resources are used mainly for crop irrigation in an important agricultural area. In order to establish the baseline hydrochemical conditions and processes determining the groundwater quality, groundwater and river water samples were collected as part of an integrated investigation that coupled multivariate statistical analysis with hydrochemical methods to identify and interpret the groundwater chemistry of the aquifer system. Three main hydrochemical types (Mg–Ca–HCO₃, Ca–Mg–SO₄–HCO₃–Cl and Na–Ca–Mg–Cl–SO₄) were identified. Further interpretation, using R-mode principal components analysis (PCA) conducted with 13 hydrochemical variables, identified two principal components which explain ⅔ of the variance in the original data. In combination with the hydrochemical interpretation, mineralogical analyses of the aquifer sediment together with inverse geochemical modelling using NETPATH showed that dedolomitization (calcite precipitation and dolomite dissolution driven by gypsum dissolution) is the principal hydrochemical process controlling the regional groundwater chemistry. Other processes such as silicate weathering, ion exchange, mixing between river water and groundwater, and agricultural practices also affect the groundwater chemistry.     

Interaction between deep and shallow groundwater systems in areas affected by Quaternary tectonics (Central Italy): a geochemical and isotope approach

Hydro- and isotope geochemistry are used to refine groundwater conceptual models in two areas of central Italy (Acque Albule Basin and Velino River Valley) affected by extensional Quaternary tectonics, where deep and shallow groundwater flow systems are interacting. The role of geology, of recent deposits filling the plains and of main tectonic features controlling groundwater flowpaths and deep-seated fluids emergences are investigated and discussed. Environmental isotopes (²H and ¹⁸O) confirm recharge in the surrounding carbonate aquifers, and meteoric origin of both shallow and deep groundwater. Major ion chemistry indicates a mixing between shallow Ca-HCO₃ groundwater from carbonate aquifers and deep Ca-HCO₃-SO₄ groundwater, characterised by higher salinity and temperature and high concentration in sulphates. Isotopic composition of dissolved sulphates (δ ³⁴S and δ ¹⁸O) and dissolved inorganic carbon (δ ¹³C), henceforth indicated as DIC, are used to verify the presence of different sources of groundwater, and to validate the mixing model suggested by the major ion analyses. Sulphate isotope composition suggests a marine origin for the groundwater characterised by elevated sulphate concentration, whose source is present in the deep buried sequences. Carbon isotope composition confirms the role of a DIC source associated to CO₂ degassing of a deep reservoir. Groundwater conceptual models are improved underlining the importance of Plio-Pleistocene sequences filling the tectonic depression. In the Acque Albule area, the travertine plateau represents a mixing stratified aquifer, where deep groundwater contribution is spread into the shallow aquifer. The alluvial–clastic–lacustrine leaky aquifer of Velino Valley enables a complete mixing of shallow and deep groundwater allowing spot-located discharge of deep groundwater along tectonic patterns and facilitating sulphate reduction in the lacustrine sediments, explaining locally the presence of H₂S.     

Influence of hydrogeochemical processes on temporal changes in groundwater quality in a part of Nalgonda district, Andhra Pradesh, India

Geochemical processes that take place in the aquifer have played a major role in spatial and temporal variations of groundwater quality. This study was carried out with an objective of identifying the hydrogeochemical processes that controls the groundwater quality in a weathered hard rock aquifer in a part of Nalgonda district, Andhra Pradesh, India. Groundwater samples were collected from 45 wells once every 2 months from March 2008 to September 2009. Chemical parameters of groundwater such as groundwater level, EC and pH were measured insitu. The major ion concentrations such as Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl⁻, and SO₄ ²⁻ were analyzed using ion chromatograph. CO₃ ⁻ and HCO₃ ⁻ concentration was determined by acid–base titration. The abundance of major cation concentration in groundwater is as Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ while that of anions is HCO₃ ⁻ > SO₄ ²⁻ > Cl⁻ > CO₃ ⁻. Ca–HCO₃, Na–Cl, Ca–Na–HCO₃ and Ca–Mg–Cl are the dominant groundwater types in this area. Relation between temporal variation in groundwater level and saturation index of minerals reveals the evaporation process. The ion-exchange process controls the concentration of ions such as calcium, magnesium and sodium. The ionic ratio of Ca/Mg explains the contribution of calcite and dolomite to groundwater. In general, the geochemical processes and temporal variation of groundwater in this area are influenced by evaporation processes, ion exchange and dissolution of minerals.     

Geochemical Eccentricity of Ground Water Allied to Weathering of Basalts from the Deccan Volcanic Province,India: Insinuation on CO<Subscript>2</Subscript> Consumption

Analyses of 72 samples from Upper Panjhara basin in the northern part of Deccan Plateau, India, indicate that geochemical incongruity of groundwater is largely a function of mineral composition of the basaltic lithology. Higher proportion of alkaline earth elements to total cations and HCO₃>Cl + SO₄ reflect weathering of primary silicates as chief source of ions. Inputs of Cl, SO₄, and NO₃ are related to rainfall and localized anthropogenic factors. Groundwater from recharge area representing Ca + Mg–HCO₃ type progressively evolves to Ca + Na–HCO₃ and Na–Ca–HCO₃ class along flow direction replicates the role of cation exchange and precipitation processes. While the post-monsoon chemistry is controlled by silicate mineral dissolution + cation exchange reactions, pre-monsoon variability is attributable chiefly to precipitation reactions + anthropogenic factors. Positive correlations between Mg vs HCO₃ and Ca + Mg vs HCO₃ supports selective dissolution of olivine and pyroxene as dominant process in post-monsoon followed by dissolution of plagioclase feldspar and secondary carbonates. The pre-monsoon data however, points toward the dissolution of plagioclase and precipitation of CaCO₃ supported by improved correlation coefficients between Na + Ca vs HCO₃ and negative correlation of Ca vs HCO₃, respectively. It is proposed that the eccentricity in the composition of groundwater from the Panjhara basin is a function of selective dissolution of olivine > pyroxene followed by plagioclase feldspar. The data suggest siallitization (L < R and R _k) as dominant mechanism of chemical weathering of basalts, stimulating monosiallitic (kaolinite) and bisiallitic (montmorillonite) products. The chemical denudation rates for Panjhara basin worked out separately for the ground and surface water component range from 6.98 to 36.65 tons/km²/yr, respectively. The values of the CO₂ consumption rates range between 0.18 × 10⁶ mol//km²/yr (groundwater) and 0.9 × 10⁶ mol/km²/yr (surface water), which indicates that the groundwater forms a considerable fraction of CO₂ consumption, an inference, that is, not taken into contemplation in most of the studies.     

Groundwater geochemical evolution in the northern portion of the Guarani Aquifer System (Brazil) and its relationship to diagenetic features

The groundwater flow pattern in the northern portion of GAS (Guarani Aquifer System) is characterized by the existence of four regional recharge areas located in São Paulo, Mato Grosso do Sul and Goiás states. From these areas of recharge the regional flow is radial and directed toward the center of the Paraná Sedimentary Basin. Local discharge occurs in portions of outcrop regions. The groundwater has low mineralization and can be classified as Ca or Ca–Mg–HCO₃ type, Na–HCO₃ type and Na–HCO₃/Cl/SO₄ type, this sequence represents the hydrochemical evolution. The mechanisms responsible for this evolution are dissolution of feldspars and removal of the carbonate cement from the sandstone mineral framework, followed by ion exchange, responsible for the increase in the Na concentration and decrease of Ca, and, finally, enrichment in Cl and SO₄ derived from underlying aquifer units. The hydrochemical evolution is consistent with diagenetic features that are observed in the sandstones, with the presence of siliceous cement in the outcrop areas, and carbonate cement toward the center of Paraná Basin.     

Saline groundwater seepage zones and their impact on soil and water resources in the Spicers Creek catchment,central west,New South Wales,Australia

Saline seepage zone development and hence dryland salinity is a major environmental problem which many arid to semiarid landscapes in Australia are experiencing. Due to the geological complexity of the regional aquifer system and the heterogeneous nature of the local groundwater system, each groundwater seepage zone in the Spicers Creek catchment, central west, New South Wales, Australia possesses different mechanisms which control its development. Saline seepage zones have formed adjacent to a fault zone, and two experimental sites were established through these groundwater discharge zones to understand geochemical processes which have led to the development of soil sodicity, gully erosion and the flushing of salts into the surface water systems. Seepage zone groundwaters contain a distinctive geochemical signature with elevated concentrations of Na, Cl, HCO₃, Ca, Sr, B, As and Li. The mixing of deep saline groundwaters together with ion exchange processes lead to a distinctive seepage zone groundwater chemistry being developed. Altering the landscape features within this rural groundwater system has developed water toxicity for crops, soil sodicity leading to land degradation, and waterlogging problems.     

A study on the hydrogeology and hydrogeochemistry of groundwater from different depths in a coastal aquifer: Annamalai Nagar,Tamilnadu, India

Chemical characterization of groundwater is essential to bring out its nature and utility. Samples from shallow and deep ground water of the same location were collected and studied for their geochemical characteristics following standard procedures (APHA 1998). Sediment samples from different depths were collected and analysed for minerals using FTIR and SEM. Resisitivity logging was carried out in the bore well to understand the variations in depth to fresh water potential. The shallow ground water is dominated by Na–Cl–HCO₃–SO₄ and deeper groundwater by Na–HCO₃–SO₄–Cl types. It is observed that there is a significant ionic variation with depth. The ionic strength of the deeper samples is lesser than in the shallower samples. Wide pH variations in the shallow water samples are due to ion exchange process. Thermodynamic stability plot was used to identify the state of stability. It is inferred that there is no major significant difference in the thermodynamic state of stability in the shallow and the deeper aquifers as the aquifer matrix for the shallow and deeper aquifers are almost similar. Saturation index of Gibbsite, Kaolinite, Calcite, Dolomite and anhydrite, were studied for shallow and deep aquifers, to identify the difference in hydro chemical signatures. The Si/Al ratios of shallow samples are less when compared with the deeper samples. Leaching of secondary salts was the chief mechanism controlling the ground water chemistry of the region.     

Statistical and geochemical assessment of groundwater quality in Teboursouk area (Northwestern Tunisian Atlas)

Teboursouk region, Northwestern Tunisia, is characterized by the diversity of its natural resources (petroleum, groundwater and minerals). It constitutes a particular site widely studied, especially from a tectonic stand point as it exhibits a complex architecture dominated by multi-scale synclinals and Triassic extrusions. It has typical karst landform that constitutes important water resources devoted for human consumption and agriculture activities, besides to the exploitation of the Mio-Plio-Quaternary aquifer (MPQ). Thus, hydrogeological investigations play a significant role in the assessment of groundwater mineralization and the evaluation of the used water quality for different purposes. Hence, the current study based on a combined geochemical–statistical investigation of 50 groundwater samples from the multilayered aquifer system in the study area give crucial information about the principal factors and processes influencing groundwater chemistry. The chemical analysis of the water samples showed that Teboursouk groundwater is dominantly of Ca–Mg–Cl–SO₄ water type with little contribution of Ca–Mg–HCO₃, Na–K–Cl–SO₄ and Na–K–HCO₃. The total dissolved solids (TDS) values range from 0.37 to 3.58 g/l. The highest values are located near the Triassic outcrops. Furthermore, the hydrogeochemistry of the studied system was linked with various processes such as carbonates weathering, evaporites dissolution of Triassic outcrops and anthropogenic activities (nitrate contamination). Additionally, the main processes controlling Teboursouk water system were examined by means of multivariate statistical analysis (PCA and HCA) applied in this study based on 10 physicochemical parameters (TDS, pH, SO₄, HCO₃, pCO₂, Ca, Mg, Na, K, Cl and NO₃). Two principal components were extracted from PCA accounting 61% of total variance and revealing that the chemical characteristics of groundwater in the region were acquired through carbonates and evaporite dissolution besides to nitrate contamination. Similarly, according to Cluster analysis using Ward’s method and squared Euclidean distance, groundwater from the studied basin belongs to five different groups suggesting that the geochemical evolution of Teboursouk groundwater is controlled by dissolution of carbonates minerals, chemical weathering of Triassic evaporite outcrops, cation exchange and anthropogenic activities (nitrate contamination).     

Hydrochemical characteristics of groundwater in the Kingston Basin,Kingston, Jamaica

The Kingston Basin in Jamaica is an important hydrologic basin in terms of both domestic and industrial sector. The Kingston hydrologic basin covers an area of approximately 258 km² of which 111 km² underlain by an alluvium aquifer, 34 km² by a limestone aquifer and the remainder underlain by low permeability rocks with insignificant groundwater resources. Rapid development in recent years has led to an increased demand for water, which is increasingly being fulfilled by groundwater abstraction. A detailed knowledge of the water quality can enhance understanding of the hydrochemical system, promoting sustainable development and effective management of groundwater resources. To achieve this, a hydrochemical investigation was carried out in the Kingston Basin. Results showed that the water is Na–Ca–Cl–HCO₃ and Na–Ca–HCO₃ type with higher concentrations of nitrate, sodium and chloride as the leading causes of contamination in most of the wells. High concentrations of nitrate correlate with wells from areas of high population density and could be attributed to anthropogenic causes, mainly involving improper sewage treatment methodologies or leaking sewer lines. Jamaica, owing to its island nature, has the continuous problem of saline water intrusion, and this is reflected in the higher levels of chloride, sodium and conductivity in the water samples collected from the wells. The wells studied show higher concentrations of chloride ranging from around 10.2 mg/l in wells located approximately (4931.45 m) from the coast to around 234 mg/l in the well located near to the coast. The conductivity values also closely correlate with the chloride levels found in the wells.     

Hydrogeochemistry and groundwater quality assessment of the multilayered aquifer in Lower Kelantan Basin,Kelantan, Malaysia

Continual expansion of population density, urbanization, agriculture, and industry in most parts of the world has increased the generation of pollution, which contributes to the deterioration of surface water quality. This causes the dependence on groundwater sources for their daily needs to accumulate day by day, which raises concerns about their quality and hydrogeochemistry. This study was carried out to increase understanding of the geological setup and assess the groundwater hydrogeochemical characteristics of the multilayered aquifers in Lower Kelantan Basin. Based on lithological data correlation of exploration wells, the study area can be divided into three main aquifers: shallow, intermediate and deep aquifers. From these three aquifers, 101 groundwater samples were collected and analyzed for various parameters. The results showed that pH values in the shallow, intermediate and deep aquifers were generally acidic to slightly alkaline. The sequences of major cations and anions were Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and HCO₃^? > Cl^? > SO₄^2? > CO₃^2?, respectively. In the intermediate aquifer, the influence of ancient seawater was the primary factor that contributed to the elevated values of electrical conductivity (EC), Cl^? and total dissolved solids (TDS). The main facies in the shallow aquifer were Ca–HCO₃ and Na–HCO₃ water types. The water types were dominated by Na–Cl and Na–HCO₃ in the intermediate aquifer and by Na–HCO₃ in the deep aquifer. The Gibbs diagram reveals that the majority of groundwater samples belonged to the deep aquifer and fell in the rock dominance zone. Shallow aquifer samples mostly fell in the rainfall zone, suggesting that this aquifer is affected by anthropogenic activities. In contrast, the results suggest that the deep aquifer is heavily influenced by natural processes.     

Fluid geochemistry of the Sardinian Rift-Campidano Graben (Sardinia,Italy): fault segmentation,seismic quiescence of geochemically “active” faults,and new constraints for selection of CO2 storage sites

Sardinia is typically seismically quiescent, displaying an almost complete lack of historical earthquakes and instrumentally recorded seismicity. This evidence may be in agreement with the presence of a ductile layer in the northern sector of the island, as suggested by the He isotopic signature in fluids rising to the surface through quiescent fault systems. The fault systems have been found to be “segmented” and therefore isolated in fluid circulation. The study of fluid behaviour along fault systems becomes strategically important when applied to solve some geological risk assessments such as Rn-indoor, or to define geological structures like potential CO₂ storage sites. Both of these have been recently requested by the exploitation in Italy of the Euratom Directive and the evolution of the KyotoProtocol policy.Four water-dominated hydrothermal areas of Sardinia, located along regional fault systems, were considered: Campidano Graben, Tirso Valley, Logudoro and Casteldoria. A fluid geochemical survey was carried out taking into account physical–chemical and environmental parameters, major elements within gaseous and liquid phases, a few minor and trace elements, selected isotope ratios (²H, ¹⁸O, ¹³C, ³He/⁴He), ²²²Rn concentration, and some dissolved gases.Two different fluids have been recognised as regards both water chemistry and dissolved gases: (i) CO₂-rich gases, poor in He and Rn, with a relatively high ³He/⁴He ratio (up to R/R_a = 2.32), associated with Na–HCO₃–(Cl) thermal and cold groundwater; (ii) gases rich in He and N₂, poor in CO₂ and Rn, with a low ³He/⁴He ratio, associated with alkaline thermal and cold waters. The distribution of these two groups of fluids characterises the Sardinian tectonic systems. In fact, gas fluxes are not homogeneous, being mainly related to the different fault segments and to the areas where Quaternary basalts crop out. The underground geochemical evolution of the Sardinian fluids, as a function of the geological and tectonic systems, provides some suggestions for solving one of the most important problems: CO₂ geological sequestration. In order to reduce the CO₂ excess produced by human activity, the best geological disposal sites are reservoirs with low hydraulic conductivity, sealed to fluid movement, or aquifers characterised by maximum pH buffering capacity of their mineralogical matrix. The knowledge of the role of faults, as permeability barriers or as deep fluid uprising pathways, is prerequisite.     

Carbonate and carbon isotopic evolution of groundwater contaminated by produced water brine with hydrocarbons

The major ionic and dissolved inorganic carbon (DIC) concentrations and the stable carbon isotope composition of DIC (δ¹³C_DIC) were measured in a freshwater aquifer contaminated by produced water brine with petroleum hydrocarbons. Our aim was to determine the effects of produced water brine contamination on the carbonate evolution of groundwater. The groundwater was characterized by three distinct anion facies: HCO₃⁻-rich, SO₄²⁻-rich and Cl⁻-rich. The HCO₃⁻-rich groundwater is undergoing closed system carbonate evolution from soil CO_2(g) and weathering of aquifer carbonates. The SO₄²⁻-rich groundwater evolves from gypsum induced dedolomitization and pyrite oxidation. The Cl⁻-rich groundwater is contaminated by produced water brine and undergoes common ion induced carbonate precipitation. The δ¹³C_DIC of the HCO₃⁻-rich groundwater was controlled by nearly equal contribution of carbon from soil CO_2(g) and the aquifer carbonates, such that the δ¹³C of carbon added to the groundwater was −11.6‰. In the SO₄²⁻-rich groundwater, gypsum induced dedolomitization increased the ¹³C such that the δ¹³C of carbon added to the groundwater was −9.4‰. In the produced water brine contaminated Cl⁻-rich groundwater, common ion induced precipitation of calcite depleted the ¹³C such that the δ¹³C of carbon added to the groundwater was −12.7‰. The results of this study demonstrate that produced water brine contamination of fresh groundwater in carbonate aquifers alters the carbonate and carbon isotopic evolution.     

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.     

Tufa and travertines of southern Italy: deep‐seated,fault‐related CO2 as the key control in precipitation

Continental carbonates of Quaternary age in southern Italy commonly exhibit the facies of calcareous tufa, often reported as related to shallow aquifers fed by meteoric waters and to organic processes. A close spatial relationship exists between the mappable tufa deposits and major Quaternary extensional faults. With respect to the Ca‐Mg‐HCO₃ composition of limestone aquifers’ springs, tufa‐depositing springs exhibit higher salinity and alkalinity, are slightly warmer, have lower pH and are enriched in SO₄ and CO₂. Their δ¹³C values are systematically positive and compatible with a deep‐seated carbon source. A clear input of soil‐derived organic carbon is indicated only for small, non‐mappable tufas deposited by perched springs. The dataset indicates that the large tufa deposits owe their origin to a supplementary source of CO₂ advected by degassing through active faults, as a necessary prerequisite for inducing a rise of total dissolved salts and alkalinity. Meteoric waters that have come from a shallow aquifer are able to precipitate only limited amount of carbonates.