Review: Thermal water resources in carbonate rock aquifers

The current knowledge on thermal water resources in carbonate rock aquifers is presented in this review, which also discusses geochemical processes that create reservoir porosity and different types of utilisations of these resources such as thermal baths, geothermal energy and carbon dioxide (CO₂) sequestration. Carbonate aquifers probably constitute the most important thermal water resources outside of volcanic areas. Several processes contribute to the creation of porosity, summarised under the term hypogenic (or hypogene) speleogenesis, including retrograde calcite solubility, mixing corrosion induced by cross-formational flow, and dissolution by geogenic acids from deep sources. Thermal and mineral waters from karst aquifers supply spas all over the world such as the famous bath in Budapest, Hungary. Geothermal installations use these resources for electricity production, district heating or other purposes, with low CO₂ emissions and land consumption, e.g. Germany’s largest geothermal power plant at Unterhaching near Munich. Regional fault and fracture zones are often the most productive zones, but are sometimes difficult to locate, resulting in a relatively high exploration uncertainty. Geothermal installations in deep carbonate rocks could also be used for CO₂ sequestration (carbonate dissolution would partly neutralise this gas and increase reservoir porosity). The use of geothermal installations to this end should be further investigated.     

Carbonate weathering and connate seawater influencing karst groundwaters in the Gevas–Gurpinar–Güzelsu basins,Turkey

There are 59 springs at the Gevas–Gurp?nar–Güzelsu basins, 38 of these springs emerge from the fractured karst aquifers (recrystallized limestone and travertine) and 21 emerge from the Yuksekova ophiolites, K?rkgeçit formation and alluvium. The groundwater samples collected from 38 out of the total of 59 springs, two streams, one lake and 12 wells were analyzed physico-chemically in the year 2002. EC and TDS values of groundwater increased from the marble (high altitude) to the ophiolites and alluvium (toward Lake Van) as a result of carbonate dissolution and connate seawater. Five chemical types of groundwater are identified: Ca–Mg–HCO₃, Mg–Ca–HCO₃, Mg–Na–HCO₃, Na–Ca–HCO₃ and Mg–Ca–Na–HCO₃. The calculations and hydrochemical interpretations show that the high concentrations of Ca²⁺, Mg²⁺ and HCO₃ ^? as predominant ions in the waters are mainly attributed to carbonate rocks and high pCO₂ in soil. Most of the karst springs are oversaturated in calcite, aragonite and dolomite and undersaturated in gypsum, halite and anhydrite. The water–rock interaction processes that singly or in combination influence the chemical composition of each water type include dissolution of carbonate (calcite and dolomite), calcite precipitation, cation exchange and freshening of connate seawater. These processes contribute considerably to the concentration of major ions in the groundwater. Stable isotope contents of the groundwater suggest mainly direct integrative recharge.     

Hydrogeochemistry and geochemical simulations to assess water–rock interactions in complex carbonate aquifers: The case of Aguadulce (SE Spain)

The hydrogeological unit of Aguadulce (Campo de Dalías aquifers, SE Spain) has a complex geometry. This fact, together with a continuous rise in water demand due to intensive agriculture and tourism create problems for groundwater quantity and quality. In this paper classic geochemical tools managed by means of GIS software and geochemical simulations are combined to delineate, identify and locate the possible physicochemical processes acting in the Aguadulce groundwater. Two main aquifers can be distinguished: the carbonate or lower aquifer of Triassic age, and the calcodetritic or upper aquifer of Plio-Quaternary age. Groundwaters from the latter are more saline and, assuming all chlorinity originates from seawater intrusion, the seawater contribution to their composition would be up to 7%. Nevertheless the carbonate aquifer appears not to be homogeneous: it is compartmentalised into 4 zones where different processes explain the different groundwaters compositions. Zone 4 samples (E margin of the carbonate aquifer) resemble those of the Plio-Quaternary aquifer, where calcite precipitation, dolomite and gypsum dissolution and some cation exchange (water–rock interaction) together with seawater–freshwater mixing occur. In contrast, water–rock interaction predominates in zones 1 and 3 of the carbonate aquifer. Moreover, zone 2 samples, located between zones 1 and 3, are explained by water–rock interaction in addition to mixing with Plio-Quaternary aquifer waters. The combination of geochemical simulations with GIS and hydrogeochemical analyses has proven to be effective in identifying and locating the different physicochemical processes in the aquifer areas, thus improving understanding of hydrogeochemistry in complex aquifers.     

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.     

Hydrochemical and isotopic study of groundwater in Wadi El Hechim–Garaa Hamra basin, Central Tunisia

Hydrochemical and isotopic study of Miocene and Mio-Plio-Quaternary (M-P-Q) aquifers in Wadi El Hechim?CGaraa Hamra basin, Central Tunisia was undertaken in order to investigate recharge mode and processes leading to mineralization of groundwater as well as interaction between both systems. The results revealed striking differences between the two aquifer systems. While the Miocene aquifer contains recently recharged waters with generally low mineralization (around 0.5?g?L^?1), stemming mainly from dissolution of carbonate minerals, the M-P-Q aquifer reveals TDS values reaching 3?g?L^?1, controlled mainly by dissolution of evaporitic minerals. Isotopic data indicate that the Miocene aquifer contains water recharged in past several decades (bomb tritium and bomb radiocarbon detected). The M-P-Q system appears to be much slower, with time scales of groundwater flow possibly reaching some thousands of years. Sharp discontinuity of hydrochemical and isotope characteristic of groundwater observed across the major tectonic fault separating the Miocene and M-P-Q aquifers supports the idea of very limited (if any) hydraulic interconnection between both studied systems. This in turn calls for revision of existing conceptual models of groundwater flow in the region postulating significant groundwater fluxes crossing the fault in the direction of M-P-Q aquifer and adjacent aquifers in the Wadi al Fakka plain.     

A geochemical and stable isotope investigation of groundwater/surface-water interactions in the Velenje Basin,Slovenia

The geochemical and isotopic composition of surface waters and groundwater in the Velenje Basin, Slovenia, was investigated seasonally to determine the relationship between major aquifers and surface waters, water–rock reactions, relative ages of groundwater, and biogeochemical processes. Groundwater in the Triassic aquifer is dominated by HCO₃ ^–, Ca²⁺, Mg²⁺ and δ¹³C_DIC indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has δ¹⁸O and δD values that plot near surface waters on the local and global meteoric water lines, and detectable tritium, likely reflecting recent (<50 years) recharge. In contrast, groundwater in the Pliocene aquifers is enriched in Mg²⁺, Na⁺, Ca²⁺, K⁺, and Si, and has high alkalinity and δ¹³C_DIC values, with low SO₄ ^2– and NO₃ ^– concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and Mg-rich clay minerals. Pliocene aquifer waters are also depleted in ¹⁸O and ²H, and have ³H concentrations near the detection limit, suggesting these waters are older, had a different recharge source, and have not mixed extensively with groundwater in the Triassic aquifer.     

Inverse geochemical modeling of groundwater salinization in Azraq Basin,Jordan

The aim is to define the mechanism of chemical reactions that are responsible for the salinization of the Azraq basin along groundwater flow path, using inverse modeling technique by PHREEQC Interactive 2.8 for Windows. The chemical analysis of representative groundwater samples was used to predict the causes of salinization of groundwater. In addition, the saturation indices analysis was used to characterize the geochemical processes that led to the dissolution of mineral constituents within the groundwater aquifer system. According to the modeling results, it was noted that the groundwater at the recharge area was undersaturated with respect to calcite, dolomite, gypsum, anhydrite, and halite. Thus, the water dissolved these minerals during water rock interaction, and therefore, the concentration of Ca, Mg, Na, and SO₄ increased along the groundwater flow path. Furthermore, the groundwater at the discharge area was oversaturated with respect to calcite and dolomite. This meant that the water would precipitate these minerals along the flow path, while the water was undersaturated with respect to gypsum and halite throughout the simulated path; this showed the dissolution processes that take place during water-rock interaction. Therefore, the salinity of the groundwater increased significantly along the groundwater flow paths.     

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

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

Geochemistry of regional aquifer systems hosted by carbonate-evaporite formations in Umbria and southern Tuscany (central Italy)

In central Italy Mesozoic carbonates represent the principal reservoir of freshwater of the region. The hydrogeological setting is linked to the geological evolution of the Apennine chain and is generally characterised by a lower aquifer and one or more shallower aquifers separated by thin aquicludes. In these systems, groundwater composition is the result of a complex array of regional and local geochemical processes. The main geochemical processes are the dissolution of calcite, the influx of deeply derived CO₂ related to a regional process of mantle degassing, dedolomitization and mixing with deep saline fluids. The occurrence of saline fluids, characterised by a Na–Cl(HCO₃) composition, is related to the presence of a deep regional aquifer at the base of Mesozoic carbonates. The extremely high pCO₂ values computed for the saline waters suggest that the deep aquifer is also a structural trap for the mantle derived CO₂ during its ascent towards the surface. In central Italy, geological and geophysical data highlight the presence of two different crustal sectors: the eastern sector, where the geometry of the Apennine thrust belt is still preserved, and the western sector, where the compressive structures are dislocated by important extensional deformations. In the western sector, the normal faults disrupting the compressive structures allow the mixing of the deep Na–Cl(HCO₃) fluids with the shallow groundwater causing a salinity increase and the natural deterioration of groundwater quality.     

Geochemical evolution of groundwater in carbonate aquifers in Taiyuan, northern China

Thirty-nine samples of both cold and thermal karst groundwater from Taiyuan, northern China were collected and analyzed with the aim of developing a better understanding of the geochemical processes that control the groundwater quality evolution in the region’s carbonate aquifers. The region’s karst groundwater system was divided into three geologically distinct sub-systems, namely, the Xishan Mountain karst groundwater subsystem (XMK), the Dongshan Mountain karst groundwater subsystem (DMK) and the Beishan Mountain karst groundwater subsystem (BMK). Hydrochemical properties of the karst groundwaters evolve from the recharge zones towards the cold water discharge zones and further towards the thermal water discharge zones. In the XMK and the DMK, the hydrochemical type of the groundwater evolves from HCO₃-Ca·Mg in the recharge - flow-through zone, to HCO₃·SO₄-Ca·Mg/SO₄·HCO₃-Ca·Mg in the cold water discharge zone, and further to SO₄-Ca·Mg in the thermal water discharge zone. By contrast, the water type changes from HCO₃-Ca·Mg to HCO₃·SO₄-Ca·Mg in the BMK, with almost invariable TDS and temperatures all along from the recharge to the discharge zone. The concentrations of Sr, Si, Fe, F⁻ and of some trace elements (Al, B, Li, Mn, Mo, Co, Ni) increase as groundwater temperature increases. Different hydrogeochemical processes occur in the three karst groundwater sub-systems. In the XMK and the DMK, the geochemical evolution of the groundwater is jointly controlled by carbonate dissolution/precipitation, gypsum dissolution and dedolomitization, while only calcite and dolomite dissolution/precipitation occurs in the BMK without dedolomitization. The hydrogeochemical data of the karst groundwaters were used to construct individual geochemical reaction models for each of the three different karst groundwater sub-systems. The modeling results confirm that dedolomization is the major process controlling hydrochemical changes in the XMK and the DMK. In the thermal groundwaters, the dissolution rates of fluorite, siderite and strontianite were found to exceed those of the cold karst groundwater systems, which can explain the higher concentrations of F⁻, Fe and Sr²⁺ that are found in these waters.     

Paleowaters in Silurian-Devonian carbonate aquifers: Geochemical evolution of groundwater in the Great Lakes region since the Late Pleistocene

Changes in the climatic conditions during the Late Quaternary and Holocene greatly impacted the hydrology and geochemical evolution of groundwaters in the Great Lakes region. Increased hydraulic gradients from melting of kilometer-thick Pleistocene ice sheets reorganized regional-scale groundwater flow in Paleozoic aquifers in underlying intracratonic basins. Here, we present new elemental and isotopic analyses of 134 groundwaters from Silurian-Devonian carbonate and overlying glacial drift aquifers, along the margins of the Illinois and Michigan basins, to evaluate the paleohydrology, age distribution, and geochemical evolution of confined aquifer systems. This study significantly extends the spatial coverage of previously published groundwaters in carbonate and drift aquifers across the Midcontinent region, and extends into deeper portions of the Illinois and Michigan basins, focused on the freshwater-saline water mixing zones. In addition, the hydrogeochemical data from Silurian-Devonian aquifers were integrated with deeper basinal fluids, and brines in Upper Devonian black shales and underlying Cambrian-Ordovician aquifers to reveal a regionally extensive recharge system of Pleistocene-age waters in glaciated sedimentary basins. Elemental and isotope geochemistry of confined groundwaters in Silurian-Devonian carbonate and glacial drift aquifers show that they have been extensively altered by incongruent dissolution of carbonate minerals, dissolution of halite and anhydrite, cation exchange, microbial processes, and mixing with basinal brines. Carbon isotope values of dissolved inorganic carbon (DIC) range from −10 to −2‰, ⁸⁷Sr/⁸⁶Sr ratios range from 0.7080 to 0.7090, and δ³⁴S-SO₄ values range from +10 to 30‰. A few waters have elevated δ¹³C_DIC values (>15‰) from microbial methanogenesis in adjacent organic-rich Upper Devonian shales. Radiocarbon ages and δ¹⁸O and δD values of confined groundwaters indicate they originated as subglacial recharge beneath the Laurentide Ice Sheet (14-50 ka BP, −15 to −13‰ δ¹⁸O). These paleowaters are isolated from shallow flow systems in overlying glacial drift aquifers by lake-bed clays and/or shales. The presence of isotopically depleted waters in Paleozoic aquifers at relatively shallow depths illustrates the importance of continental glaciation on regional-scale groundwater flow. Modern groundwater flow in the Great Lakes region is primarily restricted to shallow unconfined glacial drift aquifers. Recharge waters in Silurian-Devonian and unconfined drift aquifers have δ¹⁸O values within the range of Holocene precipitation: −11 to −8‰ and −7 to −4.5‰ for northern Michigan and northern Indiana/Ohio, respectively. Carbon and Sr isotope systematics indicate shallow groundwaters evolved through congruent dissolution of carbonate minerals under open and closed system conditions (δ¹³C_DIC = −14.7 to−11.1‰ and ⁸⁷Sr/⁸⁶Sr = 0.7080-0.7103). The distinct elemental and isotope geochemistry of Pleistocene- versus Holocene-age waters further confirms that surficial flow systems are out of contact with the deeper basinal-scale flow systems. These results provide improved understanding of the effects of past climate change on groundwater flow and geochemical processes, which are important for determining the sustainability of present-day water resources and stability of saline fluids in sedimentary basins.     

Groundwater flow and residence time in a karst aquifer using ion and isotope characterization

In order to identify the origin of the main processes that affect the composition of groundwater in a karstic aquifer, a hydrogeochemical and isotopic study was carried out of water from numerous observation wells located in Sierra de Gador, a semiarid region in SE Spain. Several natural and anthropogenic tracers were used to calculate groundwater residence time within this complex aquifer system. Analysis of major ions enabled the principal geochemical processes occurring in the aquifer to be established, and the samples were classified into four distinctive solute groups according to this criterion. Dissolution of carbonate rocks determines the chemical composition of less mineralized water. In another group, the concurrent dissolution of dolomite and precipitation of calcite in gypsum-bearing carbonate aquifer, where the dissolution of relatively soluble gypsum controls the reaction, are the dominant processes. Marine intrusion results in highly mineralized waters and leads to base exchange reactions. The groundwater enrichment of minor and trace elements allowed classification of the samples into two classes that are linked to different flow patterns. One of these classes is influenced by a slow and/or deep regional flow, where the temperature is generally elevated. The influence of sulphate reduces by up to 40 % the barium concentration due to the barite precipitation. Isotope data (T, ¹⁴C) confirm the existence of recent local flows, and regional flow system, and ages of ground water may reach 8000 years. The importance of gypsum dissolution in this aquifer is proved by the δ³⁴S content.     

Regional groundwater flow and geochemical evolution in the Amacuzac River Basin,Mexico

An approach is presented to investigate the regional evolution of groundwater in the basin of the Amacuzac River in Central Mexico. The approach is based on groundwater flow cross-sectional modeling in combination with major ion chemistry and geochemical modeling, complemented with principal component and cluster analyses. The hydrogeologic units composing the basin, which combine aquifers and aquitards both in granular, fractured and karstic rocks, were represented in sections parallel to the regional groundwater flow. Steady-state cross-section numerical simulations aided in the conceptualization of the groundwater flow system through the basin and permitted estimation of bulk hydraulic conductivity values, recharge rates and residence times. Forty-five water locations (springs, groundwater wells and rivers) were sampled throughout the basin for chemical analysis of major ions. The modeled gravity-driven groundwater flow system satisfactorily reproduced field observations, whereas the main geochemical processes of groundwater in the basin are associated to the order and reactions in which the igneous and sedimentary rocks are encountered along the groundwater flow. Recharge water in the volcanic and volcano-sedimentary aquifers increases the concentration of HCO₃ ^–, Mg²⁺ and Ca²⁺ from dissolution of plagioclase and olivine. Deeper groundwater flow encounters carbonate rocks, under closed CO₂ conditions, and dissolves calcite and dolomite. When groundwater encounters gypsum lenses in the shallow Balsas Group or the deeper Huitzuco anhydrite, gypsum dissolution produces proportional increased concentration of Ca²⁺ and SO₄ ^2–; two samples reflected the influence of hydrothermal fluids and probably halite dissolution. These geochemical trends are consistent with the principal component and cluster analyses.     

Numerical simulation of CO2 disposal by mineral trapping in deep aquifers

Carbon dioxide disposal into deep aquifers is a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO₂ disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO₂ injection, the authors have analyzed the impact of CO₂ immobilization through carbonate mineral precipitation. Batch reaction modeling of the geochemical evolution of 3 different aquifer mineral compositions in the presence of CO₂ at high pressure were performed. The modeling considered the following important factors affecting CO₂ sequestration: (1) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, (2) CO₂ solubility dependence on pressure, temperature and salinity of the system, and (3) redox processes that could be important in deep subsurface environments. The geochemical evolution under CO₂ injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO₂ sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO₂ that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO₂ dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of Fe(III) mineral precursors such as goethite or glauconite. The accumulation of carbonates in the rock matrix leads to a considerable decrease in porosity. This in turn adversely affects permeability and fluid flow in the aquifer. The numerical experiments described here provide useful insight into sequestration mechanisms, and their controlling geochemical conditions and parameters.     

Aquifer disposal of acid gases: modelling of water–rock reactions for trapping of acid wastes

The pore space of deep saline aquifers in the Alberta (sedimentary) Basin offers a significant volume for waste storage by “hydrodynamic trapping”. Furthermore, given the slow regional fluid flow in these deep saline aquifers, ample time exists for waste-water/rock chemical reactions to take place. A geochemical computer model (PATHARC) was used to compute the interaction of industrial waste streams comprising CO₂, H₂SO₄ and H₂S with the minerals in typical carbonate and sandstone aquifers from the Alberta Basin. The results support the idea that these acids can be neutralized by such reactions and that new mineral products are formed, such as calcite, siderite, anhydrite/gypsum and pyrrhotite, thereby trapping the CO₃, SO₄ and S ions that are formed when the acid gases dissolve in the formation water. Siliciclastic aquifers appear to be a better host for “mineral trapping” than carbonate aquifers, especially with regard to CO₂. Carbonate aquifers may be more prone to leakage due to high CO₂ pressures generated by reaction with H₂SO₄ and H₂S. Even though permeability decreases are expected due to this “mineral trapping”, they can be partially controlled so that plugging of the aquifer does not occur.     

Suitability of Existing Numerical Model Codes and Thermodynamic Databases for the Prognosis of Calcite Dissolution Processes in Near-Surface Sediments Due to a CO2 Leakage Investigated by Column Experiments

Among the risks of CO₂ storage is the potential of CO₂ leakage into overlaying formations and near-surface potable aquifers. Through a leakage, the CO₂ can intrude into protected groundwater resources, which can lead to groundwater acidification followed by potential mobilisation of heavy metals and other trace metals through mineral dissolution or ion exchange processes. The prediction of pH buffer reactions in the formations overlaying a CO₂ storage site is essential for assessing the impact of CO₂ leakages in terms of trace metal mobilisation. For buffering the pH-value, calcite dissolution is one of the most important mechanisms. Although calcite dissolution has been studied for decades, experiments conducted under elevated CO₂ partial pressures are rare. Here, the first study for column experiments is presented applying CO₂ partial pressures from 6 to 43 bars and realising a near-natural flow regime. Geochemical calculations of calcite dissolution kinetics were conducted using PHREEQC together with different thermodynamic databases. Applying calcite surface areas, which were previously acquired by N₂-BET or calculated based on grain diameters, respectively, to the rate laws according to Plummer et al. (Am J Sci 278:179–216, doi:10.2475/ajs.278.2.179, 1978) or Palandri and Kharaka (US Geol Surv Open file Rep 2004–1068:71, 2004) in the numerical simulations led to an overestimation of the calcite dissolution rate by up to three orders of magnitude compared to the results of the column experiments. Only reduction of the calcite surface area in the simulations as a fitting procedure allowed reproducing the experimental results. A reason may be that the diffusion boundary layer (DBL), which depends on the groundwater flow velocity and develops at the calcite grain surface separating it from the bulk of the solution, has to be regarded: The DBL leads to a decrease in the calcite dissolution rate under natural laminar flow conditions compared to turbulent mixing in traditional batch experiments. However, varying the rate constants by three orders of magnitudes in a field scale PHREEQC model simulating a CO₂ leakage produced minor variations in the pH buffering through calcite dissolution. This justifies the use of equilibrium models when calculating the calcite dissolution in CO₂ leakage scenarios for porous aquifers and slow or moderate groundwater flow velocities. However, the selection of the thermodynamic database has an impact on the dissolved calcium concentration, leading to an uncertainty in the simulation results. The resulting uncertainty, which applies also to the calculated propagation of an aquifer zone depleted in calcite through dissolution, seems negligible for shallow aquifers of approximately 60 m depth, but amounts to 35 % of the calcium concentration for aquifers at a depth of approximately 400 m.     

Deciphering interaction of regional aquifers in Southern Tunisia using hydrochemistry and isotopic tools

Groundwater is the most important source of water supply in southern Tunisia. Previous hydrogeologic and isotopic studies carried out in this region revealed the existence of two major aquifer systems: the “Complex Terminal” (CT) and the “Continental Intercalaire” (CI). Turonian carbonates constitute one of the major aquifer levels of the CT multilayered aquifer. It extends over most of southern Tunisia, and its hydrodynamic regime is largely influenced by tectonics, lithology and recharge conditions. Forty-eight groundwater samples from the CI and Turonian aquifers were collected between January and April 2004 for chemical and isotopic analyses. Hydrochemistry and isotopic tools were combined to get an insight into the processes controlling chemical composition of groundwater and wide-scale interaction of these two aquifer systems. Analysis of the dissolved constituents revealed that several processes control the observed chemical composition: (i) incongruent dissolution of carbonate minerals, (ii) dissolution of evaporitic minerals, and (iii) cation exchange. Dissolution alone cannot account for the observed high supersaturation states of groundwater with respect to calcite and dolomite. The observed supersaturation is most probably linked to geogenic CO₂ entering water-bearing horizons of the CT and CI aquifers via deep tectonic faults and discontinuities and subsequent degassing in the exploitation wells. Presence of geogenic CO₂ in the investigated region was confirmed by C isotope data of the DIC reservoir. The radiocarbon content of the Turonian samples varied between 9.5 and 43 pmc. For CI samples generally lower values were recorded, between 3.8 and 22.5 pmc. Stable isotope composition of Turonian groundwater samples varied from −8.3 to −5.3‰ for δ¹⁸O and from −60 to −25‰ for δ²H. The corresponding ranges of δ values for the Continental Intercalaire samples were from −8.9‰ to −6.9‰ for δ¹⁸O and from −68.2‰ to −45.7‰ for δ²H. Stable isotope composition of groundwater representing CT and CI aquifers provide strong evidence for regional interaction between both systems.     

Groundwater chemistry and mass transfers in the Independence aquifer,central Mexico,by using multivariate statistics and mass-balance models

In the light of progressive depletion of groundwater reservoir and water quality deterioration of the Independence aquifer, an investigation on chemical data of dissolved major and minor constituents in 246 recent groundwater samples was performed. The main objective was the detection of processes responsible for the geochemical evolution and mineralization throughout the area. Multivariate techniques revealed different sources of solutes (a) dissolution of calcium and magnesium carbonate minerals, (b) weathering of acid volcanic minerals, (c) alteration of manganese containing alkaline silicates, (d) leaching of halite deposits of meteoric origin, (e) contamination from agricultural and urban wastewaters, and (f) evaporative effects due to intensive irrigation. Although nitrate contamination is associated with pollution from intensive cultivated areas, natural contamination plays an important role in the study area. The investigation reveals that weathering of acid volcanic rocks (rhyolite) and oxidation of arsenic bearing sulfide minerals are the responsible processes for high fluorine (up to 16 mg/l) and arsenic (up to 0.12 mg/l) contents, respectively, exceeding the Mexican maximum admissible concentration for drinking water. Except for kaolinite, all recharge processes are dissolution oriented (CO₂, calcite, dolomite, K-feldspar, plagioclase). Silicate precipitation (amorphous silica and chalcedony) is of growing importance in discharge zones. Cation exchange is not an important issue in the whole study area.     

Recharge,geochemical processes and water quality in karst aquifers: Central West Bank,Palestine

The Central West Bank aquifer (CWB) is one of the most important resources of fresh groundwater of Palestine. The geology of the area consists mainly of karstic and permeable limestones and dolomites interbedded with argillaceous beds of late Albian–Turonian age. Exploitation of the CWB aquifer, combined with lack of information required to understand the groundwater pattern, represents a challenge for reservoir management. The present work reports hydrogeochemistry, microbiology and environmental isotope data from spring water samples, which were utilized to understand recharge mechanisms, geochemical evolution and renewability of groundwater in CWB aquifer. Besides the major chemical compositions, ionic ratios were used to delineate mineral-solution reactions and weathering processes. Interpretation of chemical data suggests that the chemical evolution of groundwater is primarily controlled by (1) water–rock interactions, involving dissolution of carbonate minerals (calcite and dolomite), and (2) cation exchange processes. The measured equation of the local meteoric water line is δD?=?5.8 δ¹⁸O?+?9.9. Stable isotopes show that precipitation is the source of recharge to the groundwater system. The evaporation line has a linear increasing trend from south to north direction in the study area. All analyzed spring waters are suitable for irrigation, but not for drinking purposes. The results from this study can serve as a basis for decision-makers and stakeholders, with the intention to increase the understanding of sustainable management of the CWBs.     

Impact of Carbonate Precipitation on Riverine Inorganic Carbon Mass Transport from a Mid-continent, Forested Watershed

Physiochemical controls on the carbonate geochemistry of large river systems are important regulators of carbon exchange between terrestrial and marine reservoirs on human time scales. Although many studies have focused on large-scale river carbon fluxes, there are few investigations of mechanistic aspects of carbonate mass balance and transport at the catchment scale. We determined elemental and carbonate geochemistry and mass balances for net carbonate dissolution fluxes from the forested, mid-latitude Huron River watershed, established on carbonate-rich unconfined glacial drift aquifers. Shallow groundwaters are near equilibrium with respect to calcite at pCO₂ values up to 25 times atmospheric values. Surface waters are largely groundwater fed and exhibit chemical evolution due to CO₂ degassing, carbonate precipitation in lakes and wetlands, and anthropogenic introduction of road salts (NaCl and CaCl₂). Because the source groundwater Mg²⁺/HCO₃ ^? ratio is fairly constant, this parameter permits mass balances to be made between carbonate dissolution and back precipitation after groundwater discharge. Typically, precipitation does not occur until IAP/K calcite values exceed 10 times supersaturation. Stream chemistry changes little thereafter even though streams remain highly supersaturated for calcite. Our data taken together with historical United States Geological Survey (USGS) data show that alkalinity losses to carbonate precipitation are most significant during periods of lowest discharge. Thus, on an annual basis, the large carbon flux from carbonate dissolution in soil zones is only decreased by a relatively small amount by the back precipitation of calcium carbonate.