Uncertainty in geochemical modelling of CO2 and calcite dissolution in NaCl solutions due to different modelling codes and thermodynamic databases

A prognosis of the geochemical effects of CO₂ storage induced by the injection of CO₂ into geologic reservoirs or by CO₂ leakage into the overlaying formations can be performed by numerical modelling (non-invasive) and field experiments. Until now the research has been focused on the geochemical processes of the CO₂ reacting with the minerals of the storage formation, which mostly consists of quartzitic sandstones. Regarding the safety assessment the reactions between the CO₂ and the overlaying formations in the case of a CO₂ leakage are of equal importance as the reactions in the storage formation. In particular, limestone formations can react very sensitively to CO₂ intrusion. The thermodynamic parameters necessary to model these reactions are not determined explicitly through experiments at the total range of temperature and pressure conditions and are thus extrapolated by the simulation code. The differences in the calculated results lead to different calcite and CO₂ solubilities and can influence the safety issues.This uncertainty study is performed by comparing the computed results, applying the geochemical modelling software codes The Geochemist’s Workbench, EQ3/6, PHREEQC and FactSage/ChemApp and their thermodynamic databases. The input parameters (1) total concentration of the solution, (2) temperature and (3) fugacity are varied within typical values for CO₂ reservoirs, overlaying formations and close-to-surface aquifers. The most sensitive input parameter in the system H₂O–CO₂–NaCl–CaCO₃ for the calculated range of dissolved calcite and CO₂ is the fugacity of CO₂. Hence, the largest range of dissolved calcite is calculated at high fugacities and is 210 mmol/kgw. The average deviation of the results using the databases phreeqc.dat and wateq4f.dat in combination with the code PHREEQC is lowest in comparison to the results of the specific model of Duan and Li, which represents the experimental values at best. Still, the solubility of CO₂ is overestimated in the formation water using these two databases. Therefore, the model results calculate a larger retention capacity, defined as the quantity of CO₂ dissolved in the formation water, than the Duan and Li model would do.     

Using non-conservative tracers to characterise karstification processes in the Merinos-Colorado-Carrasco carbonate aquifer system (southern Spain)

The systematic sampling of the chemical composition of the groundwater from five karst springs (including an overflow spring) and one outflowing borehole have permitted to determine distinctive chemical changes in the waters that reflect the geochemical processes occurring in a carbonate aquifer system from southern Spain. The analysis of the dissolution parameters revealed that geochemical evolution of the karst waters basically depends on the availability of the minerals forming aquifer rocks and the residence time within the aquifers. In the three proposed scenarios in the aquifers, which include the preferential flow routines, the more important geochemical processes taking place during the groundwater flow from the recharge to the discharge zones are: CO₂ dissolution and exsolution (outgassing), calcite net dissolution, calcite and dolomite sequential dissolution, gypsum/anhydrite and halite dissolution, de-dolomitization and calcite precipitation. A detailed analysis of the hydrochemical data set, saturation indices of the minerals and partial pressure of CO₂ in the waters joined to the application of geochemical modelling methods allowed the elaboration of a hydrogeochemical model of the studied aquifers. The developed approach contributes to a better understanding of the karstification processes and the hydrogeological functioning of carbonate aquifers, the latter being a crucial aspect for the suitable management of the water resources.     

Metal release from dolomites at high partial-pressures of CO2

The potential for metal release associated with CO₂ leakage from underground storage formations into shallow aquifers is an important consideration in assessment of risk associated with CO₂ sequestration. Metal release can be driven by acidification of groundwaters caused by dissolution of CO₂ and subsequent dissociation of carbonic acid. Thus, acidity is considered one of the main drivers for water quality degradation when evaluating potential impacts of CO₂ leakage. Dissolution of carbonate minerals buffers the increased acidity. Thus, it is generally thought that carbonate aquifers will be less impacted by CO₂ leakage than non-carbonate aquifers due to their high buffering potential. However, dissolution of carbonate minerals can also release trace metals, often present as impurities in the carbonate crystal structure, into solution. The impact of the release of trace metals through this mechanism on water quality remains relatively unknown. In a previous study we demonstrated that calcite dissolution contributed more metal release into solution than sulfide dissolution or desorption when limestone samples were dissolved in elevated CO₂ conditions. The study presented in this paper expanded our work to dolomite formations and details a thorough investigation on the role of mineral composition and mechanisms on trace element release in the presence of CO₂. Detailed characterization of samples from dolomite formations demonstrated stronger associations of metal releases with dissolution of carbonate mineral phases relative to sulfide minerals or surface sorption sites. Aqueous concentrations of Sr²⁺, CO²⁺, Mn²⁺, Ni²⁺, Tl⁺, and Zn²⁺ increased when these dolomite rocks were exposed to elevated concentrations of CO₂. The aqueous concentrations of these metals correlate to aqueous concentrations of Ca²⁺ throughout the experiments. All of the experimental evidence points to carbonate minerals as the dominant source of metals from these dolomite rocks to solution under experimental CO₂ leakage conditions. Aqueous concentrations of Ca²⁺ and Mg²⁺ predicted from numerical simulation of kinetic dolomite dissolution match those observed in the experiments when the surface area is three to five orders of magnitude lower than the surface area of the samples measured by gas adsorption.     

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.     

Accessing effects and signals of leakage from a CO<Subscript>2</Subscript> reservoir to a shallow freshwater aquifer by reactive transport modelling

CO₂ geological storage is a transitional technology for the mitigation of climate change. In the vicinity of potential CO₂ reservoirs in Hungary, protected freshwater aquifers used for drinking water supplies exist. Effects of disaster events of CO₂ escape and brine displacement to one of these aquifers have been studied by kinetic 1D reactive transport modelling in PHREEQC. Besides verifying that ion concentrations in the freshwater may increase up to drinking water limit values in both scenarios (CO₂ or brine leakage), total porosity of the rock is estimated. Pore volume is expected to increase at the entry point of CO₂ and to decrease at further distances, whereas it shows minor increase along the flow path for the effect of brine inflow. Additionally, electrical conductivity of water is estimated and suggested to be the best parameter to measure for cost-effective monitoring of both worst-case leakage scenarios.     

Contribution of {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} and 13CTDIC Evaluation to the Identification of CO2 Sources in Volcanic Groundwater Systems: Influence of Hydrometeorological Conditions and Lava Flow Morphologies—Application to the Argnat Basin (Chaîne des Puys, Massif Central, France)

Mineralization of groundwater in volcanic aquifers is partly acquired through silicates weathering. This alteration depends on the dissolution of atmospheric, biogenic, or mantellic gaseous CO₂ whose contributions may depend on substratum geology, surface features, and lava flow hydrological functionings. Investigations of $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ¹³C_TDIC (total dissolved inorganic carbon) on various spatiotemporal scales in the unsaturated and saturated zones of volcanic flows of the Argnat basin (French Massif Central) have been carried out to identify the carbon sources in the system. Mantellic sources are related to faults promoting CO₂ uplift from the mantle to the saturated zone. The contribution of this source is counterbalanced by infiltration of water through the unsaturated zone, accompanied by dissolution of soil CO₂ or even atmospheric CO₂ during cold periods. Monitoring and modeling of δ¹³C_TDIC in the unsaturated zone shows that both $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ¹³C_TDIC are controlled by air temperature which influences soil respiration and soil-atmosphere CO₂ exchanges. The internal geometry of volcanic lava flows controls water patterns from the unsaturated zone to saturated zone and thus may explain δ¹³C heterogeneity in the saturated zone at the basin scale.     

Modeling of water–rock interactions in an aquitard of sandy clay in the coastal area near Beihai,China

Unconsolidated sand, gravel and clay deposits near Beihai and in the Leizhou Peninsula in southern China form an unconfined aquifer, aquitard and a confined aquifer. Water and soil samples were collected from the two aquifers in the coastal Beihai area for the determination of chemical compositions, minerals and soluble ions. Hydrogeochemical modeling of three flow paths through the aquitard are carried out using PHREEQC to determine water–rock interactions along the flow paths. The results indicate that the dissolution of anorthite, fluorite, halite, rhodochrosite and CO₂, and precipitation of potash feldspar and kaolinite may be occurring when groundwater leaks through the aquitard from the unconfined aquifer to the confined aquifer. Cation exchanges between Na and Ca can also happen along the flow paths.     

Groundwater recharge and chemical evolution in the southern High Plains of Texas, USA

The unconfined High Plains (Ogallala) aquifer is the largest aquifer in the USA and the primary water supply for the semiarid southern High Plains of Texas and New Mexico. Analyses of water and soils northeast of Amarillo, Texas, together with data from other regional studies, indicate that processes during recharge control the composition of unconfined groundwater in the northern half of the southern High Plains. Solute and isotopic data are consistent with a sequence of episodic precipitation, concentration of solutes in upland soils by evapotranspiration, runoff, and infiltration beneath playas and ditches (modified locally by return flow of wastewater and irrigation tailwater). Plausible reactions during recharge include oxidation of organic matter, dissolution and exsolution of CO₂, dissolution of CaCO₃, silicate weathering, and cation exchange. Si and ¹⁴C data suggest leakage from perched aquifers to the High Plains aquifer. Plausible mass-balance models for the High Plains aquifer include scenarios of flow with leakage but not reactions, flow with reactions but not leakage, and flow with neither reactions nor leakage. Mechanisms of recharge and chemical evolution delineated in this study agree with those noted for other aquifers in the south-central and southwestern USA. Electronic Publication     

Experimental investigation of the mechanism of the reaction: 1 tremolite+11 dolomite ⇌ 8 forsterite+13 calcite+9 CO2+1H2O

Stoichiometric mixtures of tremolite and dolomite were heated to 50° C above equilibrium temperatures to form forsterite and calcite. The pressure of the CO₂-H₂O fluid was 5 Kb and \(X_{{\text{CO}}_{\text{2}} }\) varied from 0.1 to 0.6. The extent of the conversion was determined by the amount of CO₂ produced. The resulting mixtures of unreacted tremolite and dolomite and of newly-formed forsterite and calcite were examined with a scanning electron microscope. All tremolite and dolomite grains showed obvious signs of dissolution. At fluid compositions with \(X_{{\text{CO}}_{\text{2}} }\) less than about 0.4, the forsterite and calcite crystals are randomly distributed throughout the charges, indicating that surfaces of the reactants are not a controlling factor with respect to the sites of nucleation of the products. A change is observed when \(X_{{\text{CO}}_{\text{2}} }\) is greater than about 0.4; the forsterite and calcite crystals now nucleate and grow at the surface of the dolomite grains, thus indicating a change in mechanism at medium CO₂ concentrations. As the reaction progresses, the dolomite grains become more and more surrounded by forsterite and calcite, finally forming armoured relics of dolomite. Under experimental conditions this characteristic texture can only be formed if the CO₂-concentration is greater than about 40 mole %. These findings make it possible to estimate the CO₂-concentration from the texture of the dolomite+tremolite+forsterite+calcite assemblage. The results suggest a dissolution-precipitation mechanism for the reaction investigated. In a simplified form it consists of the following 4 steps:

1. Dissolution of the reactants tremolite and dolomite.
2. Diffusion of the dissolved constituents in the fluid.
3. Heterogeneous nucleation of the product minerals.
4. Growth of forsterite and calcite from the fluid.

Two possible explanations are discussed for the development of the amoured texture at \(X_{{\text{CO}}_{\text{2}} }\) above 0.4. The first is based upon the assumption that dolomite has a lower rate of dissolution than tremolite at high \(X_{{\text{CO}}_{\text{2}} }\) values resulting in preferential calcite and forsterite nucleation and growth on the dolomite surface. An alternative explanation is the formation of a raised CO₂ concentration around the dolomite grains at high \(X_{{\text{CO}}_{\text{2}} }\) values, leading to product precipitation on the dolomite crystals.     

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.     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

Solubility of carbon dioxide in aqueous fluids and mineral suspensions at 294 K and subcritical pressures

An experimental investigation has been carried on the solubility of CO₂ in water and 1 M NaCl between 0.3 and 4 MPa, in order to test the validity of the results given by various modelling codes. In addition to experiments with pure fluids, the effect of a range of likely reservoir minerals on CO₂–water interactions, including K-feldspar, kaolinite, calcite, Ca-montmorillonite and Na-montmorillonite were also investigated. In addition to measurements of CO₂ solubility, the pH of the CO₂-saturated suspensions was also measured directly at pressures of up to 1 MPa. The results demonstrate that predictions of CO₂ solubility made with PHREEQC and Geochemist’s Workbench agree to within 20% with the experimental value, provided corrections are first made off-line for the fugacity coefficient of CO₂, while predictions from standalone models are slightly more accurate. In the presence of mineral suspensions, PHREEQC and Geochemist’s Workbench give good results for calcite and kaolinite but underestimate the pH of montmorillonite-bearing assemblages while slightly overestimating the pH of K-feldspar suspensions. These results are significant because they indicate that CO₂-charged fluids reacted with clays may be less acidic than indicated by the models, which will impact predictions of the potential for dissolution of reservoir and cap rock minerals, as well as the potential for leaching of toxic metals.     

Long‐Term Reaction Characteristics of CO2–Water–Rock Interaction: Insight into the Potential Groundwater Contamination Risk from Underground CO2 Storage

CO₂ sequestration into saline aquifers is considered to be one of the most promising options for reducing industrial CO₂ emissions to the atmosphere. However, there are still many uncertainties regarding the storage of CO₂ in the subsurface because of a lack of knowledge about CO₂–water–rock interaction within CO₂ reservoirs and the potential risk of CO₂ leakage. In this study, we construct a semi‐open type experimental system that can reproduce the interactions under conditions close to those of actual CO₂ reservoirs. Using the system, we conduct CO₂–water–rock interaction experiments for 8 months to monitor the long‐term reaction and the mobilization of harmful metal elements. Altered tuffaceous rock is used in the experiment because these tuffaceous rock formations (called “Green Tuff”) are a potential candidate for CO₂ storage in Japan. The results show that the major‐element water composition will converge to the point where host rock dissolution and secondary mineral precipitation are balanced; then, the interaction will proceed under a certain groundwater composition. In addition, we found that groundwater contamination by some metal elements (Ni, Ba, and Mn) may reach unsafe levels for drinking water as a result of CO₂‐water–rock interaction.     

Evolution of groundwater chemical composition by plagioclase hydrolysis in Norwegian anorthosites

The Precambrian Egersund anorthosites exhibit a wide range of groundwater chemical composition (pH 5.40-9.93, Ca²⁺ 1.5-41 mg/L, Na⁺ 12.3-103 mg/L). They also exhibit an evolutionary trend, culminating in high pH, Na-rich, low-Ca groundwaters, that is broadly representative of Norwegian crystalline bedrock aquifers in general. Simple PHREEQC modelling of monomineralic plagioclase-CO₂-H₂O systems demonstrates that the evolution of such waters can be explained solely by plagioclase weathering, coupled with calcite precipitation, without invoking cation exchange. Some degree of reaction in open CO₂ systems seems necessary to generate the observed maximum solute concentrations, while subsequent system closure can be invoked to explain high observed pH values. Empirical data provide observations required or predicted by such a model: (i) the presence of secondary calcite in silicate aquifer systems, (ii) the buffering of pH at around 8.0-8.3 by calcite precipitation, (iii) significant soil gas CO₂ concentrations (PCO₂ > 10⁻² atm) even in poorly vegetated sub-arctic catchments, and (iv) the eventual re-accumulation of calcium in highly evolved, high pH waters.     

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.     

The geochemical effects of benzene,toluene, and xylene (BTX) biodegradation

The geochemical effects of microbially mediated degradation of aromatic hydrocarbons were observed as changes in solution composition of an artificial groundwater in packed-sand laboratory columns. Benzene, toluene, and xylene, both individually and in a combined fashion, were used as substrates in biodegradation experiments conducted under oxygenated and anoxic conditions in columns filled with quartz, calcite, or Fe³⁺-coated quartz sand. Typically, column effluent had increased concentrations of dissolved inorganic C, decreased pH, and decreased concentrations of NO₃ and dissolved O₂ relative to column influent. Efficiency of CO₂ generation was similar for the three different substrates, ranging from 22.5 to 26.6% organic C converted to CO₂. When all three substrates were combined, the percentage of CO₂ produced fell within the range observed in the single substrate experiments. Nitrate disappearance was more varied as a function of substrate identity, with greatest amounts lost when toluene was the substrate. Calcite dissolved as a result of CO₂ generated during the biodegradation reactions, and empirically calculated dissolution rates varied between 1.9 and 4.0 x 10⁻⁹ mmol cm⁻² s⁻¹. The calcite dissolution rate was slower than the biodegradation rate, as evidenced by excess generation of CO₂ relative to Ca²⁺ production. The decrease in pH was less in experiments with calcite present than in those with quartz sand present due to buffering by calcite dissolution. Dissolution of Fe oxyhydroxides was not observed under any experimental conditions.     

The chemical evolution of Kurnub Group paleowater in the Sinai-Negev province—a mass balance approach

The chemical evolution of the Kurnub Group paleowater was studied starting from rainwater in recharge areas of the Sinai and along groundwater flowpaths leading to the natural outlets of this regional aquifer. This was achieved by investigating the chemical composition of groundwater, ionic ratios, degrees of saturation with common mineral species, normative analysis of dissolved salts and by modeling of rock/water interaction and mixing processes occurring along groundwater flow paths. The initial groundwater composition used is from the Nakhel well in Sinai. It evolves from desert rainwater percolating through typical Kurnub Group lithology in Sinai. This rainwater dissolves mainly gypsum, halite and dolomite together with smaller amounts of marine aerosol and K-feldspar. At the same time it precipitates calcite, SiO₂, smectite and degasses CO₂. Between the area of Nakhel and the northern Negev the chemistry of Kurnub Group waters is influenced by dissolution of halite and lesser amounts of gypsum of surficial origin in recharge areas, small amounts of feldspars and of dolomite cement in sandstones eroded from the Arabo-Nubian igneous massif of Sinai and organic degradation-derived CO₂. Concomitantly, there is precipitation of calcite, smectite, SiO₂ and probably analcime characteristic of sediments in continental closed basins. North of the Negev, the Kurnub Group fluids are diluted and altered by mixing with Judea Group aquifer groundwaters. On the E there is mixing with residual brines from the water body ancestral to the Dead Sea, prior to discharge into the Arava valley. Rock/water interaction indicated by NETPATH and PHREEQC modeling is in agreement with lithology and facies changes previously observed in the Kurnub Group sequence.     

Saltwater intrusion and nitrate pollution in the coastal aquifer of Dar es Salaam, Tanzania

Dar es Salaam Quaternary coastal aquifer is a major source of water supply in Dar es Salaam City used for domestic, agricultural, and industrial uses. However, groundwater overdraft and contamination are the major problems affecting the aquifer system. This study aims to define the principal hydrogeochemical processes controlling groundwater quality in the coastal strip of Dar es Salaam and to investigate whether the threats of seawater intrusion and pollution are influencing groundwater quality. Major cations and anions analysed in 134 groundwater samples reveal that groundwater is mainly affected by four factors: dissolution of calcite and dolomite, weathering of silicate minerals, seawater intrusion due to aquifer overexploitation, and nitrate pollution mainly caused by the use of pit latrines and septic tanks. High enrichment of Na⁺ and Cl^? near the coast gives an indication of seawater intrusion into the aquifer as also supported from the Na–Cl signature on the Piper diagram. The boreholes close to the coast have much higher Na/Cl molar ratios than the boreholes located further inland. The dissolution of calcite and dolomite in recharge areas results in Ca–HCO₃ and Ca–Mg–HCO₃ groundwater types. Further along flow paths, Ca²⁺ and Na⁺ ion exchange causes groundwater evolution to Na–HCO₃ type. From the PHREEQC simulation model, it appears that groundwater is undersaturated to slightly oversaturated with respect to the calcite and dolomite minerals. The results of this study provide important information required for the protection of the aquifer system.     

Chemical evolution of groundwater in the Wilcox aquifer of the northern Gulf Coastal Plain,USA

The Wilcox aquifer is a major groundwater resource in the northern Gulf Coastal Plain (lower Mississippi Valley) of the USA, yet the processes controlling water chemistry in this clastic aquifer have received relatively little attention. The current study combines analyses of solutes and stable isotopes in groundwater, petrography of core samples, and geochemical modeling to identify plausible reactions along a regional flow path ～300 km long. The hydrochemical facies evolves from Ca-HCO₃ upgradient to Na-HCO₃ downgradient, with a sequential zonation of terminal electron-accepting processes from Fe(III) reduction through SO₄ ^2? reduction to methanogenesis. In particular, decreasing SO₄ ^2? and increasing δ³⁴S of SO₄ ^2? along the flow path, as well as observations of authigenic pyrite in core samples, provide evidence of SO₄ ^2? reduction. Values of δ¹³C in groundwater suggest that dissolved inorganic carbon is contributed both by oxidation of sedimentary organic matter and calcite dissolution. Inverse modeling identified multiple plausible sets of reactions between sampled wells, which typically involved cation exchange, pyrite precipitation, CH₂O oxidation, and dissolution of amorphous Fe(OH)₃, calcite, or siderite. These reactions are consistent with processes identified in previous studies of Atlantic Coastal Plain aquifers. Contrasts in groundwater chemistry between the Wilcox and the underlying McNairy and overlying Claiborne aquifers indicate that confining units are relatively effective in limiting cross-formational flow, but localized cross-formational mixing could occur via fault zones. Consequently, increased pumping in the vicinity of fault zones could facilitate upward movement of saline water into the Wilcox.     

Review: The potential impact of underground geological storage of carbon dioxide in deep saline aquifers on shallow groundwater resources

Underground geological storage of CO₂ in deep saline aquifers is considered for reducing greenhouse gases emissions into the atmosphere. However, some issues were raised with regard to the potential hazards to shallow groundwater resources from CO₂ leakage, brine displacement and pressure build-up. An overview is provided of the current scientific knowledge pertaining to the potential impact on shallow groundwater resources of geological storage of CO₂ in deep saline aquifers, identifying knowledge gaps for which original research opportunities are proposed. Two main impacts are defined and discussed therein: the near-field impact due to the upward vertical migration of free-phase CO₂ to surficial aquifers, and the far-field impact caused by large-scale displacement of formation waters by the injected CO₂. For the near-field, it is found that numerical studies predict possible mobilization of trace elements but concentrations are rarely above the maximum limit for potable water. For the far-field, numerical studies predict only minor impacts except for some specific geological conditions such as high caprock permeability. Despite important knowledge gaps, the possible environmental impacts of geological storage of CO₂ in deep saline aquifers on shallow groundwater resources appears to be low, but much more work is required to evaluate site specific impacts.