Hydrochemistry and source of high fluoride in groundwater of the Nairobi area,Kenya / Hydrochimie et origine des fortes concentrations en fluorure dans l'eau souterraine de la région de Nairobi,au Kenya

Abstract

This study aims to identify the hydrogeochemical processes influencing the high fluoride concentrations in groundwater of the Nairobi area, Kenya. For this purpose 16 groundwater samples were collected and analysed. Fluoride concentrations above the WHO standard are found in the downstream areas. The high F^? concentrations are correlated with high sodium and pH and low Ca²⁺ concentrations. Weathering of sodium-rich alkaline igneous rocks causes a pH increase resulting in an increase in HCO₃ ^? and CO₃ ^2- by dissolution of CO₂. Groundwater becomes oversaturated compared to calcite and calcite precipitation occurs, leading to a decrease in Ca²⁺. This causes a sub-saturation with respect to fluorite and dissolution of fluorite increases the F^? concentration. These reactions were modelled using the PHREEQC model and the results showed a good agreement with the measured groundwater quality, indicating that the proposed reactions are plausible for explaining the observed concentrations in groundwater.     

Mangos shale-associated alluvium

Inquiry into the dissolution kinetics of naturally occurring geologic materials, rather than individual mineral species, has been relatively neglected. This is especially true of surface processes, the realm of surface water hydrology and geomorphology. This paper focuses attention at a laboratory study of the rate of such complex reactions. Functions defining the dissolution rates of saline (0.1–20 per cent salt content) Mancos Shale-associated alluvium in distilled water follow varying patterns. Dissolution is characterized by an initial (<5 min) high rate constant, by a following phase (20 min-57 h) where rates are reduced drastically, and by a final period of encroachment to equilibrium. Initial dissolution rates increase with increase in salt content and sediment: water ratio. The time necessary to approach equilibrium is, however, found to be directly proportional to the sediment; water ratio. The concentration of Na⁺, Mg²⁺, Ca²⁺, SC^2?₄ and HCO^?₃, and the relative abundance of Ca²⁺ and HCO^?₃ increase continuously with contact time, indicating that the hydrated sodium and magnesium sulphate minerals provide most of the initial solutes, though not necessarily most of the total solute bulk. The results obtained in this study indicate that the high initial dissolution rate of soluble minerals from alluvium, and particularly from shales in contact with aqueous solutions, is too short-lived to account for most of the solutes occurring in heavily sediment-laden surface flow. Excluding input from slower, usually supersaturated subsurface flow, dissolution from sediment in transport should be a major source of solutes in originally undersaturated and kinetically unequilibrated surface water in semiarid and arid regions.     

Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.     

Rates of dissolution of aluminosilicates in seawater

Dissolution of eight clay minerals, four zeolites, and quartz in seawater has been monitored for81/2 years. For most of the minerals, dissolution can be described as a first-order reaction in which dissolved silica approaches from undersaturation steady concentration values with time. Characteristic reaction rate constants (k₁) are of the order of 10^?7 sec^?1. One of the zeolites, clinoptilolite, shows a different dissolution behavior: SiO₂ concentration in solution reaches a high value within one year, followed by a decline to a lower value, suggestive of precipitation of another silicate phase (possibly sepiolite).A mathematical solution is given for a kinetic equation combining the parabolic-rate and first-order rate processes. It is shown that in a wide range of silicate dissolution reactions taking place over long periods of time, the presence of the parabolic-rate dissolution processes cannot be detected, thereby making its inclusion in the kinetic equations unnecessary. The experimental rates of dissolution are comparable to the SiO₂^? dissolution rates in oceanic sediments near the sediment/water interface. But deeper in the sediment, the calculated dissolution rates are significantly lower than the near-interface and experimental values.     

The role of gypsum and/or dolomite dissolution in tufa precipitation: lessons from the hydrochemistry of a carbonate–sulphate karst system

The precipitation of freshwater carbonates (tufa) along karstic rivers is enhanced by degassing of carbon dioxide (CO₂) downstream of karstic springs. However, in most karstic springs CO₂ degassing is not enough to force the precipitation of tufa sediments. Little is known about the role of dissolution of gypsum or dolomite in the hydrochemistry of these systems and how this affects the formation of tufa deposits. Here we present a monitoring study conducted over a year in Trabaque River (Spain). The river has typical karst hydrological dynamics with water sinking upstream and re‐emerging downstream of the canyon. Mixing of calcium–magnesium bicarbonate and calcium sulphate waters downstream of the sink enhances the dissolution of carbonates and potentially plays a positive role in the formation of tufa sediments. However, due to the common‐ion effect, dissolution of dolomite and/or gypsum causes precipitation of underground calcite cements as part of the incongruent dissolution of dolomite/dedolomitization process, which limits the precipitation of tufa sediments. Current precipitation of tufa is scant compared to previous Holocene tufa deposits, which likely precipitated from solutions with higher saturation indexes of calcite (SIcc values) than nowadays. Limited incongruent dissolution of dolomite/dedolomitization favours higher SIcc values. This circumstance occurs when waters with relatively high supersaturation of dolomite and low SO₄^2? composition sink in the upper sector of the canyon. In such a scenario, the process of mixing waters enhances the exclusive dissolution of limestones, preventing the precipitation of calcite within the aquifer and favouring the increase of SIcc values downstream of the springs. Such conditions were recorded during periods of high water level of the aquifers and during floods. This research shows that the common‐ion effect caused by the dissolution of gypsum and/or dolomite rocks can limit [or favour] the precipitation of tufa sediments depending on the occurrence [or not] of incongruent dissolution of dolomite/dedolomitization. Copyright © 2016 John Wiley & Sons, Ltd.     

Potassium Permanganate Doped Geopolymers for Remedial Applications

This study investigates the use of KMnO₄ doped geopolymers as controlled‐release materials for remedial applications. The geopolymers were prepared by mixing alkali activated Na‐silicate solutions, metakaolin, and various amounts of granular KMnO₄. Samples were heat treated at 75 °C for 48 h. Concentrations of KMnO₄ in samples 1, 2, and 3 were 1.40 × 10^?1, 4.63 × 10^?1, and 6.07 × 10^?1 g/cm³, respectively. 1D column experiments showed that a high MnO₄^? release rate lasted for the first few hours, followed by a gradual decrease of MnO₄^? release. Neither cracks nor surface erosion of the geopolymers were observed throughout the experiments. Sample 1 approached exhaustion at the end of the Day 7. It took about 18 d for exhaustion of KMnO₄ releases in samples 2 and 3. Modeling of the observed KMnO₄ releases suggested diffusion and dissolution‐related fast transport as the most important mechanisms. This latter mechanism involves the creation of a connected secondary porosity in the geopolymers by dissolution of KMnO₄ granules. The contribution of Fickian diffusion to the total release decreased as the KMnO₄ content of the samples increased, and the dissolution mechanism became increasingly important.     

Simulation of the dissolution of weathered versus unweathered limestone in carbonic acid solutions of varying strength

A simulation was undertaken within a climatic chamber to investigate limestone dissolution under varied carbonic acid (H₂CO₃) strengths as a possible analogue for future increases in atmospheric CO₂ arising from global warming. Twenty‐eight samples cut from a block of Bath (Box Hill) limestone from Somerville College, Oxford, which had been removed during restoration after 150 years in an urban environment, were weighed and placed in closed bottles of thin plastic containing varying concentrations of H₂CO₃. Half of the stone samples were derived from exposed surfaces of the stone block (weathered) while the others were obtained from the centre of the block on unexposed surfaces (unweathered). The purpose of this was to compare dissolution of previously weathered versus unweathered surfaces in strong (pH 4·73) versus weak (pH 6·43) solutions of H₂CO₃. A temperature of c. 19 °C was maintained within the chamber representing a plausible future temperature in Oxford for the year 2200 given current warming scenarios. The simulation lasted 25 days with a few stone samples being removed midway. Stone samples show reduced weight in all cases but one. There was greater dissolution of stone samples in a strong H₂CO₃ solution as conveyed by higher concentrations of total hardness and Ca²⁺ in the water samples as well as enhanced microscopic dissolution features identified using SEM. The simulation confirms that enhanced atmospheric CO₂ under global warming, given adequate moisture, will accelerate dissolution rates particularly of newly replaced limestone building stones. However, previously weathered surfaces, such as those on historical stone exposed for a century or more, appear to be less susceptible to the effects of such increased rainfall acidity. Conservation techniques which remove weathered surfaces, such as stone cleaning, may accelerate future decay of historical limestone structures by increasing their susceptibility to dissolution. Copyright © 2006 John Wiley & Sons, Ltd.     

Application of geochemical and stable isotopic tracers to investigate groundwater salinity in the Ochi-Narkwa Basin,Ghana

Rainwater, groundwater and soil-water samples were analysed to assess groundwater geochemistry and the origin of salinity in the Ochi-Narkwa basin of the Central Region of Ghana. The samples were measured for major ions and stable isotopes (δ¹⁸O, δ²H and δ¹³C). The Cl^? content in rainwater decreased with distance from the coast. The major hydrochemical facies were Na-Cl for the shallow groundwaters and Ca-Mg-HCO₃, Na-Cl and Ca-Mg-Cl-SO₄ for the deep groundwaters. Groundwater salinization is caused largely by halite dissolution and to a minor extent by silicate weathering and seawater intrusion. Stable isotope composition of the groundwaters followed a slope of 3.44, suggesting a mixing line. Chloride profiles in the soil zone revealed the existence of salt crusts, which support halite dissolution in the study area. A conceptual flow model developed to explain the mechanism of salinization showed principal groundwater flow in the NW–SE direction.

EDITOR D. Koutsoyiannis

ASSOCIATE EDITOR K. Heal     

Fine chronology of volcanic processes using 238U-230Th systematics

The²³⁰Th-²³⁸U radioactive disequilibrium method was applied to the study of recent volcanic rocks from Costa Rica. Most samples are from the Irazu volcano. Some samples were dated by internal isochrons using the (²³⁰Th/²³²Th)-(²³⁸U/²³²Th) diagram, others were studied only by whole rock analyses. The evolution of the parent magma may be followed by the initial (²³⁰Th/²³²Th)₀ ratios of the rocks. A model involving a differentiating magma chamber that existed for 140,000 years under the Irazu volcano correlates well with the observations. Other volcanoes seem to be in earlier stages of their evolution. Continuing study may help to solve the tholeiitic to andesitic volcanism relationship.     

Leaching characteristics of ash from the May 18, 1980, eruption of Mount St. Helens volcano,Washington

Leaching of freshly erupted air-fall ash, unaffected by rain, from the May 18, 1980, eruption of Mount St. Helens volcano, Washington, shows that Ca²⁺, Na⁺, Mg²⁺, SO ₄ ^2? , and Cl^? are the predominant chemical species released on first exposure of the ash to water. Extremely high correlation of Ca with SO₄ and Na with Cl in water leachates suggests the presence of CaSO₄ and NaCl salts on the ash. The amount of water soluble material on ash increases with distance from source and with the weight fraction of small (less than 63 micrometers) ash particles of high-surface area. This suggests that surface reactions such as adsorption are responsible for concentrating the soluble material. CaSO₄, NaCl, and other salts are probably formed as microscopic crystals in the high-temperature core of the eruption column and are then adsorbed by silicate ash particles. The environmentally important elements Zn, Cu, Cd, F. Pb, and Ba are released by a water leach in concentrations which could pose short-term hazards to some forms of aquatic life. However, calculated concentrations are based on a water-to-ash ratio of 4:1 or less, which is probably an underestimation of the regionally operative ratio. A subsequent leach of ash by warm alkaline solution shows dramatic increases, in the amount of dissolved SiO₂, U, and V, which are probably caused by increased dissolution of the glassy component of ash. Glass dissolution by alkaline ground water is a mechanism for providing these three elements to sedimentary traps where they may coaccumulate as uraniferous silica or U-V minerals. Leaching characteristics of ash from Mount St. Helens are comparable to characteristics of ash of similar composition from volcanoes in Guatemala. Ashes from each locality show similar ions predominating for a given leachate and similar fractions of a particular element in the ash removed on contact with the leach solution.     

Spatial characteristics and controlling factors of chemical weathering of loess in the dry season in the middle Loess Plateau,China

Hydrochemistry methods were used to decipher the weathering and geochemical processes controlling solute acquisition of river waters in the dry season in the middle Loess Plateau (MLP), one of the most severely eroded areas and turbid riverine systems in the world. River waters were neutral to slightly alkaline with pH varying from 7.6 to 9.6. The total dissolved solids decreased from northwest to southeast with a mean value of 804 mg/l, much higher than the global average and other large rivers in China. Ternary diagram showed that river waters were dominated by Na⁺, HCO₃^?, and Cl^? with the main water‐type of HCO₃^?–Cl^?–Na⁺. Saturation index values, Mg²⁺, Ca²⁺, and HCO₃^? analyses indicated the preferential Ca²⁺ removal by calcite precipitation. Gibbs plots and stoichiometry plots indicated that the dissolved solutes were mainly derived from rock weathering with minor anthropogenic and atmospheric inputs. Samples in the northwestern basin are also influenced by evaporation. A forward model of mass budget calculation showed that, owing to high soluble characteristics, evaporite dissolution was a major feature of river waters and contributed 41% to the total dissolved cations on average, while carbonate and silicate weathering contributed 28%,and 25% on average, respectively. Besides evaporite dissolution, cation exchange is also responsible for the high concentrations of Na⁺ in river water. Spatial variations showed that evaporite dissolution and silicate weathering were higher in the northern basin, whereas carbonate weathering was higher in the southern basin. Different from most rivers in the world, the physical erosion rates (varying from 117.7 to 4116.6 t/km²y) are much higher than the chemical weathering rates (varying from 3.54 to 6.76 t/km²y) in the MLP because of the loose structure of loess and poor vegetation in the basin. In the future, studies on comparison of water geochemistry in different seasons and on influence of different types of land use and soil salinization on water geochemistry, denudation rates, and water quality should be strengthened in the MLP. These results shed some lights on processes responsible for modern loess weathering and also indicate the importance of time‐series sampling strategy for river water chemistry. Copyright © 2016 John Wiley & Sons, Ltd.     

Dissolution-filling mechanism of atmospheric precipitation controlled by both thermodynamics and kinetics

Affected by structural uplift,the Ordovician carbonate rockbed in the Tarim Basin,China,was exposed to dissolution and reformation of atmospheric precipitation many times,and formed a large quantity of karst caves serving as hydrocarbon reservoir.However,drilling in Tahe area showed that many large karst caves,small pores and fractures are filled by calcite,resulting in decrease in their reservoir ability.Calcite filled in the karst caves has very light oxygen isotopic composition and87Sr/86Sr ratio.Its 18OPDB ranges from 21.2‰to 13.3‰with the average of 16.3‰and its87Sr/86Sr ratio ranges from0.709561 to 0.710070 with the average of 0.709843.The isotope composition showed that calcite is related to atmospheric precipitation.Theoretic analyses indicated that the dissolving and filling actions of the precipitation on carbonate rocks are controlled by both thermodynamic and kinetic mechanisms.Among them,the thermodynamic factor determines that the precipitation during its flow from the earth surface downward plays important roles on carbonate rocks from dissolution to saturation,further sedimentation,and finally filling.In other words,the depth of the karstification development is not unrestricted,but limited by the precipitation beneath the earth surface.On the other hand,the kinetic factor controls the intensity,depth,and breadth of the karstification development,that is,the karstification is also affected by topographic,geomorphologic,climatic factors,the degree of fracture or fault,etc.Therefore,subject to their joint effects,the karstification of the precipitation on the Ordovician carbonate rocks occurs only within a certain depth(most about 200 m)under the unconformity surface,deeper than which carbonate minerals begin to sedimentate and fill the karst caves that were formed previously.     

Occurrence of oceanic plagiogranites in the older tectonic zone,Southwest Japan

K, Rb and Sr concentrations and Sr isotopic compositions were determined for the Dai granitic rocks of trondhjemitic composition occurring in a serpentinite mass in the Nagato tectonic zone formed in the Late Paleozoic era, and for the granitic rocks of quartz dioritic composition recently dredged from the seamount of the Kyushu-Palao Ridge. Both granitic rocks are characterized by low abundances of K and Rb, low K₂O/Na₂O ratios, high K/Rb ratios, low Rb/Sr ratios and low initial⁸⁷Sr/⁸⁶Sr ratios. These characteristics suggest that strong similarities may exist between the Dai granitic rocks and the dredged granitic rocks, and that the Dai granitic rocks may be classified as oceanic plagiogranite. These oceanic plagiogranites may plausibly represent single-stage mantle-derived granites, possibly from the suboceanic mantle.     

Seasonal δ13CDIC sourcing and geochemical flux in telogenetic epikarst of south-central Kentucky

Telogenetic epikarst carbon sourcing and transport processes and their associated hydrogeochemical responses are complex and dynamic. Carbon dioxide (CO₂) transport rates in the epikarst zone are often driven by hydrogeochemical responses, which influence carbonate dissolution and conduit formation. This study examines the influence of land use on carbon sourcing and carbonate dissolution kinetics through a comparative analysis of separate, but similar, epikarst systems in south-central Kentucky. The use of high-resolution hydrogeochemical data from multiple data loggers and isotope analysis from collected water samples reflects the processes within these epikarst aquifers, which are estimated to contribute significantly to bedrock dissolution. Results indicate that, in an agricultural setting, long-term variability and dissolution is governed by seasonal production of CO₂ . In a more urbanized, shallower epikarst system, land cover may affect CO₂ transport between the soil and underlying bedrock. This concentration of CO₂ potentially contributes to ongoing dissolution and conduit development, irrespective of seasonality. The observed responses in telogenetic epikarst systems seem to be more similar to eogenetic settings, which is suggested to be driven by CO₂ transport occurring independent of high matrix porosity. The results of this study indicate site-specific responses with respect to both geochemical and δ¹³C_DIC changes on a seasonal scale, despite regional geologic similarities. The results indicate that further comparative analyses between rural and urban landscapes in other karst settings is needed to delineate the impact of land use and seasonality on dissolution and carbon sourcing during karst formation processes. © 2019 John Wiley & Sons, Ltd.     

Identification of a hidden thermal fissure in a volcanic terrain using a combination of hydrothermal convection indicators and soil-atmosphere analysis

Mapping and characterizing fracturing in a volcanic terrain is facilitated by the analysis of physical and chemical properties of soils. The parameters analyzed include the temperature at shallow depth, the spontaneous potential (SP), and the ⁴He, ⁴⁴CO₂, and ²²²Rn contents of soil gases, as measured in situ by mass spectrometry and α counter.This analysis allowed a distinction of deep fissures not accompanied by thermal loss, characterized by a negative SP anomaly and high He levels, and of a hidden fissure with thermal loss, characterized by a positive SP anomaly and high He, Rn, and CO₂ levels. This fissure has no visible surface manifestations.This method of analysing the convective thermal transfer is useful when analysing fracturing in volcanic structures to estimate their eruptive potential.     

Seawater–freshwater mixing and resulting calcite dissolution: an example from a coastal alluvial aquifer in eastern South Korea

Abstract

In order to evaluate groundwater quality and geochemical reactions arising from mixing between seawater and dilute groundwater, we performed a hydrochemical investigation of alluvial groundwater in a limestone-rich coastal area of eastern South Korea. Two sites were chosen for comparison: an upstream site and a downstream site. Data of major ion chemistry and ratios of oxygen–hydrogen isotopes (δ¹⁸O, δD) revealed different major sources of groundwater salinity: recharge by sea-spray-affected precipitation in the upstream site, and seawater intrusion and diffusion zone fluctuation in the downstream site. The results of geochemical modelling showed that Ca²⁺ enrichment in the downstream area is caused by calcite dissolution enhanced by the ionic strength increase, as a result of seawater–groundwater mixing under open system conditions with a constant P_CO2 value (about 10^?1.5 atm). The results show that, for coastal alluvial groundwater residing on limestone, significant hydrochemical change (especially increased hardness) due to calcite dissolution enhanced by seawater mixing should be taken into account for better groundwater management. This process can be effectively evaluated using geochemical modelling.

Editor D. Koutsoyiannis; Associate editor Y. Guttman

Citation Chae, G.-T., Yun, S.-T., Yun, S.-M., Kim, K.-H., and So, C.-S., 2012. Seawater–freshwater mixing and resulting calcite dissolution: an example from a coastal alluvial aquifer in eastern South Korea. Hydrological Sciences Journal, 57 (8),1–12.     

Comprehensive geochemical identification of highly evolved marine carbonate rocks as hydrocarbon-source rocks as exemplified by the Ordos Basin

China’s widespread marine carbonate rock series are mostly characterized by intensive thermal evolu- tion and low abundance of organic matter, especially the Lower Paleozoic carbonate rocks have experienced multi-episodes of tectonics and prolonged history of thermal evolution, thus making it more complicatedethe development and distribution of hydrocar- bon-source rocks reflected in the sedimentary, bio- logical and geochemical facies. Consequently, it seems much less powerful to assess the …     

Spatial and temporal variability of groundwater quality of an Algerian aquifer: the case of Soummam Wadi

ABSTRACT

Five-year monitoring of physicochemical parameters was performed with two campaigns in low and high water periods of the Lower Soummam catchment. Data from 18 wells were processed by multivariate statistical tools in order to identify the principal factors influencing groundwater chemistry. Two matrices of 14 and 8 physicochemical parameters with 18 groundwater samples collected in wells were obtained. The correlation matrix showed strong associations between nine variables: K⁺, Ca²⁺, Na⁺, SO₄^2?, Cl^?, Mg²⁺, NO₂^?, Zn²⁺ and Sr²⁺. Principal component analysis and factor analysis showed that the cumulated variance of high and low water periods was of 83.19% and 78.55%, respectively. The variables assigned to the mineralization effect or to pollution indicators were presented by the factor analysis. The bivariate plots confirmed a mineralization model, ascribed to dissolution of geological materials, and to high levels of saline contamination attributed to leakages from sanitary systems. They also showed an increase “upstream to downstream” of the mineralization, visualization of temporal variations, and a dilution process identification of the natural mineralization during the recharge of the aquifer.

EDITOR D. Koutsoyiannis; ASSOCIATE EDITOR X. Chen     

A method for incorporating equilibrium chemical reactions into multiphase flow models for CO2 storage

CO₂ injection and storage in deep saline aquifers involves many coupled processes, including multiphase flow, heat and mass transport, rock deformation and mineral precipitation and dissolution. Coupling is especially critical in carbonate aquifers, where minerals will tend to dissolve in response to the dissolution of CO₂ into the brine. The resulting neutralization will drive further dissolution of both CO₂ and calcite. This suggests that large cavities may be formed and that proper simulation may require full coupling of reactive transport and multiphase flow. We show that solving the latter may suffice whenever two requirements are met: (1) all reactions can be assumed to occur in equilibrium and (2) the chemical system can be calculated as a function of the state variables of the multiphase flow model (i.e., liquid and gas pressure, and temperature). We redefine the components of multiphase flow codes (traditionally, water and CO₂), so that they are conservative for all reactions of the chemical system. This requires modifying the traditional constitutive relationships of the multiphase flow codes, but yields the concentrations of all species and all reaction rates by simply performing speciation and mass balance calculations at the end of each time step. We applied this method to the H₂O–CO₂–Na–Cl–CaCO₃ system, so as to model CO₂ injection into a carbonate aquifer containing brine. Results were very similar to those obtained with traditional formulations, which implies that full coupling of reactive transport and multi-phase flow is not really needed for this kind of systems, but the resulting simplifications may make it advisable even for cases where the above requirements are not met. Regarding the behavior of carbonate rocks, we find that porosity development near the injection well is small because of the low solubility of calcite. Moreover, dissolution concentrates at the front of the advancing CO₂ plume because the brine below the plume tends to reach high CO₂ concentrations quite rapidly. We conclude that carbonate dissolution needs not to be feared.