Chemical composition of natural waters and brines as a result of hydrogeochemical processes in water-rock-gas systems

Thermodynamic computer modeling was carried out to evaluate the formation of the chemical composition of main geochemical types of groundwaters. An explanation was proposed for the geochemical evolution of underground saline waters and brines along the calcic and sodic trends, the inversion of groundwater in the deep horizons of sedimentation structures, and the geochemical diversity of CO₂-rich waters in crystalline rocks. The occurrence of hydrogeochemical processes is controlled by the physicochemical conditions of the state of the water-rock-gas system. The following parameters (boundary conditions) are critical in natural hydrogeologic environments: the mass ratio of interacting rock and water (R/W), the openness (closeness) of hydrogeochemical systems with respect to CO₂ and O₂, the chemical and mineral composition of rocks, and temperature-pressure conditions. The estimation of boundary conditions showed the following.

1. The petrochemical type of rock affects the composition of the aqueous phase through the dissolution rates of minerals, especially volatile-bearing ones. A decrease in water exchange and an increase in R/W (10^?6??10²) are accompanied by an increase in the salinity of the aqueous phase and an increase in the fraction of Cl, Na, and Ca (in a closed system) or HCO₃, Cl, and Na (in a system open to CO₂).
2. The composition of the aqueous phase of water-rock systems is most strongly affected by the abundance in the rock of extractable Cl and reactive organic matter, which controls the geochemical type of the aqueous phase and its position in the Hardie-Eugster diagram.
3. The composition of the aqueous phase is shifted into the calcic field of the Hardie-Eugster diagram at the closure of the water-rock system and into the carbonate field at the opening of the water-rock system to CO₂. Waters showing pH ?? 8.5 are formed in feldspathic rocks with low contents of extractable volatiles. Alkaline waters with pH > 9 are formed in water-rock systems (a) under the influence of organic matter and (b) by the evaporative concentration waters under surface conditions.
4. The higher the degree of seawater concentration and the lower the R/W value, the more significant the effect of seawater composition on the aqueous phase chemistry of the water-rock system. With increasing degree of seawater concentration, the composition of the aqueous phase changes in the sequence Cl-SO₄-Na-Mg- ?? Cl-SO₄-Mg-Na?? Cl-Mg (at low R/W) and Cl-Na ?? Cl-Na-Mg (at high R/W). The influence of the petrochemical type of rock and CO₂ partial pressure, on the geochemical type of the aqueous phase in the seawater-rock system is more significant at high R/W.
5. A temperature increase shifts the acid-base state of the aqueous phase into the alkaline region and its redox state into the reducing region.

     

Hydrodynamic and geochemical conditions of the formation of stratiform Zn-Pb ore mineralization by chloride solutions

Ore mineralization is formed by postsedimentary (concentrated by evaporation to stage SW2) chloride brines metamorphosed in hydrogeochemical systems that are closed with respect to CO₂, evolve according to “calcic” trend, and have high 2mCa²⁺ > mHCO ₃ ^? + 2mCO ₃ ^2? ratios. In these situations at high R/W ratios (10–100) and temperatures (100–200°C), these brines concentrate ore elements (Zn, Pb, Fe, and Mn) that are geochemical analogues of Ca. The sulfide precipitation of these elements occurs under the effect of carbonate rocks at the abiogenic sulfate reduction of S(VI) of the original brines at low Eh values, which are created in carbonate rocks at higher (>100°C) temperatures. This origin of sulfide mineralization is intensified at decreasing R/W ratios during the dilution of the original brines by elision waters and an increase in the temperature. The hydrodynamics of these ore-forming brines is controlled by the elision hydrogeological regime, which is defined in hydrogeological structures by the geostatic pressure. The brines migrate into the zones of geochemical barriers during the relaxation of hydrogeological structures toward their equilibrium hydrostatic state. Hydrogeological structures, optimal for the precipitation of ore mineralization, are hydrodynamically active and able to maintain a steady (during 10⁵-10⁶ years) inflow of ore-forming brines into the zones of geochemical barriers and the maximum number of water-exchange cycles at these barriers. Modern analogues of these structures are miogeosyncline foredeeps with Cl-Na-Ca chloride brines with high concentrations of ore elements and overall flow rates ranging from 0.n to n m³/year. Stagnate hydrogeological platform structures in hydrostatic equilibrium cannot ensure water exchange needed for ore formation, and, hence, the brines of these structures are not able to deposit the ore elements contained in them, in spite of the high concentrations of these elements.     

Evidence of magmatic CO2-rich fluids in peraluminous graphite-bearing leucogranites from Deep Freeze Range (northern Victoria Land,Antarctica)

Fine-grained peraluminous synkinematic leuco-monzogranites (SKG), of Cambro-Ordovician age, occur as veins and sills (up to 20–30 m thick) in the Deep Freeze Range, within the medium to high-grade metamorphics of the Wilson Terrane. Secondary fibrolite + graphite intergrowths occur in feldspars and subordinately in quartz. Four main solid and fluid inclusion populations are observed: primary mixed CO₂+H₂O inclusions + Al₂SiO₅ ± brines in garnet (type 1); early CO₂-rich inclusions (± brines) in quartz (type 2); early CO₂+CH₄ (up to 4 mol%)±H₂O inclusions + graphite + fibrolite in quartz (type 3); late CH₄+CO₂+N₂ inclusions and H₂O inclusions in quartz (type 4). Densities of type 1 inclusions are consistent with the crystallization conditions of SKG (750°C and 3 kbar). The other types are post-magmatic: densities of type 2 and 3 inclusions suggest isobaric cooling at high temperature (700–550°C). Type 4 inclusions were trapped below 500°C. The SKG crystallized from a magma that was at some stage vapour-saturated; fluids were CO₂-rich, possibly with immiscible brines. CO₂-rich fluids (±brines) characterize the transition from magmatic to post-magmatic stages; progressive isobaric cooling (T<670°C) led to a continuous decrease off _{O 2} can entering in the graphite stability field; at the same time, the feldspars reacted with CO₂-rich fluids to give secondary fibrolite + graphite. Decrease ofT andf _{O 2} can explain the progressive variation in the fluid composition from CO₂-rich to CH₄ and water dominated in a closed system (in situ evolution). The presence of N₂ the late stages indicates interaction with external metamorphic fluids.Contribution within the network Hydrothermal/metamorphic water-rock interactions in crystalline rocks: a multidisciplinary approach on paleofluid analysis. CEC program: Human Capital and Mobility     

CO2-Brine immiscibility at high temperatures,evidence from calcareous metasedimentary rocks

Study of fluid inclusions in quartz segregations and in the rock matrix of a calcareous psammite and a carbonate schist suggests that brines containing 23–24 weight percent salt (NaCl equivalent) are immiscible with CO₂ at the metamorphic conditions of approximately 600° and 6.5 Kb. The presence of a high temperature solvus between saline brine and CO₂ is supported by other fluid inclusion studies as well as experimental measurements from the literature. As saline brines are common in metamorphic and hydrothermal systems, CO₂-brine immiscibility should play an important role in petrogenesis. The fluid inclusions preserved in the quartz segregations probably represent the fluids generated by prograde metamorphic reactions, whereas the compositions of the fluids trapped in the rock matrix quartz suggest they have reequilibrated with the matrix minerals during incipient retrograde reactions. The isochores from the densest inclusions observed in this study pass close to the inferred peak metamorphic conditions; other isochores suggest an episode of deformation and recrystallization at 275° C and 1.4 Kb. Using the density information preserved in all the inclusions, a convex-downward uplift path on a P-T diagram is inferred for these rocks.     

Fluid inclusion studies of gold-bearing quartz veins from the Yirisen deposit,Sula Mountains greenstone belt,Masumbiri, Sierra Leone

The auriferous veins at Yirisen, Masumbiri, Sierra Leone, occurring mainly in the form of sericitic quartz-sulphide lodes and stringers, are hosted in metamorphosed volcano-sedimentary assemblages invaded by at least two generations of granitic intrusions. Detailed microthermometric studies of fluid inclusions from the veins coupled with laser Raman spectroscopic analysis show that the inclusions contain aqueous fluids of variable salinity (5 to 60 wt.% NaCl equivalent) and dense carbonic fluids (pure CO₂: 1.08>d>0.88 g/cm³). Optical observations and analysis on opened inclusions by scanning electron microscopy (SEM) reveal that some of the aqueous inclusions contain a number of daughter minerals: halite, sylvite, Ca-, Fe-, Mg- and possibly Li-bearing chlorides, and anhydrite; nahcolite occurs also in some of the CO₂ inclusions. The SEM runs also detected a small amount of electrum, suggesting that silver might be a bi-product of the mineralisation. The aqueous and carbonic fluids remained immiscible throughout the formation and evolution of the hydrothermal veins. A few mixed (H₂O+CO₂) inclusions apparently resulted from accidental trapping of both fluids in the same cavity. The wide range of salinities observed in the aqueous inclusions is attributed to the mixing of relatively hot, low-salinity aqueous fluids and colder, high-salinity brines. The CO₂-rich and low-salinity H₂O inclusions are considered to be derived from the metamorphic decarbonation/dehydration of the greenstone pile whilst the high-salinity brines are believed to be basinal in origin. Pressure–temperature (P–T) conditions of entrapment, inferred from the intersection of representative isochores of the immiscible fluids, indicate that the formation of the veins started at T=400°C and P about 4 kbar, in the presence of the high-density CO₂ and low-salinity H₂O fluids. At about 200°C, pressure fluctuations (incremental opening of the vein) correspond to the trapping of the lower-density CO₂ inclusions and high-salinity brines. It is proposed that the decarbonation/dehydration processes (possibly aided by later magmatic processes) expelled and mobilised the gold from the greenstone pile and concentrated it in the CO₂-bearing hydrothermal fluid in the form of Au–chloride complexes. High thermal gradients are believed to have caused the upward migration of this fluid from the bottom of the greenstone pile through structurally controlled conduits. We contend that phase separation of the H₂O–CO₂ metamorphic fluid, aided possibly by some wall–rock alteration, most probably triggered a decrease in ligand activity and thus, precipitation of the gold into lodes. Percolation of the basinal brines is thought to have remobilised some of the gold together with some silver.     

Melting of albite and dehydration of brucite in H2O–NaCl fluids to 9 kbars and 700–900°C: implications for partial melting and water activities during high pressure metamorphism

 The melting reaction: albite_(solid)+ H₂O_(fluid) =albite-H₂O_(melt) has been determined in the presence of H₂O–NaCl fluids at 5 and 9.2 kbar, and results compared with those obtained in presence of H₂O–CO₂ fluids. To a good approximation, albite melts congruently at 9 kbar, indicating that the melting temperature at constant pressure is principally determined by water activity. At 5 kbar, the temperature (T)- mole fraction (X _(H2O) ) melting relations in the two systems are almost coincident. By contrast, H₂O–NaCl mixing at 9 kbar is quite non-ideal; albite melts ∼70 ^°C higher in H₂O–NaCl brines than in H₂O–CO₂ fluids for X _(H2O) =0.8 and ∼100 ^°C higher for X _(H2O) =0.5. The melting temperature of albite in H₂O–NaCl fluids of X _(H2O)=0.8 is ∼100 ^°C higher than in pure water. The P–T curves for albite melting at constant H₂O–NaCl show a temperature minimum at about 5 kbar. Water activities in H₂O–NaCl fluids calculated from these results, from new experimental data on the dehydration of brucite in presence of H₂O–NaCl fluid at 9 kbar, and from previously published experimental data, indicate a large decrease with increasing fluid pressure at pressures up to 10 kbar. Aqueous brines with dissolved chloride salt contents comparable to those of real crustal fluids provide a mechanism for reducing water activities, buffering and limiting crustal melting, and generating anhydrous mineral assemblages during deep crustal metamorphism in the granulite facies and in subduction-related metamorphism. Low water activity in high pressure-temperature metamorphic mineral assemblages is not necessarily a criterion of fluid absence or melting, but may be due to the presence of low a _(H2O) brines. Received: 17 March 1995/Accepted: 9 April 1996     

Armouring of well cement in H2S–CO2 saturated brine by calcite coating – Experiments and numerical modelling

The active acid gas (H₂S–CO₂ mixture) injection operations in North America provide practical experience for the operators in charge of industrial scale CO₂ geological storage sites. Potential leakage via wells and their environmental impacts make well construction durability an issue for efficiency/safety of gas geological storage. In such operations, the well cement is in contact with reservoir brines and the injected gas, meaning that gas–water–solid chemical reactions may change the physical properties of the cement and its ability to confine the gas downhole. The cement-forming Calcium silicate hydrates carbonation (by CO₂) and ferrite sulfidation (by H₂S) reactions are expected. The main objective of this study is to determine their consequences on cement mineralogy and transfer ability. Fifteen and 60 days duration batch experiments were performed in which well cement bars were immersed in brine itself caped by a H₂S–CO₂ phase at 500 bar–120 °C. Scanning electron microscopy including observations/analyses and elemental mapping, mineralogical mapping by micro-Raman spectroscopy, X-ray diffraction and water porosimetry were used to characterize the aged cement. Speciation by micro-Raman spectroscopy of brine trapped within synthetic fluid inclusions were also performed. The expected calcium silicate hydrates carbonation and ferrite sulfidation reactions were evidenced. Furthermore, armouring of the cement through the fast creation of a non-porous calcite coating, global porosity decrease of the cement (clogging) and mineral assemblage conservation were demonstrated. The low W/R ratio of the experimental system (allowing the cement to buffer the interstitial and external solution pH at basic values) and mixed species diffusion and chemical reactions are proposed to explain these features. This interpretation is confirmed by reactive transport modelling performed with the HYTEC code. The observed cement armouring, clogging and mineral assemblage conservation suggest that the tested cement has improved transfer properties in the experimental conditions. This work suggests that in both acid gas and CO₂ geological storage, clogging of cement or at least mineral assemblage conservation and slowing of carbonation progress could occur in near-well zones where slight water flow occurs e.g. in the vicinity of caprock shales.     

Formation Laws of Inorganic Gas Pools in the Northern Jiangsu Basin

In the Northern Jiangsu basin there are high pure CO2 gas pools, low condensed oil-containing CO2 gas pools, high condensed oil-containing CO2 gas pools and He-containing natural gas pools, with the δ13Cco2 (PDB) values ranging from -2.87‰ to -6.50‰, 3He/4He 3.71×10-6 to 6.42×10-6, R/Ra 2.64 to 4.5, 40Ar/36Ar 705 to 734, belonging to typical mantle source inorganic gas pools which are related to young magmatic activity. The gas layers occur in two major reservoir-caprock systems, the terrestrial Meso-Cenozoic clastic rock system and the marine Meso-Palaeozoic carbonate rock-clastic rock system. Controlled by the difference in the scale of traps in the two reservoir-caprock systems, large and medium-scale inorganic gas pools are formed in the marine Meso-Palaeozoic Group and only small ones are formed in the terrestrial Meso-Cenozoic strata. Inorganic gas pools in this basin are distributed along the two deep lithospheric faults on the west and south boundaries of the basin. Gas pools are developed     

http://www.sciencedirect.com/science/article/pii/S1674987114000590

This paper reviews the origin and evolution of fluid inclusions in ultramafic xenoliths,providing a framework for interpreting the chemistry of mantle fluids in the different geodynamic settings.Fluid inclusion data show that in the shallow mantle,at depths below about 100 km,the dominant fluid phase is CO_2±brines,changing to alkali-,carbonate-rich(silicate) melts at higher pressures.Major solutes in aqueous fluids are chlorides,silica and alkalis(saline brines;5-50 wt.%NaCl eq.).Fluid inclusions in peridotites record CO_2 fluxing from reacting metasomatic carbonate-rich melts at high pressures,and suggest significant upper-mantle carbon outgassing over time.Mantle-derived CO_2(±brines) may eventually reach upper-crustal levels,including the atmosphere,independently from,and additionally to magma degassing in active volcanoes.     

Fluid variability in 2 GPa eclogites as an indicator of fluid behavior during subduction

Fluid activity ratios calculated between millimeter- to centimeter-scale layers in banded mafic eclogites from the Tauern Window, Austria, indicate that variations in a _{H 2 O} existed between layers during equilibration at P approximately equal to 2GPa and T approximately equal to 625°C, whereas a _{CO 2} was nearly constant between the same layers. Model calculations in the system H₂O–CO₂–NaCl show that these results are consistent with the existence of different saturated saline brines, carbonic fluids, or immiscible pairs of both in different layers. The data cannot be explained by the exisience of water-rich fluids in all layers. The model fluid compositions agree with fluid inclusion compositions from eclogite-stage veins and segregations that contain (1) saline brines (up to 39 equivalent wt. % NaCl) with up to six silicate, oxide, and carbonate daughter phases, and (2) carbonic fluids. The formation of crystalline segregations from fluid-filled pockets or hydrofractures indicates high fluid pressures at 2 GPa; the record of fluid variability in the banded eclogite host rocks, however, implies that fluid transport was limited to local flow along individual layers and that there was no large-scale mixing of fluids during devolatilization at depths of 60–70 km. The lack of evidence for fluid mixing may, in part, reflect variations in wetting behavior of fluids of different composition; nonwetting fluids (water-rich or carbonic) would be confined to intergranular pore spaces and would be essentially immobile, whereas wetting fluids (saline brines) could migrate more easily along an interconnected fluid network. The heterogeneous distribution of chemically distinct fluids may influence chemical transport processes during subduction by affecting mineral-fluid element partitioning and by altering the migration properties of the fluid phase(s) in the downgoing slab.     

Experimental study of the CaMgSi2O6–CO2 system at 3–8 GPa

The melting relationships in the system CaMgSi₂O₆ (Di)–CO₂ have been studied in the 3–8 GPa pressure range to determine if there is an abrupt decrease in the temperature of the solidus accompanying the stabilization of carbonate as a subsolidus phase. Such a decrease has been observed previously in peridotitic and some eclogitic systems. In contrast, the solidus in the Di–CO₂ system was found to decrease in a gradual fashion from 3 to 8 GPa. This decrease accompanies an evolution in the composition of the melt at the solidus from silicate-rich with minor CO₂ at 3 GPa to carbonatitic at 5.5 GPa, where the carbonation reaction Diopside + CO₂ = Dolomite (Dol) + Coesite (Cst) intersects the solidus. The near-solidus melt remains carbonatitic at higher pressure, consistent with carbonate being the dominant contributor to the melt. Based on previous studies in both eclogitic and peridotitic systems, this conclusion can be extended to more complicated systems: once carbonate is a stable subsolidus phase, it plays a major role in controlling both the temperature of melting and the composition of the melt produced.     

Experimental investigations of the reaction path in the MgO–CO2–H2O system in solutions with various ionic strengths,and their applications to nuclear waste isolation

The reaction path in the MgO–CO₂–H₂O system at ambient temperatures and atmospheric CO₂ partial pressure(s), especially in high-ionic-strength brines, is of both geological interest and practical significance. Its practical importance lies mainly in the field of nuclear waste isolation. In the USA, industrial-grade MgO, consisting mainly of the mineral periclase, is the only engineered barrier certified by the Environmental Protection Agency (EPA) for emplacement in the Waste Isolation Pilot Plant (WIPP) for defense-related transuranic waste. The German Asse repository will employ a Mg(OH)₂-based engineered barrier consisting mainly of the mineral brucite. Therefore, the reaction of periclase or brucite with carbonated brines with high-ionic-strength is an important process likely to occur in nuclear waste repositories in salt formations where bulk MgO or Mg(OH)₂ will be employed as an engineered barrier. The reaction path in the system MgO–CO₂–H₂O in solutions with a wide range of ionic strengths was investigated experimentally in this study. The experimental results at ambient laboratory temperature and ambient laboratory atmospheric CO₂ partial pressure demonstrate that hydromagnesite (5424) (Mg₅(CO₃)₄(OH)₂ · 4H₂O) forms during the carbonation of brucite in a series of solutions with different ionic strengths. In Na–Mg–Cl-dominated brines such as Generic Weep Brine (GWB), a synthetic WIPP Salado Formation brine, Mg chloride hydroxide hydrate (Mg₃(OH)₅Cl · 4H₂O) also forms in addition to hydromagnesite (5424).     

Fluid flow patterns and infiltration isograds in melilite marbles from the Bufa del Diente contact metamorphic aureole, north-east Mexico

In the inner aureole of the Bufa del Diente alkali syenite (north-east Mexico), thin calcareous argillite bands horizontally embedded in impure marbles acted as contact-metamorphic aquifers for hypersaline brines of magmatic origin. Thick-bedded marbles were largely impervious. From 180 m up to the intrusion contact, argillites were completely decarbonated, resulting in melilite + wollastonite + phlogopite + perovskite-bearing parageneses. In marbles, this assemblage is confined to a narrow 7-12-m-wide infiltration zone adjacent to the contact. Up to this distance, calcite + wollastonite + diopside + alkali feldspar + titanite was stable, indicating that the fluid evolution in these marbles was internally buffered. Brine infiltration from the metaargillite aquifer into the marbles occurred perpendicular to the marble-metaargillite boundaries and was confined to a zone 4-6 cm wide above the boundaries. This is documented by the three reactions Cc + Di = Mel + CO₂, (1) Cc + Kfs + Di + H₂O = Phl + Wo + CO₂, (2) Cc + Ttn = Prv + Wo + CO₂, (3) Melilites (Ak_32-45Gh_13-32Sm_32-40 to Ak_52-72Gh_0-1Sm_28-48) occur as rims around diopsides and become continuously thicker towards the metaargillite beds. Fluid inclusion observations suggest that the infiltrating brine was hypersaline (NaCl + KCl_cq～ 65 wt%) and that the reactions took place at the water-rich side of the H₂O-CO₂-salts immiscibility field at about 600d? C (2, 3) and 660 to 680d? C (1) at P～ 1200 bar and X_co2～ 0.02. Mass balance calculations show that the amount of brine infiltrated from the aquifer into the marble was very low and decreased continuously with increasing distance from the boundary. The maximum width of brine infiltration was about 6 cm. This confirms that brine flow was largely parallel to the aquifer, not perpendicular to it. The CO₂ produced by the decarbonation reactions probably escaped as an immiscible low-density H₂O-CO₂ fluid of X_co2≤ 0.5 into overlying marble via grain-edge flow. The metaargillite-marble boundary acted as a semipermeable membrane 6 cm in thickness keeping back the brine in the aquifer and losing the in-situ produced low-density CO₂-rich fluid.     

An experimental study of phase equilibria in the systems H2O–CO2–CaCl2 and H2O–CO2–NaCl at high pressures and temperatures (500–800?°C, 0.5–0.9?GPa): geological and geophysical applications

Phase equilibria in the ternary systems H₂O–CO₂–NaCl and H₂O–CO₂–CaCl₂ have been determined from the study of synthetic fluid inclusions in quartz at 500 and 800 °C, 0.5 and 0.9 GPa. The crystallographic control on rates of quartz overgrowth on synthetic quartz crystals was exploited to prevent trapping of fluid inclusions prior to attainment of run conditions. Two types of fluid inclusion were found with different density or CO₂ homogenisation temperature (T_h(CO₂)): a CO₂-rich phase with low T_h(CO₂), and a brine with relatively high T_h(CO₂). The density of CO₂ was calibrated using inclusions in the binary system H₂O–CO₂. Mass balance calculations constrain tie lines and the miscibility gap between brines and CO₂-rich fluids in the H₂O–CO₂–NaCl and H₂O–CO₂–CaCl₂ systems at 500 and 800 °C, and 0.5 and 0.9 GPa. The miscibility gap in the CaCl₂ system is larger than in the NaCl system, and solubilities of CO₂ are smaller. CaCl₂ demonstrates a larger salting-out effect than NaCl at the same P–T conditions. In ternary systems, homogeneous fluids are H₂O-rich and of extremely low salinity, but at medium to high concentrations of salts and non-polar gases fluids are unlikely to be homogeneous. The two-phase state of crustal fluids should be common. For low fluid-rock ratios the cation compositions of crustal fluids are buffered by major crustal minerals: feldspars and micas in pelites and granitic rocks, calcite (dolomite) in carbonates, and pyroxenes and amphiboles in metabasites. Fluids in pelitic and granitic rocks are Na-K rich, while for carbonate and metabasic rocks fluids are Ca-Mg-Fe rich. On lithological boundaries between silicate and carbonate rocks, or between pelites and metabasites, diffusive cation exchange of the salt components of the fluid will cause the surfaces of immiscibility to intersect, leading to unmixing in the fluid phase. Dispersion of acoustic energy at critical conditions of the fluid may amplify seismic reflections that result from different fluid densities on lithological boundaries.Editorial responsibility: I. Parsons     

Dissolution kinetics of selected natural minerals relevant to potential CO2-injection sites − Part 1: A review

This publication provides a literature review on experimental studies of dissolution kinetics of mainly carbonates and feldspar group minerals, i.e. most common minerals at potential CO₂-injection and/or storage sites. Geochemical interaction processes between injected CO₂ and coexisting phases, namely reservoir and cap rock minerals and formation fluids close to the CO₂-injection site can be simulated by flow-through or mixed flow reactors, while processes far from the injection site and long-term processes after termination actual CO₂-injection can be mimicked by batch reactors. At sufficient small stirring rates or fluid flow rates as well as low solute concentrations flow-through reactors are also able to simulate processes far from the injection site. The experimental parameter temperature not only intensifies the dissolution process, the dominant dissolution mechanisms are also influenced by temperature. The dissolution mechanisms change from incongruent and surface controlled mechanisms at lower temperatures to congruent and transport controlled mechanisms at higher temperatures. The CO₂ partial pressure has only a second order influence on dissolution behavior compared to the influence of pH-value and ionic strength of the CO₂-bearing brine. Minerals exposed to CO₂-bearing brines at elevated temperatures and pressures are subject of alteration, leading to severe changes of reactive surfaces and potential precipitation of secondary minerals.Computational simulations of mineral reactions at potential CO₂ storage sites have therefore to include not only the time-resolved changes of dissolution behavior and hence kinetics of mineral dissolution, but also the influence of secondary minerals on the interaction of the minerals with CO₂-enriched brines.     

CO2 solubility in aqueous solutions containing Na+, Ca2+, Cl−, SO42− and HCO3-: The effects of electrostricted water and ion hydration thermodynamics

Dissolution of CO₂ into deep subsurface brines for carbon sequestration is regarded as one of the few viable means of reducing the amount of CO₂ entering the atmosphere. Ions in solution partially control the amount of CO₂ that dissolves, but the mechanisms of the ion's influence are not clearly understood and thus CO₂ solubility is difficult to predict. In this study, CO₂ solubility was experimentally determined in water, NaCl, CaCl₂, Na₂SO_4, and NaHCO₃ solutions and a mixed brine similar to the Bravo Dome natural CO₂ reservoir; ionic strengths ranged up to 3.4 molal, temperatures to 140 °C, and CO₂ pressures to 35.5 MPa. Increasing ionic strength decreased CO₂ solubility for all solutions when the salt type remained unchanged, but ionic strength was a poor predictor of CO₂ solubility in solutions with different salts. A new equation was developed to use ion hydration number to calculate the concentration of electrostricted water molecules in solution. Dissolved CO₂ was strongly correlated (R² = 0.96) to electrostricted water concentration. Strong correlations were also identified between CO₂ solubility and hydration enthalpy and hydration entropy. These linear correlation equations predicted CO₂ solubility within 1% of the Bravo Dome brine and within 10% of two mixed brines from literature (a 10 wt % NaCl + KCl + CaCl₂ brine and a natural Na⁺, Ca²⁺, Cl⁻ type brine with minor amounts of Mg²⁺, K⁺, Sr²⁺ and Br⁻).     

Percolation-theory and fuzzy rule-based probability estimation of fault leakage at geologic carbon sequestration sites

Leakage of CO₂ and displaced brine from geologic carbon sequestration (GCS) sites into potable groundwater or to the near-surface environment is a primary concern for safety and effectiveness of GCS. The focus of this study is on the estimation of the probability of CO₂ leakage along conduits such as faults and fractures. This probability is controlled by (1) the probability that the CO₂ plume encounters a conductive fault that could serve as a conduit for CO₂ to leak through the sealing formation, and (2) the probability that the conductive fault(s) intersected by the CO₂ plume are connected to other conductive faults in such a way that a connected flow path is formed to allow CO₂ to leak to environmental resources that may be impacted by leakage. This work is designed to fit into the certification framework for geological CO₂ storage, which represents vulnerable resources such as potable groundwater, health and safety, and the near-surface environment as discrete “compartments.” The method we propose for calculating the probability of the network of conduits intersecting the CO₂ plume and one or more compartments includes four steps: (1) assuming that a random network of conduits follows a power-law distribution, a critical conduit density is calculated based on percolation theory; for densities sufficiently smaller than this critical density, the leakage probability is zero; (2) for systems with a conduit density around or above the critical density, we perform a Monte Carlo simulation, generating realizations of conduit networks to determine the leakage probability of the CO₂ plume (P _leak) for different conduit length distributions, densities and CO₂ plume sizes; (3) from the results of Step 2, we construct fuzzy rules to relate P _leak to system characteristics such as system size, CO₂ plume size, and parameters describing conduit length distribution and uncertainty; (4) finally, we determine the CO₂ leakage probability for a given system using fuzzy rules. The method can be extended to apply to brine leakage risk by using the size of the pressure perturbation above some cut-off value as the effective plume size. The proposed method provides a quick way of estimating the probability of CO₂ or brine leaking into a compartment for evaluation of GCS leakage risk. In addition, the proposed method incorporates the uncertainty in the system parameters and provides the uncertainty range of the estimated probability.     

The partitioning of Fe and Mg between olivine and carbonate and the stability of carbonate under mantle conditions

We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K _d (X _Fe ^carb X _Mg ^ol /X _Fe ^ol X _Mg ^carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W _FeMg ^ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO₃ a W _FeMg ^carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K _d substantially enabling us to calculate W _CaMg ^carb -W _CaFe ^carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO₂(CMS)–CO₂ system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO₂. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.     

Ion association in concentrated NaCl brines from ambient to supercritical conditions: results from classical molecular dynamics simulations

Highly concentrated NaCl brines are important geothermal fluids; chloride complexation of metals in such brines increases the solubility of minerals and plays a fundamental role in the genesis of hydrothermal ore deposits. There is experimental evidence that the molecular nature of the NaCl–water system changes over the pressure–temperature range of the Earth's crust. A transition of concentrated NaCl–H₂O brines to a "hydrous molten salt" at high P and T has been argued to stabilize an aqueous fluid phase in the deep crust.     

Fluid evolution and thermal structure in the rapidly exhuming gneiss complex of Namche Barwa–Gyala Peri, eastern Himalayan syntaxis

High‐grade gneisses (amphibolite–granulite facies) of the Namche Barwa and Gyala Peri massifs, in the eastern Himalayan syntaxis, have been unroofed from metamorphic depths in the late Tertiary–Recent. Rapid exhumation (2–5 mm year^?1) has resulted in a pronounced shallow conductive thermal anomaly beneath the massifs and the intervening Tsangpo gorge. The position of the 300 °C isotherm has been estimated from fluid inclusions using CO₂–H₂O immiscibility phase equilibria to be between 2.5 and 6.2 km depth below surface. Hence, the near‐surface average thermal gradient exceeds 50 °C km^?1 beneath valleys, although the thermal gradient is relatively lower beneath the high mountains. The original metamorphic fluid in the gneisses was >90% CO₂. This fluid was displaced by incursion of brines from overlying marine sedimentary rocks that have since been largely removed by erosion. Brines can exceed 60 wt% dissolved salts, and include Ca, Na, K and Fe chlorides. These brines were remobilized during the earliest stages of uplift at >500 °C. During exhumation, incursion of abundant topography‐driven surface waters resulted in widespread fracture‐controlled hydrothermal activity and brine dilution down to the brittle–ductile transition. Boiling water was particularly common at shallow levels (<2.5 km) beneath the Yarlung Tsangpo valley, and numerous hot springs occur at the surface in this valley. Dry steam is not a major feature of the hydrothermal system in the eastern syntaxis (in contrast to the western syntaxis at Nanga Parbat), but some dry steam fluids may have developed locally.