Assessing dolomite surface reactivity at temperatures from 40 to 120 degrees C by hydrothermal atomic force microscopy

This study investigated the reactivity of the (1 0 4) dolomite surface in the system MgCO3–CaCO3–NaCl–H2O via a suite of aqueous solution–dolomite hydrothermal atomic force microscopy interaction experiments at temperatures from 40 to 120 °C, pH ranging from 4 to 8, pressures up to 5 bars, and over a wide range of aqueous fluid saturation state. Dolomite dissolution was observed in the presence of undersaturated aqueous fluids. Dissolution produced crystallographically well defined etch pits, consistent with the stoichiometric release of ordered lattice cations. In low to moderately saturated fluids, dolomite growth began by the growth of one or two layers of carbonate (layer height <3 Å) which morphologically reproduced the initial surface features, resembling the template effect as previously described by Astilleros et al. (2003, 2006) and Freij et al. (2004). Further growth was strongly inhibited and did not show any systematic crystallographically orientated growth morphologies. At aqueous fluid saturation states exceeding 500, nucleation and growth was observed on the dolomite surfaces at moderate rates, but these did not exhibit the characteristic dolomite crystallographic orientation after the growth of several layers. Taken together these observations suggest that the direct precipitation of dolomite from aqueous solution is disfavored at temperatures to at least 120 °C due to the poisoning of the dolomite surface for further growth by the precipitation of one to four Ca–Mg carbonate layers on these surfaces

The impact of damming on riverine fluxes to the ocean: A case study from Eastern Iceland

Anthropogenic water management has extensively altered the world's river systems through impoundments and channel diversions to meet the human's need for water, energy and transportation. To illuminate the effect of such activities on the environment, this study describes the impact of the installation of the Kárahnjúkar Dam in Eastern Iceland on the transport of riverine dissolved- and particulate material to the ocean by the Jökulsá á Dal and the Lagarfljót rivers. This dam, completed in 2007, collects water into the 2.2 km3 Hálslón reservoir and diverts water from the glacial Jökulsá á Dal river into the partially glaciated Lagarfljót lagoon via a headrace tunnel. The impact of the damming was evaluated by sampling water from both the Jökulsá á Dal and the Lagarfljót rivers over a 15 year period spanning from 1998 to 2013. The annual flux of most dissolved elements increased substantially due to the damming. The fluxes of dissolved Zn, Al, Co, Ti and Fe increased most by damming; these fluxes increased by 46–391%. These differences can be attributed to changed saturation states of common secondary minerals in the Jökulsá á Dal due to reduced discharge, increased residence time and dissolution of suspended material, and, to a lesser degree, reduced photosynthesis due to less transparency in the Lagarfljót lagoon. The removal of particulate material and thus decreasing adsorption potential in the Jökulsá á Dal is the likely reason for the Fe flux increase. In contrast, approximately 85% of the original riverine transported mass of particulate material is trapped by the dam; that which passes tends to be relatively fine grained, increasing the average specific surface area of that which continues to flow towards the ocean. Consequently, the particulate geometric surface area flux is decreased by only 50% due to the damming. The blooming of silica diatoms during the spring consumes dissolved silica from the coastal waters until it becomes depleted; making the riverine spring dissolved silica flux an important source of this nutrient. Despite extensive riverine flux changes due to the Kárahnjúkar dam construction, the total spring dissolved silica flux increased, and thus so too the potential for a silica diatom spring bloom in the coastal waters. This is likely because the spring flux is dominated by snow melting downstream of the dam

A brief history of CarbFix: Challenges and victories of the project’s pilot phase

The pilot phase of the CarbFix project ran for over a decade and consisted of the training of students, creating the scientific basis for the fixation of carbon dioxide in the subsurface through the in-situ carbonation of basalts, and the demonstration of this technology by fixing approximately 200 tons of injected CO2 as carbonate minerals during 2012 and 2013. Over the course of this effort numerous parts of this project have been reported in scientific articles, but a number of challenges including that of separating CO2 gas from a H2S-rich effluent gas, the clogging of the original CarbFix injection well and the damage to the project’s gas pipe by a third party that eventually shut down the project’s pilot phase, have yet to be detailed in the scientific literature. This brief manuscript reviews the CarbFix timeline over the past 12 years, describing in detail some of these challenges. CarbFix demonstrates how interdisciplinary collaboration between the green energy industry, academia, engineers and technicians allows for a fast and efficient development of the idea of battling climate change by permanently petrifying otherwise emitted CO2 in subsurface basalt formations into an economic industrial scale process useful to the global economy

Reaction path modelling of in-situ mineralisation of CO2 at the CarbFix site at Hellisheidi, SW-Iceland

Results from injection of 175 tonnes of CO 2 into the basaltic subsurface rocks at the CarbFix site in SW-Iceland in 2012 show almost complete mineralisation of the injected carbon in less than two years (Matter et al., 2016; Snæbjörnsdóttir et al., 2017). Reaction path modelling was performed to illuminate the rate and extent of CO 2 -water-rock reactions during and after the injection. The modelling calculations were constrained by the compositions of fluids sampled prior to, during, and after the injection, as reported by Alfredsson et al. (2013) and Snæbjörnsdóttir et al. (2017). The pH of the injected fluid, prior to CO 2 dissolution was ∼9.5, whereas the pH of the background waters in the first monitoring well prior to the injections was ∼9.4. The pH of the sampled fluids used in the modelling ranged from ∼3.7 at the injection well to as high as 8.2 in the first monitoring well. Modelling results suggest that CO 2 -rich water-basalt interaction is dominated by crystalline basalt dissolution along a faster, high permeability flow path, but by basaltic glass dissolution along a slower, pervasive flow path through which the bulk of the injected fluid flows. Dissolution of pre-existing calcite at the onset of the injection does not have a net effect on the carbonation, but does contribute to a rapid early pH rise during the injection, and influences which carbonate minerals precipitate. At low pH, Mg, and Fe are preferentially released from crystalline basalts due to the higher dissolution rates of olivine, and to lesser extent pyroxene, compared to plagioclase and glass (Gudbrandsson et al., 2011). This favours the formation of siderite and Fe-Mg carbonates over calcite during early mineralisation. The model suggests the formation of the following carbonate mineral sequences: siderite at pH 5, and calcite at higher pH. Other minerals forming with the carbonates are Al- and Fe-hydroxides and chalcedony, and zeolites and smectites at elevated pH. The most efficient carbonate formation is when the pH is high enough for formation of carbonates, but not so high that zeolites and smectites start to form, which compete with carbonates over both cations and pore space. The results of reaction path modelling at the CarbFix site in SW-Iceland indicate that this “sweet spot” for mineralisation of CO 2 is at pH from ∼5.2 to 6.5 in basalts at low temperature (20–50 °C)

Effect of solution saturation state and temperature on diopside dissolution

Steady-state dissolution rates of diopside are measured as a function of solution saturation state using a titanium flow-through reactor at pH 7.5 and temperature ranging from 125 to 175°C. Diopside dissolved stoichiometrically under all experimental conditions and rates were not dependent on sample history. At each temperature, rates continuously decreased by two orders of magnitude as equilibrium was approached and did not exhibit a dissolution plateau of constant rates at high degrees of undersaturation. The variation of diopside dissolution rates with solution saturation can be described equally well with a ion exchange model based on transition state theory or pit nucleation model based on crystal growth/dissolution theory from 125 to 175°C. At 175°C, both models over predict dissolution rates by two orders of magnitude indicating that a secondary phase precipitated in the experiments. The ion exchange model assumes the formation of a Si-rich, Mg-deficient precursor complex. Lack of dependence of rates on steady-state aqueous calcium concentration supports the formation of such a complex, which is formed by exchange of protons for magnesium ions at the surface. Fit to the experimental data yields [Formula: see text] where the Mg-H exchange coefficient, n = 1.39, the apparent activation energy, E(a )= 332 kJ mol(-1), and the apparent rate constant, k = 10(41.2 )mol diopside cm(-2 )s(-1). Fits to the data with the pit nucleation model suggest that diopside dissolution proceeds through retreat of steps developed by nucleation of pits created homogeneously at the mineral surface or at defect sites, where homogeneous nucleation occurs at lower degrees of saturation than defect-assisted nucleation. Rate expressions for each mechanism (i) were fit to [Formula: see text] where the step edge energy (α) for homogeneously nucleated pits were higher (275 to 65 mJ m(-2)) than the pits nucleated at defects (39 to 65 mJ m(-2)) and the activation energy associated with the temperature dependence of site density and the kinetic coefficient for homogeneously nucleated pits (E(b-homogeneous )= 2.59 × 10(-16 )mJ K(-1)) were lower than the pits nucleated at defects (E(b-defect assisted )= 8.44 × 10(-16 )mJ K(-1))

Ion association in concentrated NaCI 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–H(2)O brines to a "hydrous molten salt" at high P and T has been argued to stabilize an aqueous fluid phase in the deep crust. In this work, we have done molecular dynamic simulations using classical potentials to determine the nature of concentrated (0.5–16 m) NaCl–water mixtures under ambient (25°C, 1 bar), hydrothermal (325°C, 1 kbar) and deep crustal (625°C, 15 kbar) conditions. We used the well-established SPCE model for water together with the Smith and Dang Lennard-Jones potentials for the ions (J. Chem. Phys., 1994, 100, 3757). With increasing temperature at 1 kbar, the dielectric constant of water decreases to give extensive ion-association and the formation of polyatomic (Na(n)Cl(m))(n-m )clusters in addition to simple NaCl ion pairs. Large polyatomic (Na(n)Cl(m))(n-m )clusters resemble what would be expected in a hydrous NaCl melt in which water and NaCl were completely miscible. Although ion association decreases with pressure, temperatures of 625°C are not enough to overcome pressures of 15 kbar; consequently, there is still enhanced Na–Cl association in brines under deep crustal conditions

Evaluation and refinement of thermodynamic databases for mineral carbonation

Thermodynamic models are often used to quantify fluid-rock interactions. The validity of such models critically depends on the accuracy of the thermodynamic database used. This study evaluated the quality of existing PHREEQC databases (phreeqc.dat, llnl.dat, and core10.dat) through the analysis of mineral saturation states for various carbonates, sulfur-containing minerals, silicates, and hydroxides. The comparison between data from available equilibrated dissolution-precipitation experiments and predicted saturation states reveals: i) systematic deviations when using phreeqc.dat at temperatures higher than ~ 90 °C; ii) a lack of direct solubility measurements of numerous sulfide and silicate minerals; iii) systematic solubility underestimates for kaolinite and brucite. To address these issues the carbfix.dat database was created based on the core10.dat database, revising several mineral solubilities and aqueous species stabilities to improve our ability to model fluid-rock interactions during basalt-hosted mineral carbonation efforts

Convective mixing fingers and chemistry interaction in carbon storage

Dissolution of carbon-dioxide into formation fluids during carbon capture and storage (CCS) can generate an instability with a denser CO2-rich fluid located above the less dense native aquifer fluid. This instability promotes convective mixing, enhancing CO2 dissolution and favouring the storage safety. Convective mixing has been extensively analysed in the context of CCS over the last decade, however the interaction between convective mixing and geochemistry has been insufficiently addressed. This relation is explored using a fully coupled model taking into account the porosity and permeability variations due to dissolution-precipitation reactions in a realistic geochemical system based on the Hontomín (Spain) potential CCS site project. This system, located in a calcite, dolomite, and gypsum bearing host rock, has been analysed for a variety of Rayleigh and Damköhler values. Results show that chemical reactions tend to enhance CO2 dissolution. The model illustrates the first stages of porosity channel development, demonstrating the significance of fluid mixing in the development of porosity patterns. The influence of non-carbon species on CO2 dissolution shown in this study demonstrates the needs for realistic chemical and kinetic models to ensure the precision of physical models to accurately represent the carbon-dioxide injection process

Experimental determination of the solubility product of dolomite at 50–253 °C

The ‘dolomite problem’, the scarcity of present-day dolomite formation near the Earth’s surface, has attracted much attention over the past century. Solving this problem requires having reliable data on the stability and kinetics of formation of this mineral. Toward this goal, the solubility of natural dolomite (CaMg(CO3)2) has been measured from 50 to 253 °C in 0.1 mol/kg NaCl solutions using a hydrogen electrode concentration cell (HECC). The obtained apparent solubility products (Kapp-sp-dol), for the reaction: CaMg(CO3)2 = Ca2+ + Mg2+ + 2CO32−, were extrapolated to infinite dilution to generate the solubility product constants for this reaction (Ksp°-dol). The derived equilibrium constants were fit and can be accurately described by log10 Ksp°-dol = a + b/T (K) + cT (K) where a = 17.502, b = −4220.119 and c = −0.0689. This equation and its first and second derivatives with respect to T were used together with corresponding aqueous species properties to calculate the revised standard state thermodynamic properties of dolomite at 25 °C and 1 bar, yielding a Gibbs energy of formation (ΔfG298.15∘) equal to −2160.9 ± 2 kJ/mol, (log10 Ksp°-dol = −17.19 ± 0.3); an enthalpy of formation (ΔfH298.15∘) of −2323.1 ± 2 kJ/mol, an entropy (S298.15∘) of 156.9 ± 2 J/mol/K and heat capacity (Cp298.15∘) of 154.2 ± 2 J/mol/K (uncertainties are 3σ). The dolomite solubility product derived in this study is nearly identical to that computed using SUPCRT92 (Johnson et al., 1992) at 200 °C, but about one order of magnitude higher at 50 and 25 °C, suggesting that dolomite may be somewhat less stable than previously assumed at ambient temperatures