Magnesium Carbonate Minerals Research Articles

The Formation of Calcium–Magnesium Carbonate Minerals Induced by Curvibacter sp. HJ-1 under Different Mg/Ca Molar Ratios

The Formation of Calcium–Magnesium Carbonate Minerals Induced by Curvibacter sp. HJ-1 under Different Mg/Ca Molar Ratios

Solidification of sodium sulfate saline loess by biomineralization of reactive magnesium oxide binder

This study aims to solidify sodium sulfate saline loess by biomineralization of reactive magnesium oxide (MgO) binder. The impact of Na2SO4 concentration on the viability and urease activity of S. pasteurii, the mechanism and products of biomineralization of MgO, and the effectiveness of the biomineralization-MgO binder in solidifying saline loess with varying salt content (1%, 3%, and 5%) were investigated. Results showed that low and moderate concentrations of Na2SO4 favored bacterial proliferation. However, the presence of Na2SO4 inhibited bacterial urease activity, and the inhibition was more significant at higher Na2SO4 concentrations. In addition, low and moderate concentrations of Na2SO4 decreased the specific urease activity, whereas high concentrations of Na2SO4 significantly increased specific urease activity. S. pasteurii was able to use carbonate ions formed by urea hydrolysis for the mineralization of MgO and to form magnesium carbonate minerals dominated by rosette-like dypingite and hydromagnesite crystals. The primary mechanism involves microbial cells and extracellular polymeric substances leading to partial dehydration of Mg2+ ions from the Mg2+-H2O complex and allowing for further association with carbonate anions to from Mg-bearing carbonates. Unconfined compressive strength tests conducted on the saline loess samples after 7 days of curing revealed a significant influence of urea concentration on the strength of the solidified soil. The optimal urea concentration to obtain a better 7-day UCS ranged from 4 mol/L to 5 mol/L. Furthermore, solidified soil with 5% salinity yielded the highest 7-day UCS and soil with 3% salinity exhibited the lowest 7-day UCS at the same urea concentration. XRD and SEM analysis of the solidified soil samples indicated that the formation of magnesium carbonate minerals in the soil matrix by the biomineralization-MgO binder was responsible for the UCS enhancement. The remarkable 7-day UCS of saline loess solidified with biomineralization-MgO binder demonstrates the effectiveness of this material in curing saline loess.

Rare Hydrated Magnesium Carbonate Minerals Nesquehonite and Dypingite of the Obnazhennaya Kimberlite Pipe, in the Yakutian Kimberlite Province

The result of a complex mineralogical study of the first discovery of the rare hydrated magnesium carbonate minerals of Nesquehonite and Dypingite in the Obnazhennaya kimberlite pipe (of the Yakutian kimberlite province) is presented. The methods of X-ray phase analysis, electronic microscopy, and Raman spectroscopy have established that the main minerals of the samples found in the form of white crust on a small area of rock outcrop of kimberlite breccia are hydrated carbonates: Nesquehonite is MgCO3•3H2O, Dypingite is Mg5(CO3)4(OH)2•5H2O. The formation of Dypingite over Nesquehonite was shown using Raman imaging for the first time. Nesquehonite is represented as aggregates consisting of chaotically oriented prismatic crystals or kidney-shaped formations. Dypingite in the examined samples appears less frequently as rose-shaped aggregates formed from lamellar crystals. It is assumed that the formation of rare carbonates of the Obnazhennaya kimberlite pipe is mainly the result of the weathering of silicates, formation of mineralized solutions, and their subsequent crystallization, including the capture of CO2 from the air.

Mass-independent fractionation of oxygen isotopes during thermal decomposition of divalent metal carbonates: Crystallographic influence, potential mechanism and cosmochemical significance

Few physical or chemical processes defy well-established laws of mass-dependent isotopic fractionation. A surprising example, discovered two decades ago, is that thermal decomposition of calcium and magnesium carbonate minerals (conducted in vacuo, to minimise back-reaction and isotopic exchange) causes the oxygen triple-isotope compositions of the resulting solid oxide and CO2 to fit on parallel mass-dependent fractionation lines in ln(1 + δ17O) versus ln(1 + δ18O) space, with anomalous depletion of 17O in the solid and equivalent enrichment of 17O in the CO2. By investigating the thermal decomposition of other natural divalent metal carbonates and one synthetic example, under similar conditions, we find that the unusual isotope effect occurs in all cases and that the magnitude of the anomaly (Δ′17O) seems to depend on the room temperature crystallographic structure of the carbonate. A lower cation coordination number (as associated with smaller cation radius) correlates with a Δ′17O value closer to zero. Local symmetry considerations may therefore be influential. Relative to a reference fractionation line of slope 0.524 and passing through VSMOW, solid oxides produced by thermal decomposition of orthorhombic carbonates were characterised by Δ′17O = −0.367 ± 0.004‰ (standard error). The comparable figure from rhombohedral examples was −0.317 ± 0.010‰, whereas from the sole monoclinic (synthesised) specimen it was −0.219 ± 0.011‰. The numerical values are, to some extent, dependent on details of the experimental procedure. We discuss potential origins of the isotopic anomaly, including the possibility of hyperfine coupling between 17O nuclei and unpaired electrons of transient radicals (the ‘magnetic isotope effect’). A new mechanism based on the latter process is proposed. The associated transition state is compatible with that suggested by recent quantum chemical and kinetic studies of the thermal decompositions of calcite and magnesite. An earlier suggestion based on the magnetic isotope effect is shown to be incompatible with the generation of a 17O anomaly, regardless of the identity of the carbonate. We cannot exclude the possibility that a Fermi resonance between states leading to dissociation may additionally affect the magnitude of Δ′17O in some cases. Our findings have cosmochemical implications, with thermal processing of carbonates providing a potential mechanism for the mass-independent fractionation of oxygen isotopes in protoplanetary systems.

Rare hydrated magnesium carbonate minerals of the kimberlite pipe Obnazhennaya, The Yakutian Kimberlite Province

The first discovery of hydrated magnesium carbonates, dypingite and nesquehonite, in the kimberlite pipe Obnazhennaya of the Kuoyka field, the Yakutian kimberlite province is described. The pipe is composed of kimberlite breccia with abundant diverse xenoliths of practically intact mantle rocks. Olivine in phenocrysts and mantle rock is generally intact. The main body of the rock is carbonate-serpentine. Nesquehonite and dypingite are rare minerals and have first been observed in relation to kimberlites. The minerals were found in the bedrock outcrop of the Obnazhennaya pipe as white crusts up to 5 mm thick scattered over an area of a few tens of square meters. To identify and study the crusts we used the following methods: powder X-ray diffraction, electron microscopy, and Raman scattering spectroscopy. A comprehensive study suggests that the main minerals of these epigenetic formations are hydrated carbonates: nesquehonite MgCO3□3H2O and dypingite Mg5(CO3)4(OH)2□5H2O. Also, Raman scattering spectroscopy revealed a small proportion of hydromagnesite Mg5(CO3)4(OH)2□4H2O. Hydrated magnesium carbonate minerals we found make a significant contribution to the collection of kimberlites. They are epigenetic in nature, with their origin being related to weathering of silicates, in particular serpentine. Mechanisms of carbonate formation appear to be close to that suggested by Wilson et. al., 2009, with CO2 being trapped from the atmosphere to form nesquehonite. In the case of the Obnazhennaya pipe, mineral solutions form when rainwater filters through the talus at the top of the outcrop. They are enriched in Mg from minerals and trap CO2 from the atmosphere. After filtering, solutions reach the vertical wall of kimberlite breccia where modern precipitation of nesquehonite upon evaporation occurs. Further, dypingite and hydromagnesite form via decomposition of nesquehonite. A lip extending over the rock wall significantly contributes to the development and stability of nesquehonite and dypingite aggregates. Crusts of nesquehonite and dypingite are not found on rock outcrops without lips at the top. Thus, despite the fact that intrusion of the kimberlite pipe occurred during the Jurassic (Zaitsev, Smelov, 2010), formation of nesquehonite and dypingite in association with kimberlite rocks continues in the modern time due to favorable environmental factors, first of all, a unique natural outcrop of kimberlite.

Application of PM IRRAS to study structural changes of the magnesium surface in corrosive environments

Light weight metals such as magnesium and aluminum have excellent engineering properties which makes them attractive for industrial applications. Poor corrosion resistance is the major drawback for their wide applications. Corrosion of metal surfaces is a common but complex phenomenon, which depends on the sample environment. Despite intensive studies the molecular aspects of magnesium corrosion are not fully understood yet.Infrared spectroscopy is an excellent analytical technique to study the chemical composition and structure of molecules. Reflection based infrared spectroscopy techniques are applicable to investigate the structure of molecules adsorbed on surfaces. In this paper we demonstrate that magnesium with its passive layer is suitable for infrared reflection absorption spectroscopy experiments. On the pure magnesium surface the IR light is strongly reflected and the highest enhancement of the normal component of the p-polarized light (probing the species present on the surface) is obtained at grazing angles of incidence. Growth of the passive layer leads to a gradual shift of the optimal angle of incidence to lower values (60° vs. surface normal). Polarization modulation infrared reflection absorption spectroscopy is used to study changes in the composition and structure occurring during magnesium corrosion in air and in aqueous solutions. In air and in aqueous NaCl solution Mg(OH)2 and magnesium carbonate minerals coordinating water and hydroxide ions are formed on the surface. IR spectra provide clear evidence that the coordination of the Mg2+ to carbonate ions changes in time from mono- to bi- and polydentate. In the presence of orthophosphate ions in the electrolyte solution, the Mg(OH)2 layer disappears from the surface while magnesium phosphate salts crystalize on the metal surface.

Mobility of hydrous species in amorphous calcium/magnesium carbonates.

Amorphous calcium carbonate (ACC) is commonly found in many biological materials. As ACC readily crystallizes into calcite, stabilizers, such as anions, cations or macromolecules, often occur to avoid or delay unwanted crystallization. In biogenic ACC, magnesium is commonly present as one of the stabilizing agents. It is generally thought that the presence of mobile water in ACC is responsible for its limited stability and that the strong interaction of Mg2+ with water stabilizes the amorphous structure by retarding dehydration of ACC. To test this hypothesis, we studied the mobility of hydrous species in the model materials ACC, amorphous magnesium carbonate (AMC) and amorphous calcium/magnesium carbonate (ACMC), using quasi elastic neutron scattering (QENS) which is highly sensitive to the dynamics of H atoms. We discovered that hydrous species in the considered amorphous materials consist of water and hydroxide ions, as magnesium ions are incorporated in a ratio of 1 to about 0.6 with OH-. Surprisingly, we found that there is no evidence of translational diffusion of water and hydroxides when calcium is present in the samples, showing that hydrous species are highly static. However, we did observe diffusion of water in AMC with similar dynamics to that found for water in clays. Our results suggest that Mg2+-water interactions alone are not the only reason for the high stability of AMC and ACMC. The stabilizing effect of Mg ions, in addition to Mg-water binding, is likely to be caused by binding to hydroxide in amorphous calcium carbonates. In fact, the incorporation of hydroxides into the amorphous phase results in a mineral composition that is incompatible with any of the known Ca/Mg-carbonate crystal phases, requiring large scale phase separation to reach the composition of even the basic magnesium carbonate minerals artinite and hydromagnesite.

Clumped-isotope thermometry of magnesium carbonates in ultramafic rocks

Magnesium carbonate minerals produced by reaction of H2O–CO2 with ultramafic rocks occur in a wide range of paragenetic and tectonic settings and can thus provide insights into a variety of geologic processes, including (1) deposition of ore-grade, massive-vein cryptocrystalline magnesite; (2) formation of hydrous magnesium carbonates in weathering environments; and (3) metamorphic carbonate alteration of ultramafic rocks. However, the application of traditional geochemical and isotopic methods to infer temperatures of mineralization, the nature of mineralizing fluids, and the mechanisms controlling the transformation of dissolved CO2 into magnesium carbonates in these settings is difficult because the fluids are usually not preserved. Clumped-isotope compositions of magnesium carbonates provide a means to determine primary mineralization or (re)equilibration temperature, which permits the reconstruction of geologic processes that govern magnesium carbonate formation. We first provide an evaluation of the acid fractionation correction for magnesium carbonates using synthetic magnesite and hydromagnesite, along with natural metamorphic magnesite and low-temperature hydromagnesite precipitated within a mine adit. We show that the acid fractionation correction for magnesium carbonates is virtually indistinguishable from other carbonate acid fractionation corrections given current mass spectrometer resolution and error. In addition, we employ carbonate clumped-isotope thermometry on natural magnesium carbonates from various geologic environments and tectonic settings. Cryptocrystalline magnesite vein deposits from California (Red Mountain magnesite mine), Austria (Kraubath locality), Turkey (Tutluca mine, Eskişehir district) and Iran (Derakht-Senjed deposit) exhibit broadly uniform Δ47 compositions that yield apparent clumped-isotope temperatures that average 23.7±5.0°C. Based on oxygen isotope thermometry, these clumped-isotope temperatures suggest mineralization at shallow crustal depths in the presence of meteoric water. Hydrous magnesium carbonates from a 400-km latitudinal transect along the serpentinized-peridotite bodies of the California Coast Ranges record clumped-isotope temperatures between 14.2 and 22.7±2.8°C, in agreement with historical maximum temperatures during the rainy season for California. Talc–carbonate alteration of ultramafic rocks in Greenland (Isua Supracrustal Belt) and Vermont (Ludlow) yields clumped-isotope alteration temperatures of magnesite and dolomite between 326 and 490°C, broadly consistent with paragenesis and thermodynamic analysis for CO2 metasomatism of ultramafic rocks. These metamorphic carbonates extend the applicability of clumped-isotope thermometry to high-temperature magnesium carbonate systems and indicate equilibrium blocking temperatures for magnesite of ∼490°C. Our study demonstrates the applicability of the clumped isotope approach to provide information on the formation of magnesium carbonates as ore resources, surface records of climate, and metamorphic assemblages.

The continuous re-equilibration of carbon isotope compositions of hydrous Mg carbonates in the presence of cyanobacteria

The hydrous magnesium carbonate minerals dypingite (Mg5(CO3)4(OH)2·5H2O) and nesquehonite (MgCO3·3H2O) were precipitated in the presence and absence of Gloeocapsa sp. and Synechococcus sp. cyanobacteria in batch reactors. The Δ13Cmineral–DIC is similar in both biotic and abiotic systems. Stable carbon isotope analyses of the precipitated minerals and co-existing fluids indicated that the δ13C values of the precipitated carbonates co-vary over time with the δ13CDIC of the fluid phase, even after the precipitation of the carbonate is complete. This observation indicates the continuous isotopic exchange between the carbonates and the fluid, a process that efficiently resets the original δ13C values of the solids. Therefore although cyanobacterial-induced Mg carbonates are 10±5‰ enriched in 13C compared to inorganic carbonates, the δ13C values of natural hydrous Mg carbonates may reflect post precipitation processes and may not be reliable for paleo-environmental reconstructions.

Correction to Quantitative Identification of Metastable Magnesium Carbonate Minerals by Solid-State 13C NMR Spectroscopy

Correction to Quantitative Identification of Metastable Magnesium Carbonate Minerals by Solid-State ¹³C NMR Spectroscopy

Quantitative identification of metastable magnesium carbonate minerals by solid-state 13C NMR spectroscopy.

In the conversion of CO2 to mineral carbonates for the permanent geosequestration of CO2, there are multiple magnesium carbonate phases that are potential reaction products. Solid-state (13)C NMR is demonstrated as an effective tool for distinguishing magnesium carbonate phases and quantitatively characterizing magnesium carbonate mixtures. Several of these mineral phases include magnesite, hydromagnesite, dypingite, and nesquehonite, which differ in composition by the number of waters of hydration or the number of crystallographic hydroxyl groups. These carbonates often form in mixtures with nearly overlapping (13)C NMR resonances which makes their identification and analysis difficult. In this study, these phases have been investigated with solid-state (13)C NMR spectroscopy, including both static and magic-angle spinning (MAS) experiments. Static spectra yield chemical shift anisotropy (CSA) lineshapes that are indicative of the site-symmetry variations of the carbon environments. MAS spectra yield isotropic chemical shifts for each crystallographically inequivalent carbon and spin-lattice relaxation times, T1, yield characteristic information that assist in species discrimination. These detailed parameters, and the combination of static and MAS analyses, can aid investigations of mixed carbonates by (13)C NMR.

Lime mud from cellulose industry as raw material in cement mortars

This study reports the use of lime mud (LM) in cement-based-mortars. Lime mud is a waste generated in the production of cellulose by the kraft mill process. It is mainly composed of CaCO3, a small amount of magnesium carbonate and other trace minerals. Mortars were prepared by adding different amounts of LM (10, 20 and 30% by weight of cement) in dry weight. The mortar compositions were evaluated through rheology and flow table measurements, assuring that all the samples exhibited adequate conditions for testing in both equipments. The hardened state properties were also evaluated through mechanical strengths at 7, 28 and 90 days of curing. Following a waste management solution perspective, this work intend to provide a general evaluation of LM application in cement based mortars, looking at both fresh and hardened properties in order to guarantee that the final application requirements are not hindered.

A greenhouse-scale photosynthetic microbial bioreactor for carbon sequestration in magnesium carbonate minerals.

A cyanobacteria dominated consortium collected from an alkaline wetland located near Atlin, British Columbia, Canada accelerated the precipitation of platy hydromagnesite [Mg5(CO3)4(OH)2·4H2O] in a linear flow-through experimental model wetland. The concentration of magnesium decreased rapidly within 2 m of the inflow point of the 10-m-long (∼1.5 m(2)) bioreactor. The change in water chemistry was monitored over two months along the length of the channel. Carbonate mineralization was associated with extra-cellular polymeric substances in the nutrient-rich upstream portion of the bioreactor, while the lower part of the system, which lacked essential nutrients, did not exhibit any hydromagnesite precipitation. A mass balance calculation using the water chemistry data produced a carbon sequestration rate of 33.34 t of C/ha per year. Amendment of the nutrient deficiency would intuitively allow for increased carbonation activity. Optimization of this process will have application as a sustainable mining practice by mediating magnesium carbonate precipitation in ultramafic mine tailings storage facilities.

Process optimization for mineral carbonation in aqueous phase

Carbon dioxide sequestration by a pH-swing carbonation process was considered in this work. A multi-step aqueous process is described for the fractional precipitation of magnesium carbonate and other minerals in an aqueous system at room temperature and atmospheric pressure. With the aim to achieve higher purity and deliver more valuable mineral products, the process was split into four steps. The first step consists of Mg leaching from the magnesium silicate in a stirred vessel using 1M HCl at 80°C, followed by a three step precipitation in reactors in sequence to remove Fe(OH)3, then Fe(OH)2 and other divalent ions, and finally MgCO3 nucleation and growth. Hydrated magnesium carbonate [MgCO3∙3H2O, nesquehonite] crystals were confirmed using X-ray diffraction (XRD) as final products. The optimal pH of precipitation reactors based on the maximum solid purity and production was determined by carrying out detailed mass balance. The maximum productivity and highest purity for nesquehonite were found to be dependent on pH values for the two last steps. The results also demonstrated that the process is optimized at pH9 and 10 for the second and third step of precipitation, respectively. The highest carbonation efficiency expressed as the conversion of Mg ions to magnesium carbonate reached 82.5 wt %. The maximum magnesium content in the final product was 99.21 wt % of MgO when the second precipitation reactor pH was equal to 9. This experimental study demonstrates that carbon dioxide sequestration requires at least 3.74 times the weight of ore to provide the Mg for mineral production. This confirms the possibility to use this process route for CO2 mitigation.

Ab Initio Thermodynamic Model for Magnesium Carbonates and Hydrates

An ab initio thermodynamic framework for predicting properties of hydrated magnesium carbonate minerals has been developed using density-functional theory linked to macroscopic thermodynamics through the experimental chemical potentials for MgO, water, and CO2. Including semiempirical dispersion via the Grimme method and small corrections to the generalized gradient approximation of Perdew, Burke, and Ernzerhof for the heat of formation yields a model with quantitative agreement for the benchmark minerals brucite, magnesite, nesquehonite, and hydromagnesite. The model shows how small differences in experimental conditions determine whether nesquehonite, hydromagnesite, or magnesite is the result of laboratory synthesis from carbonation of brucite, and what transformations are expected to occur on geological time scales. Because of the reliance on parameter-free first-principles methods, the model is reliably extensible to experimental conditions not readily accessible to experiment and to any mineral composition for which the structure is known or can be hypothesized, including structures containing defects, substitutions, or transitional structures during solid state transformations induced by temperature changes or processes such as water, CO2, or O2 diffusion. Demonstrated applications of the ab initio thermodynamic framework include an independent means to evaluate differences in thermodynamic data for lansfordite, predicting the properties of Mg analogues of Ca-based hydrated carbonates monohydrocalcite and ikaite, which have not been observed in nature, and an estimation of the thermodynamics of barringtonite from the stoichiometry and a single experimental observation.

Selection of acid for weak acid processing of wollastonite for mineralisation of CO2

Typically, mineral carbonation comprises aqueous phase reactions involving the dissolution of naturally occurring magnesium and calcium silicate rocks, such as olivine, serpentinites and wollastonite, followed by the precipitation of magnesium and calcium carbonate minerals. In this report, we evaluated the effect of formic, acetic and DL-lactic acids on the calcium-leaching process from wollastonite between 22°C and 80°C and at atmospheric pressure. OLI Analyzer Studio 3.0 predicted equilibrium conversions of calcium and its speciation in the aqueous phase. Additionally, we measured dissolution rates, for a constant pH system, as a function of temperature for the three organic acids. All experiments involved the reaction of 17±1μm (volume mean diameter) ground rock samples with the acids in a stirred batch reactor equipped with in situ pH measurements. Inductively coupled plasma-optical emission spectrometry (ICP-OES) analysed the concentration of calcium ions in the leaching medium while scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) examined the morphology and surface chemical composition of the residual solid phase from dissolution experiments. We estimated the maximum dissolution rates of wollastonite in the limit of low but achievable pH and in the absence of diffusion limitation in pores and cracks of the SiO2 skin. At 80°C, these rates correspond to 26(±7)×10−5, 14(±3)×10−5 and 17(±4)×10−5molm−2s−1 for formic, acetic and DL-lactic acids, respectively. The apparent activation energies amount to 11±3, 47±13 and 52±14kJmol−1 for dissolution in formic, acetic and DL-lactic acids, respectively. These values indicate the initial diffusion limitation in the film around wollastonite particles for formic acid, and kinetic limitation for acetic and DL-lactic acids. The rates of dissolution rapidly decline for acetic and DL-lactic acids, but remain high for formic acid. The findings are altogether indicative of high performance of formic acid for extraction of Ca2+ for storing CO2. Further experiments are needed to assess the recycling of formic acid to determine its overall suitability as a Ca2+ carrier for the weak acid process.

Testing the cation-hydration effect on the crystallization of Ca-Mg-CO3 systems.

Dolomite and magnesite are simple anhydrous calcium and/or magnesium carbonate minerals occurring mostly at Earth surfaces. However, laboratory synthesis of neither species at ambient temperature and pressure conditions has been proven practically possible, and the lack of success was assumed to be related to the strong solvation shells of magnesium ions in aqueous media. Here, we report the synthesis of MgCO3 and MgxCa(1-x)CO3 (0 < x < 1) solid phases at ambient conditions in the absence of water. Experiments were carried out in dry organic solvent, and the results showed that, although anhydrous phases were readily precipitated in the water-free environment, the precipitates' crystallinity was highly dependent on the Mg molar percentage content in the solution. In specific, magnesian calcite dominated in low [Mg(2+)]/[Ca(2+)] solutions but gave way to exclusive formation of amorphous MgxCa(1-x)CO3 and MgCO3 in high-[Mg(2+)]/[Ca(2+)] and pure-Mg solutions. At conditions of [Mg(2+)]/[Ca(2+)] = 1, both nanocrystals of Ca-rich protodolomite and amorphous phase of Mg-rich MgxCa(1-x)CO3 were formed. These findings exposed a previously unrecognized intrinsic barrier for Mg(2+) and CO3(2-) to develop long-range orders at ambient conditions and suggested that the long-held belief of cation-hydration inhibition on dolomite and magnesite mineralization needed to be reevaluated. Our study provides significant insight into the long-standing "dolomite problem" in geochemistry and mineralogy and may promote a better understanding of the fundamental chemistry in biomineralization and mineral-carbonation processes.

Coupling Mineral Carbonation and Ocean Liming

The process by which basic/ultrabasic silicate minerals (e.g., olivine) are reacted with CO2 to produce solid carbonate minerals (“mineral carbonation”) has been suggested as a method to sequester carbon dioxide from point sources into stable carbonate minerals. Alternatively, the addition of lime (produced from calcining carbonate minerals) to the surface ocean (“ocean liming”), which results in an increase in ocean pH and a draw-down of atmospheric CO2 has been proposed as a “geoengineering” technology, which stores carbon as dissolved alkalinity in the surface ocean. Combining these approaches, in which the magnesium carbonate minerals produced from mineral carbonation are used as a feedstock for ocean liming (mineral carbonation-ocean liming; MC–OL), may reduce the limitations of individual technologies while maximizing the benefits. Approximately 1.9 metric tons of magnesium silicate (producing 0.7 ton of magnesium oxide) are required for every net ton of CO2 sequestered. A total of 0.7 ton of CO2 is produced from this activity, 70% of which is high-purity (>98%) from calcining and potentially amenable for geological storage. The technology can be conceptually viewed as an alternative to direct air capture and swaps ambient CO2 for high-purity point source CO2. MC–OL requires approximately 4.9 and 2.2 GJ of thermal and electrical energy ton–1 of CO2 sequestered. MC–OL has less demand for geological storage; only 0.5 ton of CO2 needs to be injected for every ton of CO2 removed from the atmosphere. However, manipulation of ocean chemistry in this way potentially creates an additional environmental impact (localized elevated pH or co-dissolution of trace metals) and requires additional attention.

Reactive Transport Modeling of Natural Carbon Sequestration in Ultramafic Mine Tailings

Atmospheric CO2 is naturally sequestered in ultramafic mine tailings as a result of the weathering of serpentine minerals [Mg3Si2O5(OH)4] and brucite [Mg(OH)2], and subsequent mineralization of CO2 in hydrated magnesium carbonate minerals, such as hydromagnesite [Mg5(CO3)4(OH)2·4H2O]. Understanding the CO2 trapping mechanisms is key to evaluating the capacity of such tailings for carbon sequestration. Natural CO2 sequestration in subaerially exposed ultramafic tailings at a mine site near Mount Keith, Australia is assessed with a process‐based reactive transport model. The model formulation includes unsaturated flow, equations accounting for energy balance and vapor diffusion, fully coupled with solute transport, gas diffusion, and geochemical reactions. Atmospheric boundary conditions accounting for the effect of climate variations are also included. Kinetic dissolution of serpentine, dissolution‐precipitation of brucite and primary carbonates—calcite (CaCO3), dolomite [MgCa(CO3)2], magnesite (MgCO3), as well as the formation of hydromagnesite, halite (NaCl), gypsum (CaSO4·2H2O), blödite [Na2Mg(SO4)2·4H2O], and epsomite [MgSO4·7H2O]—are considered. Simulation results are consistent with field observations and mineralogical data from tailings that weathered for 10 yr. Precipitation of hydromagnesite is both predicted and observed, and is mainly controlled by the dissolution of serpentine (the source of Mg) and equilibrium with CO2 ingressing from the atmosphere. The predicted rate for CO2 entrapment in these tailings ranges between 0.6 and 1 kg m−2 yr−1. However, modeling results suggest that this rate is sensitive to CO2 ingress through the mineral waste and may be enhanced by several mechanisms, including atmospheric pumping.

Precipitation of Magnesium Carbonates as a Function of Temperature, Solution Composition, and Presence of a Silicate Mineral Substrate

Precipitation of carbonate minerals can play important roles in geological carbon sequestration and engineered processes for mineral carbonation. Influences of temperature, solution composition, and the presence of a solid substrate on the nucleation and precipitation of magnesium carbonate minerals were examined in a set of batch experiments. Conditions studied are relevant to full-scale geological carbon sequestration systems. Aqueous phase analysis by inductively coupled plasma mass spectrometry quantified the extent of precipitation. X-ray diffraction analysis was conducted to identify solids. Temperature significantly affected the identity of the solid obtained. At 25°C and 60°C the solids were magnesium carbonate minerals, and at 100°C the solid phase was identified as brucite [Mg(OH)2]. Although magnesite (MgCO3) was predicted to be the most thermodynamically stable magnesium carbonate phase, no magnesite precipitated and instead metastable magnesium carbonate phases formed. Evolution of dissolved concentrations was consistent with precipitation of these metastable phases. Presence of the magnesium silicate forsterite had no measurable effect on the rate or extent of precipitation. Mineralization in geological systems is likely to also be controlled by ionic strength, pressure, and mineralogy of the host formation.