Calcite Phase Research Articles

U-Pb ages of pre- to post-salt carbonates, Santos and Campos basins, SE Brazil: Implications for the evolution of the South Atlantic

The exploration campaigns and independent studies conducted in the central South Atlantic basins after the discovery of giant oil accumulations in the Lower Cretaceous lacustrine carbonates sealed by the salt layer resulted in a new panorama of the tectonic framework, stratigraphic architecture, and petroleum systems of the investigated basins and passive margins in general. Despite these remarkable advances, the ages of the carbonate reservoirs and the sealing evaporites remain uncertain. Aiming to fill this gap, we present here the results of 30 U-Pb LA-ICP-MS calcite and dolomite age determinations representative of the depositional/eo-diagenetic processes and subsequent phases of carbonate cementation recorded by pre-to post-salt units of the Santos and Campos basins of southeastern Brazil. Microcrystalline calcite of a mudstone of the Itapema Formation (Santos Basin) yielded a minimum age of 126.8 ± 4.7 Ma. 19 depositional/eo-diagenetic ages obtained in mudstones, grainstones, shrubstones, spherulitestones, and travertines of the correlative Barra Velha and Macabu pre-salt lacustrine carbonates cluster around 124.1 ± 2.2 and 122.1 ± 2.3 Ma. Considering the errors, these results limit the deposition/eo-diagenesis of these units to the 126.2–120.0 Ma interval. Two determinations carried out in calcite laminae of a nodular anhydrite sample extracted from the lower portion of the Retiro Evaporite (Campos Basin) returned the ages of 119.2 ± 1.6 Ma and 119.18 ± 0.79 Ma, which we interpreted as the best approximation of the timing of the salt deposition. Analyses performed in 3 samples from the post-salt Quissamã carbonates (Campos Basin) provide a minimum age of 114.2 ± 2.8 Ma yielded by interparticle dolomite cement. Other phases of calcite and dolomite cements present in the investigated units were dated at ca. 119.4, 116.5, and 110.7 Ma. The stratigraphically coherent spectrum of ages obtained differs significantly from most available data, providing a new perspective for the ongoing discussions on the tectonic evolution of the South Atlantic and probably impacting the current views of the burial history and petroleum system of the Santos and Campos basins.

Experimental study on the products of coupling effect between microbial induced carbonate precipitation (MICP) and the pozzolanic effect of metakaolin

In this paper, the performance of the products resulting from of coupling effect between microbial induced carbonate precipitation (MICP) and the pozzolanic effect of metakaolin in the same system is analyzed and discussed in depth. The inoculation parameters of the bacterial solution were optimized, and a method of increasing pH of medium step by step was used to acclimate the alkali tolerance adaptation of Sporosarcina pasteurii. Mixed slurries (MC-M) were prepared and cured for 30 days and 180 days using a ratio of metakaolin (MK) to calcium hydroxide (CH) of 1:1, the bacterial solution as mixing water and calcium acetate as the source of introduced calcium. The compressive strength of the specimens was compared and the properties of the products cured for 180d were analyzed based on test methods such as nanoindentation, SEM, XRD, and TG-DSC. The test results show that the macroscopic mechanical properties of the MC-M specimens were effectively improved and the discrete degree of the micromechanical property parameters was reduced. The particle size distribution of the products increased, within 0.9–12 μm. The decomposition temperature of calcium carbonate in the products decreased, and the water loss temperature of the hydrated products increased. CaCO3 contains both aragonite and calcite phases, and the phase compositions of the hydrated products became more stable. This work demonstrates that MICP accelerates the depletion of CH in the pozzolanic reaction system and promotes the transformation of the hydration product phase composition. The pozzolanic effect reduces the particle size and degree of accumulation of calcite produced by MICP, resulting in a denser cured product. This phenomenon is referred to as the “coupling effect” of the two reactions and positively affects the mechanical properties, providing a new research idea on materials and methods for repairing concrete cracks.

Thermal Conversion of Coral Waste and its Utilization as Low-Cost Catalyst for Biodiesel Production

This study investigates the thermal conversion of waste coral and its utilization as a heterogeneous catalyst for biodiesel production from soybean oil. In this work, waste coral is calcined at varied temperatures of 800, 900, and 1000°C, and the effect of the calcination temperature on the physicochemical character of the solid is evaluated through Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and basicity measurement. The results show that the higher temperature facilitates the conversion of CaCO3 of the aragonite and calcite phases in raw waste coral into CaO, achieving a complete conversion at the temperature of 1000°C. Thermal conversion influences the increased surface basicity of the solid, which is associated with the higher activity for biodiesel production. Further studies on the obtained CaO as a catalyst demonstrate the catalyst dosage and the methanol-to-oil ratio as significant factors for fatty acid methyl ester production. The highest yield of 98.7% is achieved after a 3 hours reaction with 8 wt.% catalyst dosage and 9:1 methanol-to-oil ratio. The catalyst exhibits stability with an insignificantly decreased yield until the fifth usage cycle. The optimum conditions and reusability features of the calcined waste coral suggest that waste coral is a favorable CaO catalyst source for biodiesel production.

Industrial manufacturing method and characterization of Ayurvedic marine drugs: mother pearl, cowry, coral and pearl

Introduction: Ayurvedic marine drugs derived from mollusc shells and coral are regularly used by Ayurvedic physicians to treat several disease conditions like acid peptic disease, irritable bowel syndrome, osteoporosis, etc. However, standard operating procedures for manufacturing these drugs and their complete characterization have not been published in the Ayurvedic Formulary and Ayurvedic Pharmacopeia of India to date. Methods: Present study describes the traditional manufacturing process and thorough characterization using classical and advanced analytical tools. The raw materials characters, in-process parameters, and finished product specifications have been elaborated to develop monographs. Especially, the identity and purity of raw coral and pearl were checked by Raman Spectroscopy and Energy Dispersive X-ray Fluorescence analysis. Results: In the finished product analysis, the X-Ray Diffraction study revealed that incineration after trituration with Aloe barbadensis leaf pulp or rose water converted the aragonite phase of calcium carbonate into calcite phase in mother pearl, cowry, and pearl while the calcite form of raw coral was retained. The prominent bands around 1390, 870, and 712 cm−1 detected by Fourier Transform-Infrared Spectroscopy and mass loss between 39–44% (w/w) revealed by thermogravimetric analysis confirmed the carbonate form of these calcium-based drugs. The finished products were very fine grayish-white powders constituted by irregularly shaped nano-micro particulate calcium carbonate exhibiting particle size between 600 nm (D10 value) to 1.2 µm (D90 value). Conclusion: The quality control and assurance achieved in this study may be further utilized by the pharmaceutical industries to manufacture quality marine drugs and conduct efficacy studies.

Experimental study on CO2 sequestration performance of alkali activated fly ash and ground granulated blast furnace slag based foam concrete

In an effort to reduce the emission level of carbon dioxide (CO2) from metallurgical, thermal, cement burning and other enterprises, an innovative solution is proposed in this study, which aims to sequester CO2 with alkali activated fly ash (FA) and ground granulated blast furnace slag (GGBFS) based foam concrete. The fluidity of alkali activated foam concrete (AAFC) fresh paste, dry density and compressive strength after hardening, micro-pore structure, carbonation products and CO2 sequestration capacity were comprehensively explored. The experimental findings indicated that the fluidity of AAFC slurry was almost unaffected by the content of foaming agent hydrogen peroxide (H2O2). When the H2O2 content ranges between 1 % and 3 %, the dry density of uncarbonated AAFC ranges approximately 752.3–365.2 kg/m3, and the compressive strength of carbonated AAFC ranges about 1.01–0.21 MPa. Accelerated carbonation increased the dry density of uncarbonated AAFC samples. The porous structure of AAFC facilitated CO2 gas penetration into the matrix, leading to rapid carbonation. When the H2O2 content was 1 %, the compressive strength of fully carbonated AAFC was lower than that of non-carbonated AAFC; however, when the H2O2 content exceeded 1.5 %, the trend in compressive strength reversed. The carbonation kinetics of AAFC demonstrated a linear relationship with the square root of carbonation time, and the carbonation coefficient increases proportionally with H2O2 content. The porosity of AAFC increased from 61.05 % to 71.51 % as the H2O2 content increased from 1 % to 2.5 %. The main pore size distribution range of AAFC was 30–400 µm and 5–50 nm. Accelerated carbonation minimally impacted the total porosity of AAFC but transformed certain large pores into capillary pores. Accelerated carbonation would generate calcite, aragonite, vaterite and additional amorphous phases. The maximum carbon sequestration capacity of AAFC, as determined in this study, reached 26.41 kg/m3, indicating significant potential for CO2 sequestration.

Microstructural characterization of CO2-cured calcium silicate cement

Calcium silicate cement (CSC) is a non-hydraulic cement that solidifies in moist conditions with CO2 curing. To contribute to the standardization of CSC, the material has been produced locally, and the microstructural characterization of the carbonation products of CSC samples with water-to-cement (W/C) ratios of 0.35, 0.4 and 0.45 at 10% CO2 concentration using XRD, 29Si MAS NMR, 1H NMR and compressive strength tests. CSC primarily consists of Q0, Q1 and Q2 silica species, among which β-C2S and β-CS exhibit higher reactivity to CO2 curing. The obtained results confirm the presence of calcite and amorphous phases as the main carbonation products, which become more prominent with an elapse in CO2 curing. The CO2 uptake of CSC samples with a W/C ratio of 0.45 was 8 g per 100 g binder, although a higher W/C ratio induced a relatively larger capillary and gel pore width, consequently reducing the strength of CSC.

Synthesis of Calcium Carbonate from Orange Peel Waste Extract: A Mechanistic Investigation

The present work reports the mechanism and synthesis of calcium carbonate (CaCO3) formation from orange peel, which is one of the most common agriculture waste generated throughout the globe. The zest of oranges was co-distilled with distilled water to separate the essential oil content. Further, the residue was washed twice with distilled water to get the desired extract. For the green synthesis of CaCO3, a saturated solution of calcium nitrate tetrahydrate (Ca(NO3)2·4H2O) was mixed thoroughly with orange peel extract in the 1:3 proportion. This solution was kept on magnetic stirrer while maintaining temperature at 85˚C, heated at 100˚C for 13 h which was further annealed at 300˚C, 500˚C and 700˚C. X-ray diffraction (XRD) shows the presence of calcite phase corresponding to CaCO3. Fourier transform infrared spectra (FTIR) exhibits the bands corresponding to Ca-O, C-O and vibrations of CO3-2 bonds whereas UV–Visible spectroscopy shows the optical behavior of CaCO3. The qualitative analysis of orange peel extract as well as the black-brown gel formed as a result of sol–gel synthesis method was examined using Gas Chromatography & Mass Spectrometry (GCMS). It revealed the presence of acidic groups (2,3-butanediol & 1,4-benzenediol) which led to the development of a mechanism, governing the formation of CaCO3.

The Changing of Micromechanical Properties of Coal after Water Immersion: The Insight from Nanoindentation Test

The application of the hydrodynamic method has enhanced the extraction of coal bed methane (CBM). In this method, fracturing fluid rapidly penetrates the coal reservoir, altering its intrinsic pore structure and microscopic mechanical properties. These changes impact the properties of the coal reservoir and CBM depletion. It is, therefore, crucial to explore how these micro-characteristics evolve following water invasion. In this context, using nanoindentation tests, the microscopic characteristics of three coal samples were measured under dry conditions and at water saturations corresponding to 44% and 75% relative humidity. The influence of water immersion on the pore structure was also assessed using mercury injection experiments. Moreover, cluster analysis was used to categorize the extensive measured data into three sub-components: fractures (large pores), inertinite, and vitrinite, to investigate the impact of water saturation on microscopic properties. The findings indicate that cluster analysis is well-suited to these data, showing excellent agreement with porosity and maceral tests. The relationship between the elastic modulus and hardness of dry and wet coal samples varies across the sub-components. There is a notable dependency in the case of vitrinite, whereas water content tends to reduce this dependency. It is also found that water content negatively affects elastic modulus and hardness and reduces the anisotropy ratio. The mechanical properties of inertinite are highly responsive to water immersion, whereas vitrinite exhibits lesser sensitivity. The softening mechanisms of coal when immersed in water, such as calcite phase dissolution, swelling stress fracturing, and weakening of macerals, are identified. This study offers new perspectives on the impact of moisture on the alteration of micromechanical properties in coal.

Impact of Different Mineral Reinforcements on HDPE Composites: Effects of Melt Flow Index and Particle Size on Physical and Mechanical Properties.

The use of mineral reinforcements in polymer matrix composites has emerged as an alternative for sustainable production, reducing waste and enhancing the physical and mechanical properties of these materials. This study investigated the impact of the melt flow index (MFI) of HDPE and the particle size of two mineral reinforcements, Bahia Beige (BB) and Rio Grande do Norte Limestone (CRN), on the composites. All composites were processed via extrusion, followed by injection, with the addition of 30 wt.% reinforcement. Chemical analyses revealed similar compositions with high CaO content for both minerals, while X-ray diffraction (XRD) identified predominantly calcite, dolomite, and quartz phases. Variations in the MFI, reinforcement type, and particle size showed a minimal influence on composite properties, supported by robust statistical analyses that found no significant differences between groups. Morphological analysis indicated that composites with lower MFI exhibited less porous structures, whereas larger particles of BB and CRN formed clusters, affecting impact resistance, which was attributed to poor interfacial adhesion.

Synthesis of nano calcium silicates from waste calcite and aragonite phases for efficient adsorptive removal of industrial organic pollutants

The present study focuses on the adsorption efficacy of solid-state synthesized calcium silicate for removing congo red dye. Three different sources were used as calcium precursors; one was calcium carbonate, and the other two were natural waste sources, aragonite (P. globosa) and calcite (Eggshells). Structural analysis and functional groups of the samples were carried out by X-ray diffractometer (XRD), and a Fourier Transform Infrared Spectrometer (FTIR). Various well-known models/equations models such as the Liner Straight Line method of Scherrer’s equation (LSLMSE), Sahadat-Scherrer Model (SSM), Monshi-Scherrer model (MSM), Williamson-Hall model (WHM), Size-Strain plot method (SSP), and Halder-Wagner Model (HWM) were applied to compute the crystallite size of the synthesized calcium silicates; the estimated crystallite size range was 8–77 nm. The adsorption efficacy of the synthesized E-CaSiO3, S-CaSiO3, and C-CaSiO3 was assessed under various provisos for eradicating Congo red dye from wastewater. Computed results revealed that the dye removal percentages were approximately 100 % at 120 min and 200 rpm for 0.2 g E-CaSiO3. The point of zero charge evaluation showed that the pH of the adsorbents during maximum dye removal was 7 and was less than the value of pHpzc. Thermodynamics studies confirmed that the adsorption process was spontaneous. The method of adsorption of dye by the adsorbent was more clearly comprehended by Langmuir, Freundlich, and Temkin adsorption isotherm. 151.28 mg/g was the maximum adsorption capacity for S- CaSiO3 depending on the Langmuir isotherm model’s linear form (R2 = 0.924).

Hydrogenation of calcite and change in chemical bonding at high pressure: Diamond formation above 100 GPa

Synchrotron X-ray diffraction (XRD) and Raman spectroscopy in laser heated diamond anvil cells and first principles molecular dynamics (FPMD) calculations have been used to investigate the reactivity of calcite and molecular hydrogen (H2) at high pressures up to 120 GPa. We find that hydrogen reacts with calcite starting below 0.5 GPa at room temperature forming chemical bonds with carbon and oxygen. This results in the unit cell volume expansion; the hydrogenation level is much higher for powdered samples. Single-crystal XRD measurements at 8–24 GPa reveal the presence of previously reported III, IIIb, and VI calcite phases; some crystallites show up to 4% expansion, which is consistent with the incorporation of ≤ 1 hydrogen atom per formula unit. At 40–102 GPa XRD patterns of hydrogenated calcite demonstrate broadened features consistent with the calcite VI structure with incorporated hydrogen atoms. Above 80 GPa, the CO stretching mode of calcite splits suggesting a change in the coordination of CO bonds. Laser heating at 110 GPa results in the formation of CC bonds manifested in the crystallization of diamond recorded by in situ XRD at 300 K and 110 GPa and by Raman spectroscopy on recovered samples commenced with C13 calcite. We explored several theoretical models, which show that incorporation of atomic hydrogen results in local distortions of CO3 groups, formation of corner-shared CO polyhedra, and chemical bonding of H to C and O, which leads to the lattice expansion and vibrational features consistent with the experiments. The experimental and theoretical results support recent reports on tetrahedral C coordination in high-pressure carbonate glasses and suggest a possible source of the origin of ultradeep diamonds.

Diagenetic archives of the deeply-buried Cambrian Xiaoerbulake Formation microbialite reservoirs, Bachu-Tazhong area, Tarim Basin, China

The deep-burial Cambrian Xiaoerbulake Formation microbialites reservoir hosts significant hydrocarbon in the Tarim Basin. However, limited understandings of fluid-rock interactions from deposition to deep-burial regimes hamper petroleum exploration. Here, petrological observations, in-situ elemental contents and porosity-permeability analyses were performed to understand the complex interactions and the microbialites performance. Dolo-mudstone, crystalline dolostone, and four kinds of microbialites are distinguished as dolostones types. In the depositional stage, microbialites are characterized by (evaporated) seawater dolomitization with the mediation of microbial activity. The dolostone matrix shows seawater-like δ13C, δ18O and REY patterns. Thrombolitic and foam spongy dolostones from high-energy subtidal to intertidal zones show large framework pores compared to stratiform stromatolitic dolostones from low-energy intertidal zones. In near-surface settings, meteoric diagenesis generates secondary pores, while fine-crystalline dolomite cements partially fill pores. During the shallow to intermediate burial regimes, medium-to coarse-crystalline dolomite cements yield negative δ18O values and slightly flat REY patterns. The precipitation of this dolomite phase further decreases reservoir porosity. In deep burial settings, one type of saddle dolomite is likely to be formed by replacement from carbonate precursors, while the second type might be directly precipitated from hydrothermal fluids. These two types of saddle dolomites show different cathodoluminescent characteristics and geochemical data. Subsequently, two types of calcite cements are formed by the calcification of dolomite and yield significant negative δ13C values due to thermochemical sulfate reduction. Finally, the third calcite phase is likely to be a direct precipitate from burial brines. Hydrothermal activity and thermochemical sulfate reduction generate and/or re-distribute secondary pores. Based on the plethora of depositional environments and fluid-rock interactions, thrombolitic dolostone generally yields higher porosity-permeability than other types of microbialites. Thrombolite reservoir has high potential for petroleum exploration and is significant for those concerned with microbialite hydrocarbon fields.

Hydration Characteristics of Slag-Ca(OH)2-Al2O3 Binder in a 60 °C Curing Environment with Brine as Mixing Water

Recently, research results on PC-based or alkali-activated slag cement (AASC) using seawater as mixing water have been reported. Unlike seawater, reverse osmosis brine (brine) is waste discharged into the ocean from seawater desalination plants. There is a need to develop new and effective methods of disposing or utilizing brine to reduce marine pollution, protect marine ecosystems, and increase marine plant construction. However, research on cement or concrete using brine as a mixing water is very limited. Brine has almost the same composition as seawater, and the ion concentration is 2–4 times higher. Therefore, it is believed that new methods of using brine can be investigated and developed based on existing research and experimental results on seawater. The effects of brine and aluminum oxide (AO) on activated slag with calcium hydroxide (CH) were investigated for hydration and mechanical properties. 5% and 10% of CH were used, and samples using fresh water (FC) were prepared at the same time for comparison with brine. The slag sample without CH has a low initial (1 and 3d) strength of about 10 MPa for both FC and brine, but increases rapidly from 7d. Incorporation of CH was effective in improving the mechanical performance of FC and brine samples. In addition, the brine sample exhibited higher strength than the FC sample because it formed fewer C3AH6 phases that cause volume instability than the FC sample and affected the hydration promotion of slag particles. And more calcite phases were observed in the brine samples than in the FC samples. Through this study, the possibility of using brine as a building material was confirmed. In addition, the effect of chloride ion adsorption of slag mixed with AO and CH on the physical properties and mechanical performance of the hydration reaction was confirmed.

Carbon sequestration in cementitious systems through CO2-rich hydration and chemically enforced CO2 mineralization

Cementitious materials as a medium of carbon capture, and utilization (CCU) have recently attracted considerable attentions. Atmospheric CO2 can be absorbed in hardened concrete, which can be also accelerated by early age CO2 curing. Compared to the CO2 curing of concrete materials, in-situ CO2 mixing technology can be widely applied because it can be used in a batch plant without an additional curing facility. In this study, the CO2 mixing time was set as the primary variable to elucidate the precipitation of the carbonate phases in the early stages and its effect on cement hydration. The dissociated CO2 is directly mineralized into calcium carbonate (CaCO3) in calcite phase. In addition, the longer the CO2 mixing time, the greater the precipitation of calcite (i.e., CCU capacity), thereby densifying the internal microstructure and improving early strength development. Interestingly, a certain amount of calcite converted to monocarboaluminate—an important factor for quantitatively assessing the degree of mineral carbonation in cementitious materials.

Heat Treatment of Calcite to Enhance Its Removal of Color Dye Alizarin Red S

The use of color dyes in modern society presents a great challenge to the environment. Thus, extensive studies have been conducted in the last 30 years on the removal of color dyes from aqueous solutions such industrial wastewater. In this study, the removal of alizarin red S (ARS), an anionic dye, from solution by raw calcite (Cal) and heat-treated calcite (HCal) was conducted and compared under different physico-chemical conditions. Based on the isotherm study, the ARS removal capacities increased from 167 to 251 mmol/kg after the Cal was heated to 1000 °C for 3 h. The X-ray diffraction analyses showed no difference in the calcite phase between Cal and HCal after ARS sorption. Fourier-transform infrared results also showed no change in the calcite phase after ARS sorption, except a slightly increase in wavenumber from 713 to 727 cm−1 for the OCO bending of HCal at high ARS sorption levels. SEM observations showed about the same particle size and morphology before and after ARS sorption. The TGA data showed the formation of CaO after Cal was heated, and CaO converted back into calcite after being in contact with water or ARS solution for 24 h and then being air-dried. Thus, the high ARS removal could be due to CaO produced after Cal being heated. The findings from this research proved that there is great potential in the use of calcite, a low-cost and readily available Earth material, after heat treatment for the removal of contaminants from water.

A simulation-based approach for understanding CO2 capture and mineralization dynamics in desalination brine

In the pursuit of sustainability, it is crucial to repurpose waste resources into valuable chemicals. One promising avenue is sequential CO2 mineralization using natural seawater or desalination brine solution, which concurrently removes CO2 from the atmosphere while recovering valuable minerals. To realize this approach, it is paramount to grasp the factors influencing the process efficiency and product composition. Here, we present a simulation approach using the visual MINTEQ v3.1 and PHREEQC v3.7.0 models to investigate the impact of CO2 concentration and OH− (as an alkaline source) on the mineral recovery process. The findings reveal that both CO2 concentration and OH− significantly influence the mineral phase composition. Specifically, higher CO2 flow rates or elevated OH− levels promote calcite formation while suppressing the brucite phase, with limited hydromagnesite formation. Moreover, an interactive effect between OH− and CO2 is observed, with OH− essential for carbonate formation. We further validated these insights through preliminary experiments employing electrochemical methods as a source of OH−, wherein aqueous CO2 and applied current density (proportional to OH− concentration) regulated mineral phase composition. Notably, the weight percentage of the brucite phase in the precipitates ranged from 67 % to 73 %, while the calcite phase varied from 20 % to 26 % with alterations to the applied electric currents. The present study not only provides valuable insights into the recovery of potential elements and efficient capture of CO2 in non-synthesized brine solution with a combined theoretical and experimental approach but also demonstrates the viability of employing electrochemical-driven methods as a greener alkaline source for CO2 capture and mineral recovery.

Exploring the role of surface and porosity in CO2 capture by CaO-based adsorbents through response surface methodology (RSM) and artificial neural networks (ANN)

In this study, synthetic CaCO3 materials were utilized as precursors for CaO-based CO2 sorbents. The investigation examined how various operating parameters—such as synthesis temperature (ST), stirring rate (SR), and surfactant percentage (SP)—impact the properties of the adsorbents. Samples were firstly characterized by X-ray diffraction and Scanning Electron Microscopy (SEM), which revealed that the prevalence of calcite or aragonite crystal phases in the synthetic CaCO3 precursors can be tuned by adequately choosing the dose of surfactant (Triton-X100®), so that it can be used as a crystal habit and growth modifier. The calcination process applied to the CaCO3 precursors leads to the formation of partially sinterized cubic crystals of CaO, accompanied by minor quantities (< 5 %) of additional compounds like Ca(OH)2 or CaSO4. Specific surface area (SBET) and porosity were determined by measuring the N2 adsorption isotherms. A CaCO3 sample with an unprecedented value of SBET as large as 116 m2/g was prepared operating under optimal conditions. SBET and pore volumes were successfully correlated with the CO2 uptake capacity of the samples. SBET is more influential for experiments carried out under diluted CO2 atmosphere. When pure CO2 is used, the influence of meso- and micropore volumes (Vme and Vmi) is clearly predominant, which suggests that in this latter case diffusion through the porous texture of the samples plays a more remarkable role. A double-way approach through Response Surface Methodology (RSM) and the use of Artificial Neural Networks (ANNs) has been used to analyze the CO2 uptake capacity of the samples. Within the operational interval, excellent results were obtained for pure and diluted CO2 flow, and RSM and ANNs have demonstrated to be a very efficient tool to correlate the behavior of the CaO-based materials as CO2 sorbents with the surface area and pore volumes of the samples. Valuable information on (i) the importance of the different factors under study; (ii) their influence on the surface and porosity of the CaO-derived sorbents; and (iii) the subsequent CO2 capture performance of the sorbents has been obtained. The results suggest that four parameters have a statistically significant influence on CO2 uptake. These parameters are SR, the square of SR, its interaction with SP, and the square of SP. Additionally, the study assessed the stability of the CaO-based sorbents over 11 consecutive calcination-carbonation cycles. By adequately choosing the synthesis strategy and conditions, an almost negligible shrinkage effect can be achieved, resulting in a more sustained uptake capacity throughout the cycles.

Origin and modern microbial ecology of secondary mineral deposits in Lehman Caves, Great Basin National Park, NV, USA.

Lehman Caves is an extensively decorated high desert cave that represents one of the main tourist attractions in Great Basin National Park, Nevada. Although traditionally considered a water table cave, recent studies identified abundant speleogenetic features consistent with a hypogenic and, potentially, sulfuric acid origin. Here, we characterized white mineral deposits in the Gypsum Annex (GA) passage to determine whether these secondary deposits represent biogenic minerals formed during sulfuric acid corrosion and explored microbial communities associated with these and other mineral deposits throughout the cave. Powder X-ray diffraction (pXRD), scanning electron microscopy with electron dispersive spectroscopy (SEM-EDS), and electron microprobe analyses (EPMA) showed that, while most white mineral deposits from the GA contain gypsum, they also contain abundant calcite, silica, and other phases. Gypsum and carbonate-associated sulfate isotopic values of these deposits are variable, with δ34SV-CDT between +9.7‰ and +26.1‰, and do not reflect depleted values typically associated with replacement gypsum formed during sulfuric acid speleogenesis. Petrographic observations show that the sulfates likely co-precipitated with carbonate and SiO2 phases. Taken together, these data suggest that the deposits resulted from later-stage meteoric events and not during an initial episode of sulfuric acid speleogenesis. Most sedimentary and mineral deposits in Lehman Caves have very low microbial biomass, with the exception of select areas along the main tour route that have been impacted by tourist traffic. High-throughput 16S rRNA gene amplicon sequencing showed that microbial communities in GA sediments are distinct from those in other parts of the cave. The microbial communities that inhabit these oligotrophic secondary mineral deposits include OTUs related to known ammonia-oxidizing Nitrosococcales and Thaumarchaeota, as well as common soil taxa such as Acidobacteriota and Proteobacteria. This study reveals microbial and mineralogical diversity in a previously understudied cave and expands our understanding of the geomicrobiology of desert hypogene cave systems.

Preferential formation of uniform spherical vaterite by harnessing vortex flows and integrated CO2 capture and mineralization

The use of calcium bearing resources to facilitate solvent regeneration and CO2 reuse via carbon mineralization offers a low energy pathway for the production of calcium carbonate. However, a crucial challenge is the lack of specificity in the formation of various calcium carbonate polymorphs during carbon mineralization. One of the less explored but highly effective approaches to tune the morphology and crystal structure of specific carbonate phases involves tuning vortex flows. This approach is an alternative to utilizing chemical reagents that need to be regenerated for tuning the morphologies and crystalline structures to direct the formation of specific carbonate phases. In this study, the efficacy of using homogeneous vortex flows in limiting the agglomeration of carbonate particles and directing the formation of metastable vaterite phases is discussed and contrasted with the influence of inhomogeneous conventional feed flow patterns on precipitated calcium carbonate (PCC). Herein, a Taylor-Couette Carbonate Conversion (TC3) reactor is used to direct the formation of spherical vaterite particles with uniform particle size distribution preferentially over calcite and other phases. The formed vortex patterns inside TC3 reactor provide homogeneous reaction spaces conducive to PCC formation, ensuring uniform mixing throughout the process. By increasing the rotational speed and the residence time, higher purity carbonates with more uniform sizes are obtained. Furthermore, preferential vaterite formation is also observed in leachates obtained from alkaline industrial residues such as construction and demolition waste and steel slag. Thus, the proposed approach is effective in harnessing multiple waste streams such as CO2 emissions and alkaline industrial residues to produce calcium carbonate phases such as vaterite with structural and morphological specificity.

Thermodynamic assessment of the phase diagrams of calcite and CaO–CaCO3 system

The study of phase equilibria in the Ca-C-O system is complicated by the decomposition of one of the intermediate compounds, calcite. Experimental studies present an ambiguous interpretation of the results, which contain conflicting information about the phase diagrams of calcite and the CaO–CaCO3 system at pressures up to 100 MPa. Thermodynamic modelling has been used in this study for the determination of phase equilibria in these systems. Using reliable experimental phase diagram data, the thermodynamic properties of calcite and CaCO3(liq) were corrected to take into account the pressure influence. This resulted in an accurate reproduction of the experimental data on calcite phase equilibria and made it possible to construct a model of the CaO–CaCO3 system phase diagram taking into account the calcite decomposition. It will allow to further modelling of more complex processes involving calcite in the pressures range up to 30 MPa and temperatures up to 1800 K.