Formation Of Carbonate Minerals Research Articles

Laboratory experiments of carbon mineralization potential of the main terrestrial basalt reservoirs in China

Against the background of realizing the goal of “carbon peaking and carbon neutrality”, using basaltic rocks for carbon mineralization is one of the most promising approaches to reduce the rise in atmospheric CO2 concentrations. This study conducted a series of experiments to assess carbon mineralization in nine basalt samples from the main terrestrial basalt reservoirs in China within CO2-H2O/brine-rock systems at low temperatures (≤35 °C). The results indicate that the secondary carbonates formed in the CO2-H2O/brine-basalt system are predominantly calcite rather than Mg-carbonate minerals at low temperatures (≤35 °C). Hence, at low temperatures (≤35 °C), basalt rich in Ca-bearing minerals promotes the formation of stable carbonate minerals more effectively than basalt containing Mg-bearing minerals. Furthermore, under conditions of low temperatures (≤35 °C) and pressures of approximately 3 MPa, the results suggest that alkaline olivine basalt, with a higher content of Ca-minerals and typical alkaline minerals (nepheline and Na-sanidine), exhibits the highest pH value and the highest amount of calcite. Hence, the alkaline minerals, nepheline and Na-sanidine, serve as pH buffers to increase the pH and promote the precipitation of calcite within CO2-H2O– basalt systems at low temperatures (≤35 °C). Among the nine evaluated basalts, basalt from the Shandong Linqu-Changle volcanic basin exhibits the highest rate of carbon mineralization at low temperatures (≤35 °C). Hence, Cenozoic alkaline olivine basalt from Shandong Linqu-Changle volcanic basin is one of the most promising basalt reservoirs in China for future in- situ carbonation. As for ex- situ carbonation, compared with olivine, diopside or Ca-plagioclase may be more appropriate for increasing ocean negative emissions.

Chemical aging of biochar-zero-valent iron composites in groundwater: Impact on Cd(II) and Cr(VI) co-removal

Biochar (BC), zero-valent iron (ZVI), and their composites are promising materials for use in permeable reactive barriers, although further research is needed to understand how their properties change during long-term aging in groundwater. In this study, BC, ZVI and their composites (4BC-1ZVI) were subjected to the chemical aging tests in five media (deionized water, NaCl, NaHCO3, CaCl2 and a mixture of CaCl2 and NaHCO3 solutions) for 20 days. After treatment, the microscopic analysis and performance tests for the co-removal of Cd(II) and Cr(VI) were carried out. The results indicated that the removal of Cd(II) by aged 4BC-1ZVI followed a pseudo-second-order model, whereas the removal of Cr(VI) was better fitted with a pseudo-first order model. The aging mechanism of 4BC-1ZVI was primarily governed by iron corrosion/passivation, the reduction of soluble components, and the formation of carbonate minerals. Less Fe3O4/ γ-Fe2O3 was formed during aging in deionized water, NaCl and CaCl2 solutions. The corrosion products, Fe3O4/ γ-Fe2O3, FeCO3 and α/γ-FeOOH, were observed after aging in NaHCO3 and a mixture of NaHCO3 and CaCl2 solutions. The decrease in the soluble components of biochar led to a decrease in cation exchange, while carbonate minerals contributed to Cd(II) precipitation. This work provides insights into the aging processes of BC-ZVI composites for long-term groundwater remediation applications.

Shallow lake response to Holocene climate variation in south-central Minnesota, USA

Sedimentary deposits in lakes across the upper Midwest record the co-evolution of climate and biogeochemistry since the retreat of the Laurentide Ice Sheet at the end of the last glacial period. Here, we report on a Holocene lake sediment record from Chub Lake, a shallow (3 m depth) eutrophic lake system in south-central Minnesota. High-resolution elemental data from scanning XRF along with variations in organic matter, carbonate minerals, clastic material, biogenic silica, charcoal, and carbon isotopes reveal internally consistent patterns of hydroclimatic influence on this shallow lake system from 11,300 years BP to present. In particular, authigenic carbonate mineral formation and preservation in Chub Lake appears to be well suited as a moisture proxy beginning around 9700 BP up until ∼2300 BP, when a combination of more humid climates and basin-infilling change the hydrology of Chub Lake. This work emphasizes the importance of evaluating shallow lake sediment records both as important archives of climate proxies and case studies on how changing climates impact aquatic systems.

Effects of different Mg/Ca molar ratio on the formation of carbonate minerals in microbially induced carbonate precipitation (MICP) process

Traditional MICP technology has been extensively applied to improve soil properties and solidify heavy metal contaminated soil. However, the traditional product performance of calcite is far less than that of huntite, dolomite, and other carbonate minerals. Therefore, the soil strength and environmental safety after curing cannot reach the safety index. This study has examined the distribution of carbonate minerals induced by microorganisms under different Mg/Ca ratio. Compared with the sample with 0 Mg/Ca content, the unconfined compressive strength (UCS) can be increased by 1–5 times by increasing the content. By X-ray diffraction (XRD) and thermogravimetric analysis (TGA), the contents of different carbonate minerals under different Mg/Ca content were determined semi-quantitatively. The microscopic results have also shown that the introduction of microorganisms can provide nucleation sites for the synthesis of dolomite and huntite. MICP experiment coupled with Quantum ESPRESSO calculations revealed the mechanism of microbial influence on the formation of carbonate minerals under different Mg/Ca conditions through first principles calculations and nucleation kinetics. These findings advance our understanding of the reaction mechanisms and pathways of biogenic precipitation of carbonate minerals, and provide insights into the artificial quantitative synthesis of dolomite.

Modeling bicarbonate formation in an alkaline solution with multi-level quantum mechanics/molecular dynamics simulations

Understanding carbonate speciation and how it may be modulated is essential for the advancement of carbon dioxide (CO2) capture and storage technologies, which often rely on the transformation of CO2 into carbonate, e.g. via the formation of carbonate minerals. To date, few atomic-level, quantum-mechanics-based simulations have been carried out to characterize how carbonic acid (H2CO3) and bicarbonate ( HCO 3 − ) form in aqueous solution, and how pH affects this process. Recently, Martirez and Carter utilized rare-event sampling density functional theory molecular dynamics simulations in combination with multi-level embedded correlated wavefunction theory, thus accounting for both solvent dynamics and electron correlation accurately, to elucidate the mechanism of H2CO3 formation in neutral solution (J. Am. Chem. Soc., 145, 12561, 2023). Here, we perform a complementary simulation using the same method to map out the energetics of HCO 3 − formation from dissolved CO2 in basic solution. We find that, as in H2CO3 formation, including water dynamics is important to obtain an accurate prediction of the energetics for the aforementioned reaction. Furthermore, only with MD did we identify the correct pathway for the reaction, in which water – not hydroxide – acts as the initial nucleophile and only at the transition state does it lose a proton.

A process-based geochemical framework for carbonate sediments during marine diagenesis

A significant proportion of marine calcium carbonate sediments are comprised of metastable minerals that are susceptible to diagenetic alterations during burial. These reactions can reset the geochemical signature of sediments and pore fluids and influence elemental cycling in the ocean. However, the timing and mechanisms by which these reactions take place are poorly constrained. This study uses cores drilled on the slope of the Great Bahama Bank to provide quantitative constraints on important diagenetic reactions; namely respiration-driven dissolution, authigenic carbonate mineral formation, and conversion of aragonite to low Mg calcite (LMC). We perform detailed mineralogical characterization using newly acquired, high resolution X-ray diffraction (XRD) data and over 1000 reanalyzed XRD scans, characterize sediments texturally and elementally using electron microprobe data, calculate pore fluid saturation state with respect to aragonite using a Pitzer ion interaction approach, and use pore fluid chemistry and experimental distribution coefficients to predict authigenic carbonate compositions. These data suggest that aerobic organic matter oxidation, enabled by the advection of oxygenated seawater throughout the upper ∼ 30 m interval of sediment, causes undersaturation and thus dissolution of biogenic high Mg calcite (HMC) and aragonite. Deeper, anaerobic organic matter oxidation takes over and causes supersaturation, promoting authigenic precipitation in the form of HMC, which in turn decreases pore fluid Mg/Ca and promotes aragonite conversion to LMC. One novel aspect of this study is the identification of three types of calcites using the newly acquired XRD and electron microprobe data. Based on their unique crystallographic characteristics and chemical compositions, these types of calcites are interpreted to represent pelagic biogenic LMC, bank-derived biogenic HMC, and authigenic HMC precipitated from pore fluids. Notably, the composition of the authigenic calcite matches that predicted to precipitate from pore fluids using an empirical Mg partition coefficient in calcite. Calcites that form authigenically and from aragonite via replacement are suggested to recrystallize with burial as evidenced by the decrease in Mg content and micro-strain. This process-based geochemical framework assigns diagenetic processes to a specific depth window within the sediment column and paves the way for a mechanistic understanding of carbonate diagenesis, one that is rooted in thermodynamic and kinetic bases.

Carbonate precipitation and phosphate trapping by microbialite isolates from an alkaline insular lake (Bagno dell'Acqua, Pantelleria Island, Italy).

The Bagno dell'Acqua lake is characterized by CO2 emissions, alkaline waters (pH = 9) and Eh values which indicate strongly oxidizing conditions. A typical feature of the lake is the presence of actively growing microbialites rich in calcium carbonates and silica precipitates. Mineralogy, petrography and morphology analyses of the microbialites were coupled with the analysis of the microbial community, combining molecular and cultivation approaches. The DNA sequencing revealed distinct patterns of microbial diversity, showing pronounced differences between emerged and submerged microbialite, with the upper layer of emerged samples exhibiting the most distinctive composition, both in terms of prokaryotes and eukaryotes. In particular, the most representative phyla in the microbial community were Proteobacteria, Actinobacteriota, and Bacteroidota, while Cyanobacteria were present only with an average of 5%, with the highest concentration in the submerged intermediate layer (12%). The role of microorganisms in carbonate mineral formation was clearly demonstrated as most of the isolates were able to precipitate calcium carbonate and five of them were characterized at molecular level. Interestingly, when microbial isolates were cultivated only in filtered water, the precipitation of hazenite was observed (up to 85%), opening new prospective in P (phosphate) recovery from P depleted environments.

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.

Element mobility during basalt-water-CO2 interaction: observations in natural systems vs. laboratory experiments and implication for carbon storage

Today, carbon dioxide removal from the atmosphere is the most ambitious challenge to mitigate climate changes. Basalt rocks are abundant on the Earth’s surface (≈ 10%) and very abundant in the ocean floors and subaerial environments. Glassy matrix and minerals constituting these rocks contain metals (Ca2+, Mg2+, Fe2+) that can react with carbonic acid to form metal carbonates (CaCO3, MgO3 and FeCO3). Here, we present a data compilation of the chemical composition of waters circulating in basalt aquifers worldwide and the results of simple basalt-water-CO2 experiments. Induced or naturally occurring weathering of basalts rocks release elements in waters and elemental concentration is closely dependent on water CO2 concentration (and hence on water pH). We also performed two series of experiments where basaltic rock powder interacts with CO2-charged waters for one month at room temperature. Laboratory experiments evidenced that in the first stages of water-rock interaction, the high content of CO2 dissolved in water accelerates the basalt weathering process, releasing in the water not only elements that can form carbonate minerals but also other elements, which depending on their concentration can be essential or toxic for life. Relative mobility of elements such as Fe and Al, together with rare earth elements, increases at low pH conditions, while it decreases notably at neutral pH conditions. The comparison between experimental findings and natural evidence allowed to better understand the geochemical processes in basaltic aquifers hosted in active and inactive volcanic systems and to discuss these findings in light of the potential environmental impact of CO2 storage in mafic and ultramafic rocks.

Discovery of a hyperalkaline liquid condensed phase: significance toward applications in carbon dioxide sequestration.

Bicarbonate ion-containing solutions such as seawater, natural brines, bovine serum and other mineralizing fluids have been found to contain hyperalkaline droplets of a separate, liquid condensed phase (LCP), that have higher concentrations of bicarbonate ion (HCO3 -) relative to the bulk solution in which they reside. The existence and unique composition of the LCP droplets have been characterized by nanoparticle tracking analysis, nuclear magnetic resonance spectroscopy, fourier transform infrared spectroscopy, dissolved inorganic carbon analysis and refractive index measurements. Carbon dioxide can be brought into solution through an aqueous reaction to form LCP droplets that can then be separated by established industrial membrane processes as a means of concentrating HCO3 -. Reaction of calcium with the LCP droplets results in calcium carbonate precipitation and mineral formation. The LCP phenomenon may bear on native mineralization reactions and has the potential to change fundamental approaches to carbon capture, sequestration and utilization.

A bicarbonate-rich liquid condensed phase in non-saturated solutions in the absence of divalent cations.

Bicarbonate (HCO3 -) and sodium (Na+)-containing solutions contain droplets of a separate, bicarbonate-rich liquid condensed phase (LCP) that have higher concentrations of HCO3 - relative to the bulk solution in which they reside. The existence and composition of the LCP droplets has been investigated by nanoparticle tracking analysis, nuclear magnetic resonance spectroscopy, refractive index measurements and X-ray pair distribution function analysis. The bicarbonate-rich LCP species is a previously unaccounted-for, ionic phenomenon which occurs even in solutions with solely monovalent cations. Its existence requires re-evaluation of models used to describe and model aqueous solution physicochemistry, especially those used to describe and model carbonate mineral formation.

Effect of Ba2+ on the biomineralization of Ca2+ and Mg2+ ions induced by Bacillus licheniformis.

The effect of barium ions on the biomineralization of calcium and magnesium ions is often overlooked when utilizing microbial-induced carbonate precipitation technology for removing barium, calcium, and magnesium ions from oilfield wastewater. In this study, Bacillus licheniformis was used to bio-precipitate calcium, magnesium, and barium ions. The effects of barium ions on the physiological and biochemical characteristics of bacteria, as well as the components of extracellular polymers and mineral characteristics, were also studied in systems containing coexisting barium, calcium, and magnesium ions. The results show that the increasing concentrations of barium ions decreased pH, carbonic anhydrase activity, and concentrations of bicarbonate and carbonate ions, while it increased the contents of humic acids, proteins, polysaccharides, and DNA in extracellular polymers in the systems containing all three types of ions. With increasing concentrations of barium ions, the content of magnesium within magnesium-rich calcite and the size of minerals precipitated decreased, while the full width at half maximum of magnesium-rich calcite, the content of O-C=O and N-C=O, and the diversity of protein secondary structures in the minerals increased in systems containing all three coexisting ions. Barium ions does inhibit the precipitation of calcium and magnesium ions, but the immobilized bacteria can mitigate the inhibitory effect. The precipitation ratios of calcium, magnesium, and barium ions reached 81-94%, 68-82%, and 90-97%. This research provides insights into the formation of barium-enriched carbonate minerals and offers improvements for treating oilfield wastewater.

Controls of temperature and mineral growth rate on lithium and sodium incorporation in abiotic aragonite

The use of Li/Ca, Na/Ca and Li/Mg ratios in biogenic aragonite exhibits high potential for reconstructing environmental parameters such as temperature and/or salinity. To date however, only a little is known about the mechanisms controlling the incorporation of monovalent metals such as Li+ and Na+ in aragonite. In this study, the effects of temperature and growth rate on Li and Na incorporation into abiotically precipitated aragonite were experimentally investigated. The results for aragonite overgrowths at 5, 15 and 25 °C and for the surface normalized growth rate range 10–8.6 ≤ rp ≤ 10–7.1 (mol/m2/s) suggest that apparent distribution coefficients (i.e., DMe+=CMe+CCaaragonitemMe+mCasolution) of Li and Na are mainly controlled by mineral growth rate, whereas temperature has a minor effect. The combined effect of growth rate and temperature on DLi and DNa can be described as:LogDLi=0.836±0.028Logrp−0.026±0.002T+2.958±0.221;R2=0.97LogDNa=0.456±0.030Logrp−0.018±0.002T−0.253±0.234;R2=0.90where Log rp is the growth rate in mol/m2/s and T is the temperature in degrees Celsius.The DLi and DNa values increase at increasing mineral growth rate, but also decrease as a function of temperature in experiments with similar normalized growth rate. These observations suggest that the incorporation of Li and Na in abiotic aragonite is controlled by the density of mineral surface defect sites that are correlated with the degree of saturation of the reactive solution with respect to aragonite. Interestingly, no correlation between Li/Mg in the aragonite overgrowths and temperature of formation was observed in this study. This difference of Li/Mg and temperature correlations between abiotic aragonite and natural biogenic samples is intriguing and underlines the need for robust understanding of elemental incorporation during carbonate mineral formation, and proxy calibrations specific for growth conditions (e.g., abiotic versus biogenic). The results of this study do not support the use of Li/Mg as a temperature proxy in abiotic aragonite.

Exploring the potential of stable isotope methods for identifying the origin of CO2 in the carbonation process of cementitious materials within the carbon capture and storage environment

This study investigates the potential of stable isotope (δ13C) methods for exploring the carbonation process of cementitious materials, including well cement paste, portlandite (CH), and calcium silicate hydrate (C–S–H). Through comprehensive chemical and isotopic characterization, along with extensive data analysis, several key conclusions emerge. Firstly, the pH of the solution, as well as the solubility and pH characteristics of mineral phases (CH and C–S–H), are identified as influential factors impacting the kinetics, thermodynamics, and distribution of carbon isotopes (12C and 13C) during the reaction process. Secondly, the study uncovered that higher final pH values correlated with a DIC pool enriched with 13C and a higher εDIC-CO2 isotopic enrichment factor (10.7–12.6 ‰). Furthermore, higher levels of DIC content, solution electrical conductivity, and lower pH lead to higher δ13C–CaCO3 and greater εCaCO3-DIC isotope fractionation (−12.9 to −7.5 ‰). These conditions favor the formation of carbonate minerals with higher isotopic signature (δ13C–CaCO3), thus better preserving the δ13C-DIC isotope ratio. It was identified that the carbonate mineral (δ13C–CaCO3) formed through the carbonation of cementitious materials (class G cement, CH, and C–S–H) appears to preserve the isotopic signature of the δ13C–CO2 source. In conclusion, stable isotope methods could be a valuable tool for assessing and monitoring the cement carbonation process in Carbon Capture and Storage (CCS) wells, particularly when it is crucial to distinguish between injected and endogenous CO2.

Dissolved Mn2+ promotes microbially-catalyzed protodolomite precipitation in brackish oxidized water

Manganese (Mn) is a common trace element in dolomite, yet its precise role in dolomite precipitation, if any, has not been explored. This study aims to investigate carbonate mineral formation in the presence of extracellular polymeric substances produced by Bacillus licheniformis Y1 in 14 cross-over experiments within the MgCl2-CaCl2-MnCl2 system. The study involved the analysis and comparison of water chemistry, mineralogy and bacterial metabolites. The findings indicate that B. licheniformis Y1 induces the formation of Mg-free calcite and low-Mg calcite in Mn-free solutions (Mg/Ca < 2). The addition of 0.001 mol/L Mn2+ results in the precipitation of Mg-rich calcite. In the presence of a relatively high Mg2+ content in the solution (Mg/Ca > 6), B. licheniformis Y1 in a Mn-free solution induces the formation of aragonite and dypingite, whereas the addition of 0.001 mol/L Mn2+ leads to the formation of Mn-bearing dolomite in the precipitate. Notably, at Mg/Ca = 6, an increase in Mn2+ content of the fluid to 0.002 and 0.003 mol/L yields Mn-rich dolomite. The Mn-bearing dolomite exhibits a regular spherical aggregate morphology with diameters ranging from 15 to 60 μm. The 2θ position of the (104) crystal face is close to that of dolomite, and the thermal decomposition temperature is lower than that of calcite. XPS results show that MnO bonds exist on the mineral surface. Acidic amino acids such as glutamic acid as well as humic acid in EPS, especially fulvic acid analogues, actually rise with increasing Mn2+ concentration and contain a large number of functional groups including carboxyl groups. Molecular dynamics simulations show that fulvic acid can effectively promote the dehydration of Mg-water complexes, thus promoting the formation of dolomite. These experiments indicate that the presence of Mn ions in the solution, along with bacteria and EPS, promote the precipitation of protodolomite.

Bacterial templated carbonate mineralization: insights from concave-type crystals induced by Curvibacter lanceolatus strain HJ-1.

The elucidation of carbonate crystal growth mechanisms contributes to a deeper comprehension of microbial-induced carbonate precipitation processes. In this research, the Curvibacter lanceolatus HJ-1 strain, well-known for its proficiency in inducing carbonate mineralization, was employed to trigger the formation of concave-type carbonate minerals. The study meticulously tracked the temporal alterations in the culture solution and conducted comprehensive analyses of the precipitated minerals' mineralogy and morphology using advanced techniques such as X-ray diffraction, scanning electron microscopy, focused ion beam, and transmission electron microscopy. The findings unequivocally demonstrate that concave-type carbonate minerals are meticulously templated by bacterial biofilms and employ calcified bacteria as their fundamental structural components. The precise morphological evolution pathway can be delineated as follows: initiation with the formation of bacterial biofilms, followed by the aggregation of calcified bacterial clusters, ultimately leading to the emergence of concave-type minerals characterized by disc-shaped, sunflower-shaped, and spherical morphologies.

Assessing biochar's permanence: An inertinite benchmark

The natural removal of carbon dioxide and its permanent storage by the Earth system occurs through (i) inorganic carbon and (ii) organic carbon pathways. The former involves the “mineralization” of carbon and formation of carbonate minerals, whereas the latter employs the “maceralization” or natural carbonization of biomass into the “inertinite maceral”. The production of biochar is a carbon dioxide removal (CDR) method that imitates the geological organic carbon pathway, using controlled pyrolysis to rapidly carbonize and transform biomass into inertinite maceral for permanent storage. Therefore, the main challenge in assessing biochar's permanence is to ensure complete transformation has been achieved.Inertinite is the most stable maceral in the Earth's crust and is hence considered an ultimate benchmark of organic carbon permanence in the environment. Therefore, this study aims to measure the degree of biochar's carbonization with respect to the well-established compositional and microscopic characteristics of the inertinite. The random reflectance (Ro) of 2% is proposed as the “inertinite benchmark” (IBRo2%) and applied to quantify the permanent pool of carbon in a biochar using the Ro frequency distribution histogram. The result shows that 76% of the studied commercial biochar samples have their entire Ro distribution range well above IBRo2% and are considered pure inertinite biochar. The oxidation kinetic reaction model for a typical inertinite biochar indicates a time frame of approximately 100 million years for the degradation and loss of half of the carbon in the biochar. This estimate assumes exposure to a highly oxidizing environment with a constant surface temperature of 30°C, highlighting the inherent “permanent” nature of the material. In a less hostile environment, the expected permanence of inertinite is generally anticipated to be even longer.In addition to the inertinite that constitutes the largest fraction of the typical commercial biochar, an incompletely carbonized biochar may contain up to three other organic pools in descending order of stability. The relative concentration of these pools in a biochar can be quantified by a combination of geochemical pyrolysis and random reflectance methods. Furthermore, the Ro can be used to calculate the carbonization temperature (CT oC) of a biochar, which is the maximum temperature to which biochar fragments have been exposed during pyrolysis. This indicator provides important information about the efficiency of the carbonization process and subsequently the biochar's stability, with respect to production temperature (PT oC), heating residence time, and thermal diffusivity. Short summaryThe Earth's carbon dioxide removal and storage occur via inorganic and organic pathways: mineralization and maceralization. Biochar, imitating the organic pathway, undergoes controlled pyrolysis to transform biomass feedstock through a carbonization process into the inertinite maceral, which is a permanently stable form of organic carbon. Kinetic modeling in this study confirms inertinite's carbon stability over geological time scale.Assessing biochar's permanence hence hinges on achieving complete carbonization and transformation. Inertinite serves as the gold standard for organic carbon permanence, guiding this study to measure biochar's carbonization against inertinite characteristics. Analyzing the random reflectance (Ro) of biochar reveals that 76% of studied samples qualify as pure inertinite. Apart from inertinite, other organic pools in biochar, quantifiable through geochemical pyrolysis and Ro methods, affect stability. Determining the carbonization temperature offers insights into biochar's efficiency and stability concerning production variables.

Unraveling the Potential of Electrochemical pH-Swing Processes for Carbon Dioxide Capture and Utilization.

Global warming, driven by the accumulation of anthropogenic greenhouse gases, particularly CO2, in the atmosphere, has garnered significant attention due to its detrimental environmental impacts. To combat this critical issue, the deployment of CO2 capture and utilization (CCU) strategies has been considered as one of the technology-based solutions, leading to extensive scientific and engineering research. Electrochemical pH-swing (EPS) processes offer a promising approach to diverse CCU pathways, such as the delivery of pure CO2 gas, the delivery of bicarbonate (e.g., for microalgae cultivation), and the formation of carbonate minerals. In this study, we discuss several CCU pathways using EPS and provide an in-depth analysis of its mechanisms and potential applications, outlining its limitations from both thermodynamic and kinetic standpoints. The EPS process has demonstrated remarkable capabilities, achieving a CO2 capture efficiency of over 90% and unlocking valuable opportunities for CCU applications. We also develop an initial techno-economic assessment and provide the perspectives and challenges for future development and deployment of EPS. This study sheds light on the integration of EPS with CCU, closing the carbon cycle by effectively utilizing the products generated through the process, such as carbonate minerals and bicarbonate solution. For instance, the bicarbonate product can serve as a viable feedstock for bicarbonate-based microalgae production systems, with the added benefit of reducing costs by 40-80% compared to traditional gaseous CO2 delivery approaches. By integration of electrochemical technologies with CCU methods, this study underscores the immense potential for mitigating CO2 emissions and advancing sustainable practices to combat global warming. This study not only addresses the urgent need for effective solutions but also paves the way for a greener and more sustainable future.

Mars' atmosphere, volatiles, and climate as the sun heats up over the next 6 billion years

As the solar luminosity continues to increase over the next 6 billion years, the Martian surface will heat up to above the melting temperature of water ice. Water ice currently in the polar caps and ground ice will melt, potentially repopulating crater lakes or a very small ocean, with the abundance possibly enhanced due to diffusion upward of water currently locked in the deep crust. CO2 adsorbed in the regolith and locked up in the south-polar ice cap will diffuse into the atmosphere, providing up to 50 mbar total pressure; this will further increase the temperature via greenhouse warming. There are two end-member scenarios for the climate under these conditions: (i) Surface water could drive an atmospheric water cycle somewhat analogous to present-day Earth's, which would create a global clement climate conducive to the existence of widespread surface life. (ii) The widespread presence of liquid water could cause CO2 to form carbonate minerals and H2O to hydrate surface/subsurface minerals (or allow H released from water to escape to space), and CO2 and H2O could be lost to space, leaving Mars with a dry environment. The climate could end up between these end-members and also could vary with time. This uncertain climate end state informs our view that exoplanet evolution and habitability can be driven by endogenous processes associated with a terrestrial planet as well as by the ability of EUV and a stellar wind from the host star to strip away atmosphere.

Semiarid Lakes of Southwestern Siberia as Sentinels of On-Going Climate Change: Hydrochemistry, the Carbon Cycle, and Modern Carbonate Mineral Formation

Towards a better understanding of factors controlling carbon (C) exchange between inland waters and atmosphere, we addressed the inorganic carbon cycle in semiarid lakes of Central Eurasia, subjected to the strong impact of on-going climate change. As such, we assessed the hydrochemical variability and quantified its control on the formation of authigenic carbonate minerals, occurring within the upper layer of sediments in 43 semiarid lakes located in the southwest of Western Siberia (Central Eurasia). Based on measurements of pH, total dissolved solids (TDS), cationic and anionic composition, dissolved organic and inorganic C, as well as textural and mineralogical characterization of bottom sediments using X-ray diffraction and scanning electron microscopy, we demonstrate that lake water pH and TDS are primarily controlled by both the lithological and climatic context of the lake watershed. We have not revealed any direct relationships between lake morphology and water chemistry. The most common authigenic carbonates scavenging atmospheric CO2 in the form of insoluble minerals in lake sediments were calcite, aragonite, Mg-calcite, dolomite and hydromagnesite. The calcite was the most common component, aragonite mainly appears in lakes with sediments enriched in gastropod shells or artemia cysts, while hydromagnesite was most common in lakes with high Mg/Ca molar ratios, as well as at high DIC concentrations. The relationships between mineral formation and water chemistry established in this study can be generalized to a wide suite of arid and semiarid lakes in order to characterize the current status of the inorganic C cycle and predict its possible modification under on-going climate warming such as a rise water temperature and a change in hydrological connectivity, primary productivity and nutrient regime.