Carbonate Crystals Research Articles

A new bioslurry-induced restoration method via biomineralization for fragmented ceramic cultural relics

This study presents a new restoration method for fragmented ceramic cultural relics using bioslurry-induced biocementation via a microbially induced calcium carbonate precipitation (MICP) process. Bioslurry is highly urease active calcium carbonate crystals, which serve as filling and cementitious material with newly induced calcite precipitation when supplying cementation solution (urea and calcium source). With the pre-filling of bioslurry and newly induced calcite crystals, the fragmented ceramic can be connected and the gap along the fracture surface can be sealed. Due to the high urease active bacteria cells embedded in bioslurry, the ceramic restoration can be completed in 24 h with the optimal concentration of cementation solution of 1.6 M. Taking the advantage of bonding effect gained from newly induced calcite precipitation, the tensile strength was improved up to 0.92 MPa through a customized tensile strength test. This is satisfactory to ensure the stability and integrity of fragmented ceramic after bioslurry-induced restoration. A demonstrative restoration has been completed on fragmented ceramics from Ming Dynasty. With the good bonding strength and high stability of bioslurry-induced calcite precipitation, the proposed bioslurry-induced restoration method contributes valuable insights to the conservation of ceramic cultural relics. Other prospective applications include the restoration of masonry relics and bone relics.

Cementor: A toolbox to generate bio-cemented soils with specific microstructures

Bio-cemented soils can exhibit various types of microstructure depending on the relative position of the carbonate crystals with respect to the host granular skeleton. Different microstructures can have different effects on the mechanical and hydraulic responses of the material, hence it is important to develop the capacity to model these microstructures. The discrete element method (DEM) is a powerful numerical method for studying the mechanical behaviour of granular materials considering grain-scale features. This paper presents a toolbox that can be used to generate 3D DEM samples of bio-cemented soils with specific microstructures. It provides the flexibility of modelling bio-cemented soils with precipitates in the form of contact cementing, grain bridging and coating, and combinations of these distribution patterns. The algorithm is described in detail in this paper, and the impact of the precipitated carbonates on the soil microstructure is evaluated. The results indicate that carbonates precipitated in different distribution patterns affect the soil microstructure differently, suggesting the importance of modelling the microstructure of bio-cemented soils.

Selection and purification of Li2CO3 precursor for bolometric double beta decay experiments

This paper describes the preparation of radiopure lithium carbonate powder for the needs of low-background research, in particular, AMoRE-II, the second phase of a search for the neutrinoless double-beta decay (0νDBD) of the 100Mo isotope using over 100 kg of 100Mo contained in 200 kg of ultra-pure Li2100MoO4 bolometric crystals. About 150 kg of pure Li2CO3 powder is required to synthesize the crystals. The desired radiopurity for the lithium powder is 40K below 100 mBq/kg, and Th/U and Ra are at a few mBq/kg. Several commercially available powders were tested with ICP-MS and HPGe detectors at the Center for Underground Physics (CUP) of the Institute for Basic Science in Korea. The lowest purity of the tested products was 99.99%. The results of the powders’ radioassay at CUP showed that none of the tested products were suited for the 0νDBD search application. A special purification technology had to be developed to remove the original contamination of the powder with potassium (K), thorium (Th), uranium (U), and radium (Ra). Lithium carbonate crystallization via carbonization technique was inefficient in removing radiochemical impurities. Lithium formate fractional recrystallization effectively removed Ra, K, and Th, but the synthesis of the final lithium carbonate product had a low yield and required the introduction of additional chemicals. The analysis results of raw and purified powders, the decontamination efficiency, and plans are described in the article.

Relative Strength of Polycation Adsorption on Oxide Surfaces.

Polyelectrolyte adsorption onto surfaces is widely employed in water treatment and mining. However, little is known of the relative interaction strengths between surfaces and polymer. This fundamental property is assumed to be dominated by electrostatics, i.e., attractive interactions between opposite charges, which are set by the overall ionic strength ("salt concentration") of the solution, and charge densities of the surface and the polymer. A common, counterintuitive finding is a range of salt concentrations over which the amount of adsorbed polyelectrolyte increases as electrostatic interactions are tempered by the addition of salt. After an adsorption maximum, higher salt concentrations then produce the expected gradual desorption of polyelectrolyte. In this work, the salt response of the adsorption of the same narrow molecular weight distribution polycation, poly(N-methyl-4-vinylpyridinium), PM4VP, to a variety of surfaces was explored. Oxide powders for adsorption included Al2O3, SiO2, Fe2O3, Fe3O4, TiO2, ZnO, and CuO. Planar surfaces included silicon wafers, mica, calcium carbonate, and CaF2 single crystals. The PM4VP was radiolabeled with 14C so that sensitive, submonolayer amounts could be detected. The position of the peak maximum, or the lack of a peak, in response to added salt was used to rank the electrostatic component of the interaction. The importance of charge regulation, a shift in the surface pKa in response to solution species, was highlighted as a mechanism for adsorption on the "wrong" side of the isoelectric point and also as a factor contributing to the difficulty of reaching the totally desorbed state even at the highest salt concentrations.

Microstructural Evolution of Calcium Sulfoaluminate Cement during the Wet-Carbonation Process

Calcium sulfoaluminate (CSA) cement, as a type of low-carbon cement, can contribute to further reduction in carbon emissions with carbonation technologies. However, the detailed microstructure development of CSA cement during the carbonation process has been rarely analyzed. In this paper, wet carbonation was applied to CSA cement to investigate the microstructure evolution of carbonation products and carbon absorption capacity of CSA cement by means of pH measurement, X-ray diffraction (XRD) measurement, thermogravimetric (TG) measurement, Fourier-transformed infrared spectroscopy (FT-IR) measurement and scanning electron microscope measurement. During the carbonation process, the formed ettringite product and the dicalcium silicate clinker were carbonated immediately to generate calcium carbonate crystals, silica gel and aluminum hydroxide (AH3) gel. With the trend of pH increasing first and notably decreasing later, the coupling interaction between the hydration and carbonation reactions of CSA cement was revealed. From the XRD and TG results, three types of calcium carbonate crystal forms (calcite, vaterite and aragonite) were detected, and the content of calcium carbonate increased with the increase in carbonation time. FT-IR analysis further confirmed the existence of calcium carbonate, silica gel and AH3 gel with their characteristic vibrations. Moreover, the microstructure of carbonation products with different morphologies was observed. The application of wet carbonation to CSA cement provides a more comprehensive insight to the carbonation mechanism of this low-carbon cement.

Characteristics and evolution of quartz-calcite-sulfide veins in the Nazca-Ocoña belt, Peru

The Nazca-Ocoña metallogenic belt in southern Peru host about 70 recognized Au-Ag and base metal (Pb-Cu-Zn) deposits such as Orión, Caravelí, Ishihuica, Calpa, Arirahua, Mollehuaca, and San Juan de Chorunga. These deposits are spatially associated with Cretaceous intrusive rocks of the coastal Batholith in a zone that extends more than 350 km along the Central to Southern part of Peru. Gold and silver are structurally controlled in mineralized NW-SE, N-S and W-E-trending fault-fill veins that are less than one-meter wide, crosscutting granodiorite and diorite bodies. The origin of the veins is still debated, and they may be classified as intrusion-related gold deposits (IRGD), orogenic or mesothermal deposits. In this study, we focus on two representative deposits in the Nazca-Ocoña metallogenic belt: Mollehuaca and San Juan de Chorunga. At both sites, the mineralization is composed of quartz-calcite sulfide veins hosted in Cretaceous Coastal Batholith intrusions. Petrographic and chemical analyses on pyrite were performed with field-emission scanning electron microscopy (FE-SEM), electron microprobe analysis (EMPA), nano-scale secondary ion mass spectrometry (NanoSIMS), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).Native gold and Au-rich silver are disseminated throughout the veins as micro to sub-micron inclusions in pyrite and chalcopyrite, and in pyrite as cavity and fracture fill. The are three pyrite generations and these have complex internal zonation and are host to precious (Au, Ag) and base metals (Co, Ni, Cu) metals, and also metalloids (As, Sb) as lattice-bound impurities and micron inclusions. The San Juan de Chorunga pyrite has δ34S values ranging from 0.4 to 1.4 ‰, and the Mollehuaca pyrite δ34S from 5.8 to 7.4 ‰. In both San Juan de Chorunga and Mollehuaca, the highest Au concentrations occur in pyrite zones with the heaviest δ34S values. Fluid inclusion petrography of these veins shows recrystallized, wispy quartz with implosion and explosion fluid inclusion textures, indicative of pressure variations during quartz vein formation. The presence of CO2 in these inclusions requires mid-crustal pressure conditions. However, the main stage of gold mineralization occurs with carbonate, chlorite, and euhedral quartz crystals lacking post-entrapment recrystallization textures or CO2. Our observations suggest that most of the gold in these veins formed in association with a shallower hydrothermal event, potentially in association with the emplacement of batholiths and shallower intrusions in the Late Cretaceous.

Effect of pitch crystallinity on electrochemical performance of graphite carbon coatings

Natural graphite has been primarily used as an active anode material for lithium-ion batteries, and carbon coatings are commonly used to enhance its performance. Pitch has been proposed as a promising material for carbon coatings, but it comprises various chemical species and cannot be regarded as a single substance. Consequently, different types of pitch variably alter the electrochemical properties of the graphite carbon coating. In this study, we focus on the relationship between the crystallinity and electrochemical performance of the carbon coating layer, which is formed based on the optical properties of pitch and can be categorized as isotropic or mesophase. To apply the pitch onto the natural graphite, a dry coating method was employed and it was then heat-treated with a temperature range of 900–1700 °C. Both carbon coatings enhanced the initial Coulombic efficiency by reducing the edge plane of natural graphite. In particular, the carbon layer coated with an isotropic pitch exhibited a disordered structure, thereby improving the output characteristics. The synergistic effect of the conductivity of the carbon coating layer and the amorphous arrangement of the carbon crystals provided a pathway for ion diffusion, effectively reducing the polarization resistance that arose during the charge and discharge cycles. This report establishes a connection between graphite-coated carbon layers and electrochemical performance and provides a novel evaluation of the properties of coating pitches that are in high demand for commercial applications.

Searching for microbial contribution to micritization of shallow marine sediments.

Micritization is an early diagenetic process that gradually alters primary carbonate sediment grains through cycles of dissolution and reprecipitation of microcrystalline calcite (micrite). Typically observed in modern shallow marine environments, micritic textures have been recognized as a vital component of storage and flow in hydrocarbon reservoirs, attracting scientific and economic interests. Due to their endolithic activity and the ability to promote nucleation and reprecipitation of carbonate crystals, microorganisms have progressively been shown to be key players in micritization, placing this process at the boundary between the geological and biological realms. However, published research is mainly based on geological and geochemical perspectives, overlooking the biological and ecological complexity of microbial communities of micritized sediments. In this paper, we summarize the state-of-the-art and research gaps in micritization from a microbial ecology perspective. Since a growing body of literature successfully applies in vitro and in situ 'fishing' strategies to unveil elusive microorganisms and expand our knowledge of microbial diversity, we encourage their application to the study of micritization. By employing these strategies in micritization research, we advocate promoting an interdisciplinary approach/perspective to identify and understand the overlooked/neglected microbial players and key pathways governing this phenomenon and their ecology/dynamics, reshaping our comprehension of this process.

Fluid Evolution of Greisens from Krupka Sn-W Ore District, Bohemian Massif (Czech Republic)

The Sn-W ore deposits in the Krupka surroundings are associated with greisens, which occur in the upper parts of Late Variscan granitoid intrusions. Fluid inclusions were studied in samples of quartz, cassiterite, apatite, fluorite, and topaz in greisenized granites, greisens, and hydrothermal veins with Sn-W mineralization. The greisenization process took place at temperatures 370–490 °C and pressures 155–371 bars, and associated fluids had predominantly low salinity and a low gas (CO2, N2 and CH4) content. The post-greisenization stage was connected with the formation of (i) low-salinity (0–8 wt. % NaCl eq.) fluid inclusions with homogenization temperatures <120–295 °C and (ii) high-salinity (18 to >35 wt. % NaCl eq.) fluid inclusions with homogenization temperatures 140–370 °C, often containing trapped crystals of quartz, topaz, and sulfides, or daughter crystals of salts and carbonates, which were identified by microthermometric measurements, electron microprobe analysis, and Raman spectroscopy. Analyses of fluid inclusion leachates have shown that Na and Ca chlorides predominate in fluids. According to hydrogen stable isotopes, the source of greisenizing and post-greisenizing fluids was not only magmatogenic but also meteoric water or fluids derived from sedimentary rocks.

Didymium arenosum, a myxomycete new to science from the confluence of deserts in northwestern China.

A new myxomycete species, Didymium arenosum, was described based on morphological evidence and phylogenetic analyses. The species was discovered in the arid region at the confluence of the Badain Jaran desert and Tengger desert on the leaves of Betula platyphylla and was cultivated in a moist chamber culture. Morphologically, the species is distinguished by the greenish-yellow calcium carbonate crystals on the surface and the spores covered with small warts, some of which are connected into a short line. A phylogenetic analysis of D. arenosum strongly supports its classification as a separate clade. The spore to spore agar culture of D. arenosum requires 23 days, and this study provides a detailed description of its life cycle.

Purification of Produced Water from a Sour Oilfield in South Kuwait. 2. Oil-Water Separation and Crystallization of Calcium Carbonate

Purification of Produced Water from a Sour Oilfield in South Kuwait. 2. Oil-Water Separation and Crystallization of Calcium Carbonate

Systematic comparisons of preparative protocols to generate various types of stone-related crystals for in vitro study of renal calculi

In vitro studies of stone-related crystals and crystals-cell interactions have been extensively done to investigate cellular, molecular and pathogenic mechanisms leading to renal calculi. Effective preparation of various types of stone-related crystals is thus crucial for such studies. Nevertheless, various protocols for preparing these stone-related crystals were scatteredly reported without comparative analysis of their efficacies and yields. Herein, we systematically compared our protocols (with the suffix “-Si”) for preparing calcium oxalate (CaOx) monohydrate (COM), CaOx dihydrate (COD), magnesium ammonium phosphate (struvite), uric acid (UA), calcium phosphate dihydrate (brushite), hydroxyapatite (HAP), and calcium carbonate (CaCO3) crystals with other protocols published previously. The morphological evaluation revealed that our protocols provided the most homogeneous and most typical monoclinic prismatic, bipyramidal, coffin lid and rectangle shapes of COM, COD, struvite and UA crystals, respectively. There were comparable morphological results for brushite, HAP and CaCO3 crystals generated by different protocols. Our protocols provided the greatest yield for generating brushite crystals but with lower yields for others. Chemical analysis by Fourier transform infrared (FTIR) spectroscopy revealed comparable results among different protocols to generate each crystal type. In summary, all these protocols can be used to generate each crystal type. But our protocols offer the best quality, in terms of homogeneity and typical shape, for generating COM, COD, struvite and UA crystals.

Prediction of pure carbon crystals with intrinsic antiferromagnetism: polymerized from C20 fullerenes.

Pure carbon materials with magnetic properties have attracted considerable research interest due to their advantages over traditional magnetic materials. Nevertheless, such materials are exceedingly rare. Disrupting the Kekulé valence structures in carbon materials potentially leads to the emergence of magnetism. In this study, using first principles calculations, we developed a range of pure carbon allotropes derived from the smallest fullerene C20 which potentially disrupts the Kekulé valence structures after polymerization. The results indicate that some of the allotropes disrupting the Kekulé valence structures exhibit intrinsic antiferromagnetic ordering, and the magnetism originates from the presence of isolated three-fold coordinated C atoms. The other allotropes adhering to the Kekulé valence structures show non-magnetism with all three-fold coordinated C atoms forming dimers. In all magnetic polymers, magnetism arises from unpaired electrons on the isolated three-fold coordinated carbon atoms, with magnetic moments of about 0.40μB at these sites. The adsorption of dopant atoms can significantly alter the magnetic properties of polymers, for instance, the C20-71 polymer with Immm symmetry undergoes a transition from non-magnetic to anti-magnetic ordering upon adsorption of hydrogen atoms. Electronic calculations indicate that these polymers display a range of electronic properties, encompassing both metallic and semiconducting characteristics. Notably, certain magnetic phases exhibit superhard properties, with the hardness value exceeding 40 GPa. This study presents a potential method for designing magnetic carbon materials. Specifically, certain compounds address the gap in magnetic superhard materials composed of light elements, and can be utilized in the field of spintronics where traditional superhard materials are unsuitable.

Surface Treatment of Rammed Earth Heritage Sites Using MICP Technology: An Investigation of Rainwater Erosion Resistance via Indoor Experiments and In Situ Testing

Rammed earth, a commonly used building material in ancient times, differs from natural sedimentary layers in that it is more compact. Buildings constructed from historical rammed earth sites frequently encounter the issue of rainwater erosion. Microbially induced calcium carbonate precipitation (MICP) is commonly applied to sand soil treatment, yet reports on its use for stabilizing rammed earth are scarce. This study focused on the rammed earth of the Shanhaiguan Great Wall and explored the efficacy of MICP in mitigating rain erosion through permeation tests, splash experiments, and scouring trials. The findings indicate that the forms of rain erosion damage under MICP treatment vary across different operational conditions. In laboratory experiments, as the concentration of the cementation solution increases, the amount of calcium carbonate crystals also increases. However, the permeability, splash resistance, and rain erosion resistance initially increase and then decrease. When the cementation solution concentration is 1.0 mol/L, the penetration rate is the highest, lasting 712.55 s. The splash pit rate is the lowest, at only 1.2 mm, and the soil erosion rate is the lowest, at only 4.13%. The rain erosion resistance in the field test exhibit the same trend, and the optimal concentration is 1.2 mol/L. The optimal concentration mechanism involves the aggregation of calcium carbonate crystals at suitable cementation solution concentrations, which begin to fill the soil particle pores, effectively resisting rainwater erosion. At lower concentrations of the cementation solution, calcium carbonate crystals are merely adsorbed by soil particles without blocking the pores. Due to the high compressibility of rammed earth, which results in lower porosity, a higher concentration of the cementation solution leads to rapid pore clogging by excessive calcium carbonate crystals, which accumulate on the surface to form a white crust layer. The MICP technique can effectively alleviate rainwater erosion in rammed earth, and the optimal concentration needs to be tailored to the porosity of the rammed earth. This mechanism was also validated in field scouring experiments on the Shanhaiguan Great Wall’s rammed earth.

Project M: investigating the effect of additives on calcium carbonate crystallisation through a school citizen science program

Crystallisation pathways of calcium carbonate are strongly influenced by the presence of additives. Through X-ray diffraction, samples made by the Project M Scientists reveal the effect of amino acid and related additives on the crystal structures of calcite and vaterite.

Triaxial compression test of MICP sand column and simulation of failure process

Microbially induced calcium carbonate precipitation (MICP) technology can induce calcium carbonate crystals with cementation and stable performance in the process of microbial metabolism or enzymization through the regulation of environmental factors MICP can be used as a cementing agent to cement cohesionless sand particles to form the materials with the characteristics of higher strength, better durability and environmental friendliness, as well as a good engineering application prospect. In this paper, the shear strength of sand column was tested by triaxial compression tests, and the strength index was obtained. In order to further study the micro-strength mechanism and the failure process, based on the discrete element method, a numerical model of MICP cemented sand column was established considering the factors of matrix soil particle gradation, particle morphology, content ratio of induced calcium carbonate, pore distribution characteristics, inter-particle cementation and so on. The failure process of MICP cemented sand column under load was analysed by numerical simulation, and the reliability of the numerical model was tested by combining with the stress intensity curve of samples under test conditions. The results indicate that compared with the actual triaxial tests of MICP cemented sand column, although there are deviations in stress and strain, cohesion and internal friction angle, the numerical simulation shows similar development law and intensity amplitude, and the same failure trend. The work in this paper verifies the reliability of the numerical model and provides a theoretical basis for the subsequent analysis of the factors influencing the geotechnical mechanical properties of biomineralized materials.

The smallest Schwarzite carbon with only heptagonal carbon rings.

Carbon materials with full sp2-hybridized buckling is a major challenge pervading fundamental nanoscience and nanotechnology research. Carbon atoms that are sp2 hybridized prefer to form hexagonal rings, such as in carbon nanotubes and graphene, which are low-dimensional materials. The incorporation of heptagonal, octagonal, and/or larger rings into a hexagonal sp2 carbon meshwork has been identified as a strategy for assembling three-dimensional (3D) sp2 carbon crystals, and one of the typical representatives are Schwarzite carbons, which possess a negative surface Gaussian curvature as well as unique physical properties. Herein, a 3D Schwarzite carbon consisting of only sp2-buckled heptagonal carbon rings, which is referred to as Hepta-carbon, is proposed based on first-principles calculations. Hepta-carbon is mechanically and thermodynamically stable, and energetically more favourable than experimental graphdiyne, fullerene C20 and most Schwarzite carbons under ambient conditions. Molecular dynamics simulations indicate that Hepta-carbon exhibits high-temperature thermostability up to 1500 K. Band structure and mechanical property simulations indicate that Hepta-carbon is a semi-metallic material with electron conduction and exhibits impressive mechanical properties such as high strength with quasi-isotropy, high incompressibility similar to diamonds, elastic deformation behaviour under uniaxial stress, and high ductility. Hepta-carbon presents a porous network with a low mass density of 1.84 g cm-3 and connected channels with diameters of 3.3-6.1 Å. Theoretical simulations of gas adsorption energy demonstrate that Hepta-carbon can effectively adsorb and stabilize greenhouse gases, including N2O, CO2, CH4, and SF6.

Main minerals of the Araxá alkali-carbonatite complex, Minas Gerais State, Brazil

The Araxá alkali-carbonatitic complex is a significant source of niobium and phosphate and accounts for approximately 75% of global niobium production. The complex contains magmatic niobium ore minerals, such as natrium-pyrochlore and calcium-pyrochlore, and hydrothermal niobium ore minerals in the form of kenopyrochlore and natrium-pyrochlore. The magmatic micas in the complex are tetraferriphlogopites that exhibit Mg-rich cores surrounded by one or two rims of tetraferriphlogopites formed by hydrothermal alteration. These rims have lower IVAl and Mg apfu (atom per formula unit) values but higher IVFe3+ and Fe2+ contents than the original phlogopite. Microphlogopitite dikes that formed during several episodes of magmatism between 83.48 and 77.4 Ma contain tetraferriphlogopites, phlogopite, eastonite, biotite, and annite-siderophyllite. These micas exhibit variations in Mg2+ and Fe2+ concentrations owing to the magmatic differentiation and subsequent hydrothermal alteration, resulting in rims with higher Mg and lower Fe2+ concentrations than the mica core. The Araxá complex also contains magmatic magnetite that has been further altered by hydrothermal processes, resulting in the formation of ilmenite and the oxidation and crystallization of titaniferous hematite. Magnetite within the microphlogopitites displays variations in the concentrations of Fe3+ and Ti, likely owing to the timing of the intrusion of the microphlogopitites into the Araxá complex. The degree of oxidation of the oxidized ilmenite of the Araxá complex varies based on the intrusions, which occurred before or during hydrothermal activity. Apatite is concentrated in carbonatites, which form a ring around the core of the complex, and disseminated in phlogopite-rich rocks hosting norsethite carbonatite veins in the center of the complex. The apatite in the core rocks exhibits complex zonation with unexpected changes in Ca, P, and Sr concentrations. Apatite in the carbonatite ring was generated during the differentiation of the carbonatite magma, whereas that in the core rocks exsolved from the phosphorus-saturated carbonatite magma (in press). The carbonate minerals dolomite, norsethite, and calcite exhibit compositions grouped around their end-members, suggesting that they formed during different stages of magmatic source differentiation. Strontium differentiation occurs in the magmas corresponding to each endmember, and carbocernaite is exsolved from the Sr-saturated crystals, thus forming micro-inclusions in some carbonate crystals that have been displaced by late-magmatic hydrothermal fluids.

Unveiling the Carbonation Behavior and Microstructural Changes of Magnesium Slag at 0 ℃

Magnesium slag (MS) is an industrial byproduct with high CO2 sequestration potential. This study investigates the carbonation behavior and microstructural changes of MS during wet carbonation at 0 °C. XRD, TG, FTIR, SEM, and BET techniques were used to characterize the phase composition, microstructure, and porosity of MS samples carbonated for different durations. The results showed that the main carbonation products were calcite, vaterite, and highly polymerized silica gel, with particle sizes around 1 μm. The low-temperature environment retarded the carbonation reaction rate and affected the morphology and crystallization of calcium carbonate. After 480 min of carbonation, the specific surface area and porosity of MS increased substantially by 740% and 144.6%, respectively, indicating improved reactivity. The microstructure of carbonated MS became denser with calcite particles surrounded by silica gel. This study demonstrates that wet carbonation of MS at 0 °C significantly enhances its properties, creating an ultrafine supplementary cementitious material with considerable CO2 sequestration capacity.

Damage of porous building stone by sodium carbonate crystallization and the effect of crystallization modifiers

Salt crystallization is an aggressive weathering mechanism affecting porous building materials. The extensive use of Portland cement, a source of alkalis, in modern buildings and restoration interventions makes sodium carbonate salts important weathering agents. Herein, we study salt damage to a porous stone commonly used in the Andalusian built heritage (Santa Pudia limestone) due to stress generation associated with the precipitation of natron (Na2CO3·10 H2O). We performed cyclic crystallization tests combined with thermodynamic and poromechanical calculations to determine salt crystallization pressure and effective tensile stress suffered by the material. The outcome reveals that in-pore natron crystallization during cooling/evaporation generates stresses exceeding the tensile strength of the wet substrate, leading to extensive damage by fracturing and material loss. Damage is reduced using aminotris(methylenephosphonic) acid (ATMP), a common phosphonate-based crystallization modifier that induces non-damaging efflorescence growth as opposed to damaging subflorescence growth, which takes place in its absence.