Search Results (26)

This study investigates the impact of different temperatures and initial Mg²⁺/Ca²⁺ molar ratios in the solution on the wet-accelerated carbonation of β-dicalcium silicate (β-C₂S). The x-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), thermogravimetric analyzer (TGA), and field emission scanning electron microscopy (FE-SEM) analysis results indicated that temperature and the Mg²⁺/Ca²⁺ molar ratio are key factors in the nucleation of aragonite. Aragonite formed at a temperature above 60 °C, and the high temperature promoted the crystallinity of needle-like aragonite with a length of 1–6 μm and a diameter of ~1 μm. Moreover, 80 °C was the most favorable temperature for the formation of aragonite with a large aspect ratio in the carbonation system of β-C₂S. Mg²⁺ had a significant effect on inhibiting the transformation of aragonite to calcite and promoting the stability of aragonite. Aragonite became the dominant CaCO₃ polymorph instead of calcite when the Mg²⁺/Ca²⁺ molar ratio was above 1.0, and pure aragonite-style calcium carbonate was formed at a Mg²⁺/Ca²⁺ molar ratio of 1.5. Full article

Aragonite calcium carbonate (CaCO₃), derived from cockle shell waste, was successfully used as a renewable calcium source to synthesize calcium citrate (CCT) using citric acid (C₆H₈O₇). The three CCT products (CCT-2, CCT-3, and CCT-4) were prepared using three different acid concentrations: 2, 3, and 4 M. The physicochemical characteristics of the newly synthesized CCT were investigated. Fourier-transform infrared (FTIR) spectra revealed the vibrational modes of the citrate anionic group (C₆H₅O₇³⁻), which preliminarily confirmed the characteristics of CCT. However, X-ray diffraction (XRD) revealed that the concentration of citric acid altered the structural property and the chemical formula of the synthesized CCT. Employing 2 M citric acid, a pure tetra-hydrated phase (Ca₃(C₆H₅O₇)₂·4H₂O, earlandite mineral) was obtained. However, a mixture of hydrated (Ca₃(C₆H₅O₇)₂·4H₂O) and anhydrous (Ca₃(C₆H₅O₇)₂) phases was precipitated when 3 and 4 M citric acid was used in the preparation process. The lower mass loss observed in the thermogravimetric analysis (TGA) of CCT-3 and CCT-4 compared to that of CCT-2 further confirmed that CCT-3 and CCT-4 were composed of hydrated and anhydrous CCTs. The synthesized CCT decomposed in four major processes: the first dehydration, the second dehydration, CaCO₃ formation, and decarbonization, generating calcium oxide (CaO) as the final product. X-ray fluorescence (XRF) results showed that the CCT mainly consisted of CaO with a quantity of >98%. The scanning electron microscopic (SEM) image revealed the irregular plate-like CCT crystallites. The concentration of citric acid is a key factor that influences the productive parameters of CCT, including production yield, reaction time, and solubility. 2 M citric acid provided the optimal balance between productivity and cost-effectiveness, with the highest yield and soluble fraction and the lowest reaction time. The results suggest that the preparation of CCT from cockle shell waste can potentially replace the use of commercial calcite from mining, which is a limited and non-renewable resource. Full article

Mineral scaling and corrosion pose significant challenges in groundwater distribution, increasing hydraulic resistance, reducing flow rates, and raising operational costs. Magnetic water treatment (MWT) has gained attention as a non-chemical method to mitigate scale formation by promoting the transformation of calcite, a hard and adherent CaCO₃ polymorph, into aragonite, a softer and less adherent form. In Chihuahua, Mexico, mineral scaling has disrupted the drinking water distribution system, reducing flow and impairing service. This study evaluates MWT’s potential to mitigate scaling by analyzing magnetized water treated under various MWT configurations. Comparative analyses were conducted via XRD and SEM to assess changes in calcium carbonate polymorphs. Finite element method (FEM) simulations in COMSOL Multiphysics 6.0 were used to evaluate the magnetic field distribution. The results show no systematic trend in CaCO₃ polymorph transformation following MWT exposure, and FEM simulations indicate negligible magnetic field gradients in certain configurations. These findings highlight the critical role of optimizing magnetic field alignment and gradient strength. Future research should refine MWT configurations and incorporate real-time monitoring to enhance its effectiveness in scale prevention. Full article

In the prehistoric period on the Balkan Peninsula, the technology of white decoration underwent a drastic change. At the beginning of the Neolithic white pigment was applied as paint on a polished surface. At the end of the epoch, white paste was inlaid in incised channels on the surfaces of vessels. This study is focused on the identification of mineral pigments used for white decoration of Neolithic and Chalcolithic pottery from the territory of Bulgaria. The aim of this work is to answer the question of whether the composition of the white pigment varies according to the technique of decoration (paint and inlay). A set of 41 pottery fragments from 11 archaeological sites on the territory of Bulgaria was analyzed utilizing two spectroscopic techniques: laser-induced breakdown spectroscopy (LIBS) and Fourier-transform infrared spectroscopy (FTIR). Additionally, the experimental data from the LIBS were statistically treated with the multivariate technique, principal component analysis (PCA). The results from the spectral analysis indicated that the main constituent in the white decorated sherds is calcite in various combinations with carrier materials like quartz, feldspars, and metal oxides. The statistical analysis revealed that the primal constituent in the inlaid sherds is calcite while in the painted part, the carrier material is dominant. In some particular sherds, gypsum, hydroxylapatite, kaolinite, and aragonite were also detected. Full article

Powdered biogenic calcium carbonate from butter clams shows variations in its tendency to convert from aragonite to calcite when suspended in water, depending on whether the suspension has additional calcite or not. Our investigations treat these biogenic samples as complex hierarchical materials, considering both their mineral and organic components. We assess the mineral composition from Attenuated Total Reflection Fourier Transform Infrared spectroscopy peak shifts, as well as quantitative assessments of lattice constant refinements (powder X-ray diffraction). To isolate the mineral portions, we compare results from samples where the periostracum is removed mechanically and samples that are heated to temperatures that are sufficient to remove organic material but well below the temperature for thermal phase conversion from aragonite to calcite. The results show that the total organic content does not play a significant role in the aqueous mineral phase conversion. These results have potential implications for understanding carbonate mineral interactions in ocean sediments. Full article

Microbial mineralization of calcium–magnesium carbonate has been a hot research topic in the fields of geomicrobiology and engineering geology in the past decades. However, the formation and phase transition mechanism of calcium–magnesium carbonate polymorphs at different Mg/Ca ratios still need to be explored. In this study, microbial induced carbonate mineralization experiments were carried out for 50 days in culture medium with Mg/Ca molar ratios of 0, 1.5, and 3 under the action of Curvibacter sp. HJ-1. The roles of bacteria and the Mg/Ca ratio on the mineral formation and phase transition were investigated. Experimental results show that (1) strain HJ-1 could induce vaterite, aragonite, and magnesium calcite formation in culture media with different Mg/Ca molar ratios. The increased stability of the metastable phase suggests that bacterial extracellular secretions and Mg²⁺ ions inhibit the carbonate phase-transition process. (2) The morphology of bacteriological carbonate minerals and the formation mechanism of spherical minerals were different in Mg-free and Mg-containing media. (3) The increased Mg/Ca ratio in the culture medium has an influence on the formation and transformation of calcium–magnesium carbonate by controlling the metabolism of Curvibacter sp. HJ-1 and the activity of bacterial secretion. Full article

In this study, a circulating water experimental system was constructed to investigate the scale inhibition, scale removal, corrosion inhibition, and disinfection effects of industrial circulating water under the combined action of electromagnetic and electrochemical fields. The influence of these effects on water quality parameters and their scale inhibition and corrosion inhibition effects on hanging plate experiments were examined. Qualitative and quantitative analyses of scale samples were conducted using XRD (X-ray diffraction) and SEM (scanning electron microscopy), along with the evaluation of changes in water quality parameters (such as conductivity, hardness, Chemical Oxygen Demand (COD), turbidity, iron ions, and chloride ions) before and after the experiments. The results showed that after 360 h of circulation experiment, at a water temperature of 30 °C, electromagnetic field frequency of 1 kHz, electrochemical scale removal device voltage of 24 V, current of 10 A, and water flow rate of 0.6 m/s, the transformation of calcite to aragonite in CaCO₃ scale samples occurred, with a 76.6% increase in aragonite content. Moreover, the conductivity decreased by 11.6%, hardness decreased by 42.0%, COD decreased by 59.7%, turbidity decreased by 48.1%, and chloride and iron ion concentrations decreased by 36.6% and 63.1%, respectively. The scale inhibition efficiency reached 53.8%, surpassing the effects of electromagnetic and electrochemical actions individually. These findings demonstrate that the combined action of electromagnetic and electrochemical fields can effectively enhance scale inhibition, scale removal, corrosion inhibition, and disinfection and algae removal effects. Full article

Microbially induced carbonate precipitation (MICP), a widespread phenomenon in nature, is gaining attention as a low-carbon alternative to ordinary Portland cement (OPC) in geotechnical engineering and the construction industry for sustainable development. In the Philippines, however, very few works have been conducted to isolate and identify indigenous, urease-producing (ureolytic) bacteria suitable for MICP. In this study, we isolated seven, ureolytic and potentially useful bacteria for MICP from marine sediments in Iligan City. DNA barcoding using 16s rDNA identified six of them as Pseudomonas stutzeri, Pseudomonas pseudoalcaligenes, Bacillus paralicheniformis, Bacillus altitudinis, Bacillus aryabhattai, and Stutzerimonas stutzeri but the seventh was not identified since it was a bacterial consortium. Bio-cementation assay experiments showed negligible precipitation in the control (without bacteria) at pH 7, 8, and 9. However, precipitates were formed in all seven bacterial isolates, especially between pH 7 and 8 (0.7–4 g). Among the six identified bacterial species, more extensive precipitation (2.3–4 g) and higher final pH were observed in S. stutzeri, and B. aryabhattai, which indicate better urease production and decomposition, higher CO₂ generation, and more favorable CaCO₃ formation. Characterization of the precipitates by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) and attenuated total reflectance Fourier transform spectroscopy (ATR-FTIR) confirmed the formation of three carbonate minerals: calcite, aragonite, and vaterite. Based on these results, all six identified indigenous, ureolytic bacterial species from Iligan City are suitable for MICP provided that the pH is controlled between 7 and 8. To the best of our knowledge, this is the first report of the urease-producing ability and potential for MICP of P. stutzeri, P. pseudoalcaligenes, S. stutzeri, and B. aryabhattai. Full article

Herein, activated red mud particles are used as adsorbents for phosphorus adsorption. HCl solutions with different concentrations and deionized water are employed for desorption tests, and the desorption mechanism under the following optimal conditions is investigated: HCl concentration = 0.2 mol/L, desorbent dosage = 0.15 L/g, desorption temperature = 35 °C, and desorption time = 12 h. Under these conditions, the phosphate desorption rate and amount reach 99.11% and 11.29 mg/g, respectively. Notably, the Langmuir isothermal and pseudo-second-order kinetic linear models exhibit consistent results: monomolecular-layer surface desorption is dominant, and chemical desorption limits the rate of surface desorption. Thermodynamic analysis indicates that phosphorus desorption by the desorbents is spontaneous and that high temperatures promote such desorption. Moreover, an intraparticle diffusion model demonstrates that the removal of phosphorus in the form of precipitation from the surface of an activated hematite particle adsorbent primarily occurs via a chemical reaction, and surface micromorphological analysis indicates that desorption is primarily accompanied by Ca dissolution, followed by Al and Fe dissolutions. The desorbents react with the active elements in red mud, and the vibrations of the [SiO₄]⁴⁻ functional groups of calcium–iron garnet and calcite or aragonite disappear. Further, in Fourier-transform infrared spectra, the intensities of the peaks corresponding to the PO₄³⁻ group considerably decrease. Thus, desorption primarily involves monomolecular-layer chemical desorption. Full article

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. Full article

Biomineralization is a universal process that has implications in a variety of areas, from civil engineering to medicine. While crystallization of amorphous CaCO₃ formed in vitro is known to precede the vaterite-calcite/aragonite pathway, this process could be significantly altered when induced by bacteria, particularly within the extracellular matrix (ECM) of microbial cells. We used a combination of SEM, SANS, SAXS, FTIR and XRD methods to investigate the structure of CaCO₃ formed during biomineralization induced by planktonic Bacillus cereus. Formation of precipitates in the presence of CaCl₂ and urea was observed both during bacterial growth and in the medium devoid of bacteria and ECM (cell-free system). The pathway for polymorphic transformations of CaCO₃ from the amorphous phase to vaterite and further to calcite was confirmed for the bacterium-induced mineralization and did not depend on the concentration of Ca²⁺ and urea. The structure of CaCO₃ sediments differed when formed in cell-free and bacterial systems and varied depending on time and the medium composition. The rate of precipitation was accelerated in the presence of DNA, which had little effect on the solid phase structure in the cell-free system, while strongly affecting the structure and polymorphic composition of the precipitates in bacterial culture. Full article

While heating a seawater spiral shell (Euplica scripta), thermally induced aragonite–calcite (A–C) transformation occurred within the temperature region of multistep thermal dehydration. Here, the kinetic interplay between the A–C transformation and thermal dehydration was studied as a possible cause of the reduction in the A–C transformation temperatures. The kinetics of the A–C transformation was systematically investigated under isothermal conditions by powder X-ray diffractometry and under linear nonisothermal conditions by Fourier transform infrared spectroscopy. The thermal dehydration was characterized as a partially overlapping, three-step process by thermogravimetry–differential thermal analysis coupled with mass spectroscopy for the evolved gases. The A–C transformation occurred in the temperature range of the final part of the second dehydration step and the initial part of the third dehydration step. The kinetics of A–C transformation and thermal dehydration were characterized by contracting geometry-type models, in which the respective transformations were regulated by a constant linear advancement rate and diffusional removal of water vapor, respectively. Based on the kinetic results, the mutual interaction of those thermally induced processes is discussed as a possible cause of the reduction in the A–C transformation temperature. Full article

Calcium isotopes of carbonate rocks can trace calcium cycles and record changes in the marine environment. As published calcium isotope profiles of carbonate rocks at the Permian-Triassic boundary are rare, comparative studies on deep-water profiles were lacking for the major extinction event that occurred during this time. We present sections of different water depths in the Chibi area of southern China that we have selected for a comparative study. We analyzed carbon isotopes, calcium isotopes, as well as major and trace elements of carbonates from two sections (Chibi North and Chibi West) to obtain information on the volcanic activity, ocean acidification, as well as sea level rise and fall in the Chibi area during the mass extinction period. All carbon and calcium isotopes of carbonates from both sections are all negative after the mass extinction boundary. Carbonates from the Chibi North section have higher δ^44/40Ca values and lower Sr/Ca ratios than the rocks from the Chibi West section. We propose that the negative bias of the calcium isotopes in the two sections result from diagenesis. Diagenesis transforms primary aragonite into calcite, showing the characteristics of high δ^44/40Ca value and low Sr/Ca. By comparing our data with three published profiles of shallow-water carbonate rock, we recognize that calcium isotopes record gradients at different water depths. In the slope environment, the enhancement of pore fluid action near the coast caused an increase of the fluid buffer alteration, and we propose that a regression event occurred in the Chibi region during the Late Permian. Full article

A multi-analytical approach is proposed for the detection and quantitative characterization of waxes in wall paintings from the Vesuvian area, in particular in the House of the Skeleton, the House of the Deer and the House of the two Atriums in Herculaneum (Italy). Different types of waxes, of animal, vegetable, mineral and artificial origin, were investigated, as reference materials, by Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy and gas chromatography coupled with mass spectrometry (GC/MS). The obtained results were compared with those found on samples from the wall paintings of Herculaneum. By non-destructive techniques, Raman and FTIR spectroscopies, waxes were generally found in the wall painting fragments investigated. A more quantitative characterization by GC/MS analysis, performed on three representative samples on the three houses, allowed highlighting the features of beeswax. In addition to beeswax, candelilla wax and an artificial wax, compatible with the formulated candelilla wax, were also detected. The presence of candelilla, a vegetable wax introduced in Europe after the sixteenth century, suggests maintenance works probably carried out with the aim of preserving the original colors of the paintings. In addition, by Raman and FTIR spectroscopies hematite and Egyptian blue pigments were identified. Calcite, aragonite and gypsum were also detected. Full article

In this study, coralline-activated materials were prepared using ball-milled coral powder as cementitious material and coral sand as fine aggregate. XRF (X-ray fluorescence) and chemical dissolution tests were carried out to determine the content and reactivity of various elements in coral powder. The compressive strength of the developed composites was evaluated at different ages, and the formation and transformation of mineral crystals in coralline-activated samples were further analyzed by XRD (X-ray diffractometer). The results show that the calcium content in coral powder was as high as 89.5% (loss on ignition). However, only 56% of the active calcium could participate in the polymerization reaction. The silicon and aluminum content was too low, and the slag addition could improve the deficiency of silicon and aluminum in coral powder. With the increase in slag content (from 0% to 50%), the compressive strength of the composites increases significantly. Nevertheless, the enhancement is not pronounced when the slag content exceeds 50%. The increase in slag amount can stimulate the transformation of calcium minerals, e.g., aragonite and calcite, into hydrated calcium silicate and calcium aluminosilicate gels, which significantly enhances the resulting compressive strength. Full article