This work presents a new discussion about the vibrational properties of the carbonate ion displayed in several different environments, not only the microparameters introduced by cation substitution and different crystal lattices but also the crystal aggregation, showing how their active Raman modes are affected by these changes by using data obtained with four different laser excitation sources. New Raman spectra excited at 1064 nm are reported for calcite, aragonite, and dolomite groups, also including magnesite, witherite, rhodochrosite, siderite, malachite and azurite. These new data contribute to the discussion and understanding of these materials and their spectra, bringing new observations based on the Raman modes, focusing on the internal symmetrical and asymmetrical stretching and bending modes of the carbonate ion, highlighting the differences observed in the relative intensity and width of the bands. The results indicate some evidence of the influence of the crystal habit and/or the growth of the mineral itself in the Raman spectrum. In addition, the data show the influence of the cation substitution upon the Raman band width and that small cations contribute to less rigid crystalline structures and, consequently, larger Raman bandwidths.

The mechanism underlying microbiologically induced carbonate precipitation have not been thoroughly characterized, although numerous scholars and experts have specifically investigated questions regarding minerals induced by bacteria. The study of the precipitation of carbonate minerals induced by halophilic bacteria has aroused wide concern. The present study aimed to investigate the characterization and process of biomineralization in high salt systems by a halophilic bacterium, Chromohalobacter israelensis strain LD532 (GenBank: KX766026), which was isolated from the Yinjiashan Saltern in China. Carbonate minerals induced by LD532 were investigated in several sets of comparative experiments that employed magnesium sulfate and magnesium chloride as Mg resources. Magnesium calcite and aragonite were induced by LD532 bacteria, whereas these minerals did not appear in the control group. The mineral phases, micromorphologies, and crystal structures were analysed using X-ray powder diffraction, scanning electron microscopy, and energy dispersive X-ray detection. The carbonic anhydrase and urease secreted by strain LD532 through metabolism increased the pH value of the liquid medium and promoted the process of carbonate precipitation. Further study using high resolution transmission electron microscopy, energy dispersive X-ray detection and analysis of ultrathin slices showed that the nucleation sites of carbonate minerals were located on extracellular polymeric substances and the membranes of intracellular vesicles of LD532 bacteria, which provided favourable conditions for the growth of carbonate mineral crystals. The morphologies and compositions of minerals formed in solutions of MgSO₄ and MgCl₂ display significant differences, indicating that different sources of Mg²⁺ may also affect the physiological and biochemical activities of microorganisms and thus mineral deposition. This study will be of some interest for the interpretation of carbonate biomineralization in natural salt environments and has some value as a reference in understanding sedimentary carbonates in ancient marine environments, such as tidal flats.

Carbonate precipitation induced by microorganism has become a hot spot in the field of carbonate sedimentology, while the effect of different magnesium on biominerals has rarely been studied. Therefore, magnesium sulfate and magnesium chloride were used to investigate the significant role played on carbonate minerals. In this study, Staphylococcus epidermidis Y2 was isolated and identified by 16S rDNA homology comparison. The ammonia, pH, carbonic anhydrase, carbonate and bicarbonate ions were investigated. The mineral phase, morphology and elemental composition were analyzed by XRD and SEM-EDS. The ultrathin slices of bacteria were analyzed by HRTEM-SAED and STEM. The result showed that this bacterium could release ammonia and carbonic anhydrase to increase pH, and elevate the supersaturation via a large number of carbonate and bicarbonate ions released through carbon dioxide hydration catalyzed by carbonic anhydrase. The crystal cell density of monohydrocalcite was lower in magnesium chloride medium than that in magnesium sulfate medium. The crystal grew in a mode of spiral staircas in magnesium sulfate medium, while in a concentric circular pattern in magnesium chloride medium. There was no obvious intracellular biomineralization. This study may be helpful to further understand the biomineralization mechanism, may also provide some references for the reconstruction of paleogeological environment.

Mapping or quantitative inversion through remote sensing technology is an active way for mineral monitoring in large or uncultivated forest areas. Different spectral features of minerals, induced by ionic composition, can be identified which are related to mineral type or abundance. Based on the distinctive spectral absorption around 2.33µm induced by the carbonate ion, we use it as an analytic target to propose an improved continuum removal (ICR) algorithm to couple with normalized abundance to evaluate the relationship between continuum removal band depth (CRBD) and carbonate ion abundance. Through experimentally testing with synthetic and real image data, ICR with ratio abundance normalization can enhance the linear relation of CRBD and abundance. We find this technique performs best for abundance retrieval. The lowest root mean square error is 0.0400 for synthetic data and the mean relative error is as low as 6.80% for real image data. Compared with five other algorithms, coupling normalized carbonate mineral abundance with ICR can improve the quantitative retrieval accuracy of carbonate ion. By using a hyperspectral library, we also present a way to retrieve abundance without ground samples. These results make the quantitative inversion of mineral abundance more reasonable by distinct or enhanced features and provide great potential for use to extend mineral information extraction in the absence of sample data, even for surveys of the Moon and Mars for mineral quantitative analysis.

This study explores pressure, miscibility, and pore medium effects on heavy hydrocarbon recovery up to 65 MPa from four rock types: sand, tight sandstone, cavernous limestone, and oil sand. Results reveal MMP at 50 MPa, with peak recovery at 93% (56 MPa). Interestingly, recovery trends counter traditional expectations, notably decreasing in tight sandstone (42-56 MPa) and oil sand (50-65 MPa). Varied recoveries in cavernous limestone (25-56 MPa) highlight porosity and vug influence. Higher pressures hinder recovery due to SC-CO2's density and viscosity, favoring the immiscible process for efficient heavy hydrocarbon extraction.

Most of the current methods for stabilizing electric arc furnace (EAF) slag are time-consuming and cannot be completely stabilized. In view of this, this study aimed to apply microbial‑induced calcium carbonate precipitation (MICP) technology in the stabilization of EAF reducing slag, and this was to be achieved by using the reaction between carbonate ions and free calcium oxide (f-CaO) in reducing slag to form a more stable calcium carbonate to achieve the purpose of stabilization. The test results showed that, when the EAF reducing slag aggregates (ERSAs) were immersed in Bacillus pasteurii bacteria solution or water, the f-CaO contained in it would react such that stabilization was achieved. The titration test results showed that the f-CaO content of the ERSAs immersed in the bacterial solution and water decreased. The expansion test results of the ERSAs that were subjected to hydration showed that the seven-day expansion of ERSAs after biomineralization could meet the Taiwan regulation requirement of a less than 0.5% expansion rate. The thermogravimetric analysis showed that both the experimental group and the control group might contain calcium carbonate compounds. The results of the X-ray diffraction analysis showed that the CaCO3 content in the ERSAs that were immersed in the bacterial solution was significantly higher than those that were immersed in water. Moreover, the compressive strength test results of concrete prepared with ERSAs showed that the compressive strength of the control group concrete began to decline after 28 days. In contrast, the experimental group concrete had a good stabilization effect, and there was no decline in compressive strength until the age of 180 days. At the age of 240 days, the surface cracks of the experimental group were particularly small, while the surface of the control group showed obvious cracks. These results confirmed that a mineralization reaction with B. pasteurii bacteria could be used as a stabilization technology for ERSAs.

The interaction of poly(trimethylene carbonate) (PTMC) with alcohols were investigated as a model for polymer blending with polysaccharides. While 1-butanol, 2-butanol, ethylene glycol, 1,2-cyclohexanediol showed almost no detectable interaction with PTMC at both of solution state with 1H NMR and solid states of FT-IR, glucose and cellobiose suggests slight change of spectral pattern in FT-IR analysis. The thermal properties of the blending samples of PTMC and these alcohols were also investigated. Although the blend of PTMC with 1-butanol, 2-butanol, and ethylene glycol did not influence on thermal degradation behaviors due to the low boiling points to maintain the structure at blend sample preparation, however, the blend with PTMC and glucose or cellobiose tend to increase thermal resistances and increase glass transition temperature, hence, showed an existence of interaction through hydrogen bonding.

Two polyurethanes (PUs) were similarly synthesized by reacting a cycloaliphatic isocyanate with 1,4 butanediol and two polyols of different nature (polyester, polycarbonate diol) with molecular weights of 1000 Da. The PU made with polycarbonate diol polyol (YCD) was the only showing intrinsic self-healing at 20 °C. For assessing the mechanism of intrinsic self-healing of YCD, a structural characterization by molecular weights determination, infrared and X-ray photoelectronic spectroscopies, differential scanning calorimetry, X-ray diffraction, thermal gravimetric analysis and dynamic mechanical thermal analysis was carried out. It was concluded that the self-healing at 20 °C of YCD was due to non-covalent dynamic exchange interactions among the carbonate groups of the soft segments. Therefore, the chemical nature of the polyol played a key role in developing PUs with intrinsic self-healing at 20 °C.

In the present study, a five-year follow-up was performed by remote sensing of the calcium carbonate precipitation in La Gitana karstic lake (located on the province of Cuenca, Spain). The important role that calcium carbonate precipitation plays in the ecology of the lake is well known for its influence on the vertical migrations of phytoplankton, the concentration of bioavailable phosphorus and, therefore, the eutrophication and quality of the waters. Whiting take place between the months of July and August, and it can be studied at this time through its optical properties, with the main objective of offering updated data on a phenomenon traditionally studied and establishing possible relationships between abiotic factors such as temperature and/or rainfall. The atmospheric temperature data collected by the meteorological station suggest a possible relationship between the appearance of the white phenomenon and a pulse of previous maximum temperatures. On the other hand, no apparent relationship was found between rainfall and water bleaching.

Excessive CO₂ emissions and alternative energy fuels are two major difficult issues. The utilization of CO₂ into fine chemicals is an optimal route. Diethyl carbonate (DEC) is an extremely versatile chemical intermediate. DEC is used in gasoline, pharmaceutical, chemical and other fields. DEC synthesis from CO₂ and ethanol is a typical green synthetic route. Ni-Cu@Na₃PW₁₂O₄₀ catalysts were synthesized by two novel methods of supported and mixed. The catalyst prepared by mixed method showed nice catalytic performance. It was confirmed that water removal was the key to improving conversion efficiency. In the presence of dehydrating agent of ethylene, ethanol conversion increased from ca. 3% to ca. 40%. Propylene oxide (PO) was participated in the reaction and ethanol conversion continued to reach to ca.90% while DEC selectivity dropped by half. Under optimal conditions, our Ni-Cu@Na₃PW₁₂O₄₀ catalyst effectively solved the two major issues above.

To address the insufficient mechanical properties of calcined phosphogypsum, this research aims to investigate the utilization of basalt fiber and calcium carbonate whiskers as reinforcing agents. The study examines their impact on the flexural and compressive strength, toughness, water resistance, and tensile strength of calcined phosphogypsum. In the individual tests, basalt fibers with different lengths (3 mm, 6 mm, 9 mm, and 18 mm) were added at dosages of 0%, 0.5%, 1.0%, and 1.5% respectively. The findings demonstrate that basalt fiber effectively enhances the flexural and compressive strength, toughness, and tensile strength of calcined phosphogypsum, albeit potentially compromising water resistance. Among the various fiber lengths, the 6 mm fibers exhibit the most advantageous influence on the performance of calcined phosphogypsum. A subsequent test was conducted to investigate the impact of cross-scale fibers on the properties of calcined phosphogypsum by mixing 6 mm basalt fibers and calcium carbonate whiskers. The results illustrate that calcium carbonate whisker refines the pores, thereby improving the flexural strength and toughness of calcined phosphogypsum. Furthermore, it compensates for the water resistance limitations associated with the sole utilization of basalt fiber while further augmenting the tensile strength and strain capacity. However, it should be noted that increasing the dosage of both calcium carbonate whiskers and basalt fibers concurrently leads to increased porosity of phosphogypsum and reduced compressive strength.

Powders with phase composition including syngenite K2Ca(SO4)2·H2O and/or calcium sulfate di-hydrate (gypsum) CaSO4·2H2O were synthesized from powder of calcium carbonate CaCO3 and water solutions of potassium hydrosulfate KHSO4 of various (0.5M, 1M and 2M) concentrations. Molar ratio of starting salt KHSO4/CaCO3=2 were used to provide formation of syngenite K2Ca(SO4)2·H2O. But when using 0.5M water solution of potassium hydrosulfate KHSO4 the phase composition of synthesized powder was presented by calcium sulfate dihydrate (gypsum) CaSO4·2H2O. When using 1M and 2M water solution of potassium hydrosulfate KHSO4 the syn-genite K2Ca(SO4)2·H2O was found as predominant phase in synthesized powders. According es-timations made from thermal analysis data when 1.0M and 2.0M water solutions of potassium hydrosulfate KHSO4 were used the content of calcium sulfate dihydrate (gypsum) CaSO4·2H2O in these powders were not higher then as 7.9 and 1.9 % respectively. Phase composition of products isolated from mother liquors via water evaporation consisted of syngenite K2Ca(SO4)2·H2O and potassium sulfate (arcanite) K2SO4. Synthesized powders can be used in preparation of biocom-patible bioresorbable materials with phase composition in the K2O‑CaO‑SO3‑H2O system; as matrix of thermo- or photo-luminescent materials; as components reducing the setting time and increasing strength of sulfate cements; in the fertilizing industry and also as a components of Martian regolith simulant.

A series of supported CuO-based nanoparticle catalysts were prepared by impregnation method and used for the synthesis of glycerol carbonate from glycerol and CO2 in the presence of 2-cyanopyridine as a dehydrant and DMF as a solvent. The effects of supports (activated alumina, silicon dioxide, graphene oxide, graphene, and activated carbon), CuO loading amount, calcination temperature, and reaction parameters on the catalytic activity of catalyst were investigated in detail. XRD, FTIR, SEM, BET, and CO2-TPD were used for the characterization of the prepared catalysts. It is found that CuO/Al2O3 shows a higher catalytic activity, which depends on the CuO loading amount and calcination temperature. The surface area and amount of basic sites of the catalyst exhibit crucial effect on the catalytic activity of CuO/Al2O3. Furthermore, there is a synergistic effect between the catalyst and 2-cyanopyridine that the former has higher activation ability for glycerol and the latter acts not only as a dehydrant, but also as a promoter for CO2 activation. Recycling experiments reveal that this catalyst can be reused at least five cycles without any inactivation. Based on the experiment results and FTIR characterization, a possible reaction mechanism for the carbonylation of glycerol and CO2 is proposed.

CO₂ geological storage in deep saline aquifers was recently developed at industrial scale mainly in sandstone formations. Experiences on CO₂ injections in carbonates aquifers for permanent trapping are quite limited, mostly from US projects such as AEP Mountaineer, Michigan and Williston Basin. The behavior of fractures in carbonates plays a key role in those reservoirs in which porous matrix permeability is very poor, which drives the CO₂ plume migration through the fracture network where hydromechanics and geochemical effects take place due to injection. Hontomín (Spain) is the actual on-shore injection pilot in Europe (EP Resolution of 14 January 2014), whose reservoir is comprised of fractured carbonates. Existing experiences from field scale tests conducted on site have supported to better understand the behavior of this type of reservoirs for CO₂ geological storage. Innovative CO₂ injection strategies are being carried out in ENOS Project (EU H2020 Programme, http://www.enos-project.eu). First results based on field tests conducted at Hontomín, and the advanced modelling developed so far will be analyzed and discussed in this article, as well as, the description of future works. The evolution of operating parameters such as flow rate, pressure and recovery term during the tests confirm the CO₂ migration through the fractures.

Limonene epoxide (1,2 limonene oxide) readily reacts with carbon dioxide in a ring opening copolymerization reaction with insertion of CO₂ and formation of polycarbonates of exceptional chemical and physical properties. Both poly(limonene carbonate) and poly(limonene dicarbonate) can be synthesized using low cost Zn or Al homogeneous catalysts. This study addresses selected relevant questions concerning the technical and economic feasibility of limonene and carbon dioxide polymers en route to the bioeconomy.

Carbonate reservoirs, influenced by depositional and diagenetic processes and characterized by features like faults and vugs that impact storage capacity, require more than traditional Borehole Imaging logs (BHI) for accurate porosity data. This data is essential for geological assessments, production forecasting, and reservoir simulations. This work aims to address this limitation by developing methods to measure and monitor the sustainability of carbonate reservoirs and exploring the application of sustainability principles to their management. The study integrates BHI and conventional logs from two wells to classify porosity-based facies within the Barra Velha Formation (BVF) in the Santos Basin. The methodology involves four steps: (i) analyzing conventional logs; (ii) segmenting BHI logs; (iii) integrating conventional and segmented BHI logs using Self-Organizing Maps (SOM); and (iv) interpreting the resulting classes. Matrix porosity values and non-matrix pore sizes categorize the porosity into four facies (A to D). Facies A has high non-matrix porosity with 14,560 small megapores, 5,419 large megapores, and 271 gigapores (71.9%, 26.76%, and 1.34% of the 20,250 pores, respectively). Facies B shows moderate non-matrix porosity with 8,669 small megapores, 2,642 large megapores, and 33 gigapores (76.42%, 23.29%, and 0.29% of the 11,344 pores, respectively) and medium matrix porosity. Facies C exhibits low non-matrix porosity with 7,749 small megapores, 2,132 large megapores, and 20 gigapores (78.27%, 21.53%, and 0.20% of the 9,901 pores, respectively) and medium matrix porosity. Facies D has low non-matrix porosity with 9,355 small megapores, 2,346 large megapores, and 19 gigapores (79.82%, 20.02%, and 0.16% of the 11,720 pores, respectively) and low matrix porosity. The novelty of this work lies in integrating data from two sources to classify porosity across the Pre-Salt reservoir interval, serving as a proxy for preliminary litho-facies identification without core data. This study advances our understanding of carbonate reservoir sustainability and heterogeneity, offering valuable insights for robust, sustainable reservoir characterization and management in the context of global environmental and geological changes.

The article describes the use of microwave irradiation in the synthesis of bis(cyclo carbonate) compounds (BCC) in bulk (without solvent) from carbon dioxide capture using an epoxidized compound - a commercial epoxy resin, and compares this process to the conventional method. CO2 cycloaddition to epoxides is an ecological and efficient method for the formation of bis(cyclic carbonates). Moreover, the introduction of gas into the reaction mixture was carried out at atmospheric pressure with a controlled flow rate, which is advantageous from an economic point of view. Progressive structural changes and the presence of characteristic chemical groups were monitored using attenuated total reflectance infrared spectroscopy with Fourier transform. The obtained crude products were purified to obtain three fractions, which were subjected to detailed structural analysis using FT-IR and 13CNMR. The formation of the main product with two cyclic carbonates was confirmed. The presence of monomers, dimers and trimers in individual fractions as well as their thermal stability were determined, and the molecular masses in individual fractions were determined using gel permeation chromatography (GPC).

The Chiltan Formation is a potential hydrocarbon-producing reservoir in the Indus Basin, Pakistan. However, its diagenetic alterations and heterogeneous behavior lead to significant challenges in accurately characterizing the reservoir and production performance. This manuscript aims to utilize Chiltan Limestone core samples to conduct a detailed analysis of the diagenetic impacts on reservoir quality. The formation evaluation was carried out through thin section analysis, SEM-EDS and FTIR investigation, as well as plug porosity and permeability measurements under different stress conditions. In results, Petrography revealed three microfacies with distinct diagenetic features and micro-nano fossil assemblages, including intraclasts, pelloids, bioclasts, and stylolites. Diagenesis has a significant impact on petrophysical properties, leading to increased reservoir heterogeneity. The specified depositional environment exposed the alteration of the Chiltan formation during distinct diagenetic phases in marine, meteoric, and burial settings. Pore morphology and mineralogy reveals complex micro-pore structure with various carbonate mineral phases and cement types in the formation samples. The average porosity and permeability of the core samples were found to be 3.4% and 0.449 mD respectively, indicating poor reservoir quality. Stress sensitivity was determined using Klinkenberg corrected permeability, which indicated a reduction in measured and absolute permeability due to increasing confining stress, further reducing the pore throat structure of the formation. In conclusion, the Chiltan formation possesses intricate reservoir heterogeneity and varied micro-pore structure caused by diagenesis and depositional settings. The formation is classified as a low-quality reservoir due to its non-uniform pore geometry, which exhibits low petrophysical properties resulting from overburden stress. The results of this study provide solid foundation in reservoir characterization and quality assessment which has implications for exploring and exploitation of indigenous resources.

For the first time, it is shown that inhaled ambient air-dust particles settled in the human lower respiratory tract induce lung calcification. Chemical- and mineral compositions of pulmonary calcium precipitates in the lung right lower-lobe (RLL) tissues of 12 individuals who lived in Upper Silesia Conurbation in Poland and who had died from causes not related to lung disorder were determined by transmission- and scanning electron microscopy. Whereas calcium salts in lungs are usually reported as phosphates, calcium salts precipitated in RLL are almost exclusively carbonates, i.e. Mg-calcite and calcite. These constitute 37% of 1652 mineral particles examined. Mg-calcite predominates in the submicron size range with the MgCO3 content up to 50 mol%. Magnesium plays a significant role in the lung mineralization, a fact so far overlooked. The calcium phosphate (hydroxyapatite) content in RLL is negligible. The predominance of carbonates is explained by increased CO2 fugacity in RLL. Carbonates enveloped inhaled mineral-dust particles, including uranium-bearing oxides, quartz, aluminosilicates, and metal sulfides. Three possible pathways for the carbonates precipitation on the dust particles are postulated: (1) precipitation of amorphous calcium carbonate (ACC) followed by its transformation to calcite; (2) precipitation of Mg-ACC followed by its transformation to Mg-calcite; (3) precipitation of Mg-free ACC causing a localized relative enrichment in Mg ions and subsequent heterogeneous nucleation and crystal growth of Mg-calcite. The actual number of inhaled dust particles may be significantly greater than observed because of the masking effect of the carbonate coatings. There is no simple correlation between smoking habit and lung calcification.

Two important types of metal oxide nanoparticle catalysts Copper (II) oxide (CuO) and Cerium oxide (CeO₂) are prepared by a suitable method which was traditional precipitation (PT) method at calcination temperature of 400^oC for 5h and used for the synthesis of glycerol carbonate GC (C₄H₆O₄) from the direct reaction by the carbonylation of Glycerol GL (C₃H₈O₃) with Carbone Dioxide. The precipitation (PT) was an important route for the preparation of nanoparticles catalyst. The effects of performance of (CuO and CeO₂) nanoparticle catalysts on the conversion of glycerol GL, yield of glycerol carbonate GC, selectivity of glycerol carbonate are researched. XRD, XPS, BET, FT-IR, CO₂-TPD, H₂-TPR are used for the characterization of the prepared catalysts. Comparing the optimal performance between them under reaction conditions were 150 ^oC, 4MPa (40 bar.), 5h, and both CuO and CeO₂ catalyst amount 37.6 % (based on ratio of glycerol weight) by using 2-pyridinecarbonitrate (C₆H₄N₂) as dehydrating agent and dimethylformamide (DMF), (C₃H₇NO) as solvent. The glycerol conversion (X_GL), glycerol carbonate yield (Y_GC) and glycerol carbonate selectivity (S_GC) over 0.7g CuO are 57.151%, 47.524%, and 83.156%, respectively, and glycerol carbonate yield over 0.7 CeO₂ is 36.2185% or 35.076%, and the yield of GC could reach as high as 78.234% over 1.73g CeO₂, the both catalysts could be easily regenerated by washing with methanol and water after a reaction and then dried at 60 ^oC overnight after that calcination at 400 ^oC for 5h without loss of activity after five recycling times, In addition to, the (ICP- MS) results confirmed that the leaching of CuO and CeO₂ was below the detection limit.

The region of Eastern Europe & Turkey contributed to the SISAL (Speleothem Isotopes Synthesis and AnaLysis) global database with stable carbon- and oxygen isotope time-series from 18 entities from 14 cave systems. The currently available oldest record from this region is the ABA-2 flowstone record (Abaliget Cave; Hungary) reaching back to MIS 6. The temporal distribution of the compiled 18 entities points out a ~20-kyr-long period, centering around 100 ka, lacking speleothem stable isotope record in the region. The regional subset of SISAL_v1 records displays a continuous coverage for the past ~90 kyr for both δ¹⁸O and δ¹³C, with a mean temporal resolution of ~12 yr for the Holocene, and >50 yr for the pre-Holocene period. The highest temporal resolution both for the Holocene and the pre-Holocene was achieved in the So-1 record (Sofular Cave; Turkey). Assessing the data, an important split was found regarding the climatic interpretation of speleothem δ¹⁸O. While the oxygen isotope composition of more continental formations is thought to reflect mainly temperature variations and changes in moisture transport trajectories, it may strongly reflect fluctuations of precipitation amount in the southern part of the region. Variations of δ¹³C primarily interpreted as humidity changes reflecting dry/wet periods across the region. Elevation gradients from three non-overlapping time periods from the region - for the last 5kyr - indicated systematically prevailing elevational gradients around -0.26‰ 100m^-1 in δ¹⁸O. The regional comparison of SISAL_v1 speleothem δ¹⁸O and the temporal distribution of coarsely crystalline cryogenic cave carbonate occurrences back to 45ka does not appear to confirm the finding that occurrence of the latter coincides with the warming from stadial to interstadial conditions.

In this work, non-ordered and ordered CeO2-based catalysts are proposed for the CO2 conversion to dimethyl carbonate (DMC). Particularly, a non-ordered mesoporous CeO2, consisting of small nanoparticles of about 8 nm, is compared with two highly porous (635-722 m2/g) ordered CeO2@SBA-15 nanocomposites obtained by two different impregnation strategies (a two-solvent impregnation (TS) and a self-combustion (SC) method), with a final CeO2 loading of 10 wt%. The Rietveld analyses on XRD data combined with TEM imaging evidence the influence of the impregnation strategy on the dispersion of the active phase: nanoparticles of 8 nm for the TS composite vs. 3 nm for the SC composite. The catalytic results show comparable activity for the mesoporous ceria and the CeO2@SBA-15_SC nanocomposite, while a lower DMC yield was found for the CeO2@SBA-15_TS nanocomposite. This finding is presumably ascribed to a partial obstruction of the pores by the CeO2 nanoparticles in the case of the TS composite, which leads to a reduced accessibility of the active phase. On the other hand, in the case of the SC composite, where the CeO2 particle size is much lower than the pore size, there is an improved accessibility of the active phase to the molecules of the reactants.

Nano- and microparticles are increasingly widely used in biomedical research and applications, particularly as specific labels and targeted delivery vehicles. Silica has long been considered the best material for such vehicles, but it has some disadvantages limiting its potential, such as the proneness of silica-based carriers to spontaneous drug release. Calcium carbonate (CaCO3) is an emerging alternative, being easily available, cost-effective, biocompatible material with high porosity and surface reactivity, which makes it an attractive choice for targeted drug delivery. CaCO3 particles are used in this field in the form of either bare CaCO3 microbeads or core/shell microparticles representing polymer-coated CaCO3 cores. In addition, they serve as removable templates for obtaining hollow polymer microcapsules. Each of these types of particles has its specific advantages in terms of biomedical applications. CaCO3 microbeads are primarily used due to their capacity for carrying pharmaceutics, whereas core/shell systems ensure better protection of the drug-loaded core from the environment. Hollow polymer capsules are particularly attractive because they can encapsulate large amounts of pharmaceutical agents and can be so designed as to release their contents in the target site in response to specific stimuli. This review focuses first on the chemistry of the CaCO3 cores, core/shell microbeads, and polymer microcapsules. Then, systems using these structures for the delivery of therapeutic agents, including drugs, proteins, and DNA, are outlined. The results of systematic analysis of available data are presented. They show that the encapsulation of various therapeutic agents in CaCO3-based microbeads or polymer microcapsules is a promising technique of drug delivery, especially in cancer therapy, enhancing drug bioavailability and specific targeting of cancer cells while reducing side effects. To date, research in CaCO3-based microparticles and polymer microcapsules assembled on CaCO3 templates has mainly dealt with their properties in vitro, whereas their in vivo behavior still remains poorly studied. However, an enormous potential of these highly biocompatible carriers for in vivo applications is undoubted. This last issue is addressed in depth in the Conclusion and Outlook sections of the review.

Fingerprints are essential for human identification and are valuable tools in criminal investigations. The pursuit of new materials for digital printing is expanding, with increasing interest in natural compounds such as bixin, sourced from annatto seeds. Despite its traditional use as a natural dye with medicinal properties, the potential of bixin in papilloscopy remains largely untapped. In this study, we meticulously extracted bixin from annatto seeds and meticulously developed composites incorporating zinc carbonate (bixin/ZnCO3) and kaolinite (bixin/kaolinite). UV-visible spectroscopy was used for characterization, and the extracted bixin showed absorption peaks at 429, 453, and 481 nm, which were very similar to standard peaks at 429, 457, and 487 nm. The two samples also had the same retention times (7.07 min) according to further liquid chromatography analysis. Sweat pores were easier to detect thanks to the effectiveness of the bixin/ZnCO3 and bixin/kaolinite composites in creating high contrast sebaceous and natural latent fingerprints. These results highlight the composites’ potential as novel and fascinating instruments for papilloscopy applications, which might also improve forensic investigations.

This study aims at the sustainable valorization of eggshells (ES) from different countries of origin in cement concrete as a cement replacement for Hong Kong. For this purpose, sixteen different eggs from different regions across the world were selected from the local market. Firstly, the extent of uniformity in the weight and mineral content of sampled eggshells were assessed by a specific gravity test and thermogravimetric analysis (TGA), respectively. It was found that specific gravity varies between 2.02 and 2.39, with an average value of 2.20 ± 0.01, whereas CaCO₃ varies between 94.65% and 97.23%, with an average value of 96.33%. These values were a bit lower than those of extra-pure limestone (LS) because of the organic part and the porous structure of eggshells. Secondly, three different eggshells were selected for cement replacement in cement concrete, both in the uncalcined and calcined states, based on having the highest, medium, and lowest CaCO₃ content, respectively. To get the calcined eggshells, the eggshells were calcined at 800^oC for three hours. It was found that the strength of eggshells varies with CaCO₃, but the variation was acceptable. The calcined eggshells showed comparatively more compressive strength and were close to the LS because of the free CaO and the absence of an organic part. In general, the variation in the basic properties of eggshells from different regions across the world is negligible and suitable to use as a cement replacement with acceptable variation in strength in Hong Kong.

Maxillary sinus augmentation with a lateral approach (MSA) is a well-established treatment. In this prospective study, we evaluated risk factors for postoperative bone-graft displacement and report the clinical application of long-term resorbable GMEM-B-2 (L-lactic acid/-caprolactone [P(LA/CL)]) as a barrier membrane to cover the open window in the lateral wall in MSA. Twenty-four patients underwent MSA according to the relevant criteria; CT data obtained before and 1 week (1W) and 5–6 months (5M) post-MSA, bone height changes, bone height reduction rates at 1W and 5M post-MSA, bone-graft displacement measurements, and risk factors were examined. All patients showed bone height increments (p < 0.005). However, no difference was observed between 1W and 5M post-MSA. Bone-graft displacement was observed in eight patients; the reduction rate from 1W to 5M post-MSA was 8.38% ± 4.88%. Sex, septa, maxillary sinus floor–palatal bone distance, and maxillary sinus floor–natural mouth distance were associated with bone-graft displacement (p < 0.05). Height from the maxillary sinus floor to the palatal bone and the sinus angle influenced the augmentation amount (p < 0.05). The L-lactic acid/ε-caprolactone [P(LA/CL)] membrane compared favourably with other membranes and may be useful as a barrier membrane for the MSA open window.

The wettability of the oil-brine-rock systems is very challenging mainly for the carbonate reservoirs and it plays a significant role to enhance the oil recovery (EOR). Carbonate rocks are mad-up of complex lithology, hence these requires careful treatments in controlling their wetting behavior for enhanced oil recovery. Therefore, it is extremely important to modify their wettability from an oil-wet rock behavior to a water-wet so that the residual oil can be produced efficiently. Thus, the present study has examined the effectiveness of alumina nanofluid as well as a new chemical methyl blue to alter the wettability. The methyl blue is released on massive scale from various industries i.e. pharma, textile and food industry which is a key environmental concern which contaminates the water table. Hence the study, explores the effects of MB and alumina nanofluid on the wettability. The effect of nanofluids formulated via dispersing the alumina nanoparticles in aqueous solutions at various concentration (0. 0.05, 0.3, 0.50, 0.75 and 1.0 wt. %) were tested for wettability modification under different physio-thermal conditions. Subsequently, the wettability change was examined for the samples treated with different concentrations of MB (10, 15, 30, 50 and 100 mg/L) for 7-days at two different temperatures of (25 and 50 0C). The results showed that hydrophobicity of the SML carbonate rock has significantly reversed while treating with alumina nanofluids and MB. Thus, the wettability modification/reversal via treatment of MB and alumina nanofluid can be an effective mechanism to hydrogen injection and for EOR processes.

Heavy metal contamination is listed among the most alarming threats to the environment and human health. The detrimental effects of heavy metals in the natural environment span from a reduction of biodiversity to toxic effects on marine life - through microplastic born heavy metals -, to impairment of microbial activity in the soil, and to detrimental effects on animal reproduction. A host of different chemical and biological technologies have been proposed to alleviate environmental contamination by heavy metals. Relatively less attention has been paid to the microbial precipitation of heavy metals, as a side mechanism of the most general process of microbially induced calcite precipitation (MICP). This process is currently receiving a great deal of interest from both a theoretical and practical standpoint, because of its possible practical applications in concrete healing and soil consolidation, and its importance in the more general framework of microbial induced mineral precipitation. In this study, we analyse the ability of the marine bacteria Vibrio harveyi in co-precipitating CaCO3 minerals, together with Cd, Cr, Pb, and Zn added in form of nitrates, from solutions containing CaCl2. The precipitated carbonatic minerals were a function of the different heavy metals present in the solution. The process of co-precipitation appears to be rather effective and fast, as the concentrations of the 4 heavy metals were reduced in 2 days by 97.2%, on average, in the solutions.

In order to understand the impact of lithologic heterogeneity of continental mixed fine-grained sedimentary rocks on reservoir brittleness in western Qaidam basin, the mechanical properties of the rocks and their correlation with mineral composition and petrographic characteristics were studied by measns of mineralogy, petrography and triaxial stress test. The results show that the reservoir rocks can be divided into 5 different types according to the mechanical properties of the reservoir (characteristics of stress-strain curves), among them Type I and III belong to similar elastoplastic failure model, type II shows a special pulse failure mode for plastic material, type IV shows a failure mode of mixed characteristics, and type V exhibits a typical plastic failure model. The correlation between minerals and mechanical properties indicates that quartz and feldspar, which are often considered brittle minerals, do not contribute much to the brittleness of continental fine-grained sedimentary rocks. The main minerals affecting reservoir brittleness are dolomite and clay minerals, and their contributions to reservoir brittleness are positive and negative, respectively. The petrographic analysis results prove that the abnormal correlation between rock mechanical properties and quartz and feldspar is caused by the different rock fabrics. When dolomite forms a rock skeleton, it typically exhibits greater strength, brittleness and physical properties than other minerals. Based on the results, a brittleness evaluation standard for continental fine-grained sedimentary rock reservoir is proposed, and the validity of the standard is verified by the spatial correlation between the lithology probability model and the micro-seismic monitoring data, indicating that the spatial heterogeneity of dolomite-rich rock is the main controlling factor for the development of ‘sweet spot’ in the Cenozoic continental fine-grained sedimentary rock reservoir in the Western Qaidam Basin.

This paper concerns about a stepwise modelling procedure for groundwater flow simulation in a complex carbonate, folded and faulted, multilayer aquifer, in the Apennine chain in Central Ita-ly, which constitutes a source of good quality water for human consumption. A perennial river acts as the main natural drain for groundwater while sustaining valuable water related ecosys-tems. The spatial distribution of recharge was estimated using the Thornthwaite-Mather method on 60 years of climate data. The system was conceptualized as three main aquifers separated by two locally discontinuous aquitards. Three numerical models were implemented by gradually adding complexity to the model grid: single layer (2D), three layers (Quasi-3D), and five layers (Fully-3D), using an equivalent porous medium approach, in order to find the best solution with a parsimonious model setting. To overcome dry-cell problems in the Fully-3D model, the New-ton-Raphson formulation for MODFLOW-2005 was invoked. Calibration results show that a Fully-3D model was required to match the observed distribution of aquifer outflow to the river baseflow. The numerical model demonstrated the major impact of folded and faulted geological structures on controlling the flow dynamics in terms of flow direction, water heads and spatial distribution of the outflows to the river and springs.

The search for sustainable resources remains a subject of global interest and the conversion of the abundantly available bivalve shell wastes to advanced materials is an intriguing method. By grinding, each shell of bivalves (cockle, mussel, and oyster) was transformed to the same crystal type of calcite phase of CaCO3, revealed by FTIR and XRD results. Each individual shell powder was reacted with H3PO4 and H2O to prepare Ca(H2PO4)2•H2O giving an anorthic crystal structure. The mixture of each shell powder and its produced Ca(H2PO4)2•H2O was heated at 900 °C for 3 h, giving rhombohedral crystal -Ca3(PO4)2 powder. FTIR and XRD results of the CaCO3, Ca(H2PO4)2•H2O, and Ca3(PO4)2 prepared from each shell powder are quite similar showing no impurities. Thermal behaviors of CaCO3 and Ca(H2PO4)2•H2O produced from each shell are slightly different. Particle sizes and morphologies of all products are significantly different, affected by the kind of shells used. Overall, the bivalve shell wastes were successfully converted to CaCO3, Ca(H2PO4)2•H2O, and Ca3(PO4)2 by a simple, rapid, environmentally benign, and cost-effective approach, which can be a huge potential in many industries providing both economic and ecological benefits according to the Bio-Circular-Green Economy (BCG) model.

This paper addresses the effect of both microstructure and relative humidity on the long-term creep properties of sustainable calcium carbonate (CaCO₃) cements. Those can be prepared by mixing amorphous calcium carbonate and vaterite with water. A larger starting amount of vaterite, X_V, within the mixture design gives a higher elasticity and resistance to the specimens due to the larger overall bridging area within the newly formed calcite crystals. Regarding creep properties for a given relative humidity, the amplitude of creep strain decreases with X_V, and makes the relation between the elastic modulus, E, and hardness, H, of the samples to be linear with the contact creep modulus, C. On the other hand, for a given composition, the amplitude of creep increases with the relative humidity, making the contact creep modulus, Ci, to rise exponentially with the elastic modulus, E, and hardness, H, of the specimens. The most probable creep mechanisms for this kind of cement seem to be a combination of microcraking in the early stages and dissolution and reprecipitation of calcite in the long-term (also known as pressure solution theory). The presence of water in pores with increasing relative humidity might enhance the local dissolution of calcite, and hence the creep amplitude.

Acid proteins capable of nucleating Ca2+ and displaying aggregation capacity play key roles in the formation of calcium carbonate biominerals. EF-hands are among the largest Ca2+-binding motif in proteins. Gad m 1, an Atlantic cod β-parvalbumin isoform, is a monomeric EF-hand protein that acts as a Ca2+ buffer in fish muscle and is able to form amyloids under acidic conditions. Since nucleating Ca2+ protein have a propensity to form extended β-strand structures, we wondered whether amyloid assemblies of a protein containing refolded EF-hand motifs were able to influence the in vitro calcium carbonate crystallization. Here we have used the Gad m 1 chain as model to generate monomeric and amyloid assemblies and analyze their effect on in vitro calcite formation. We found that only amyloid assemblies alter calcite morphology.

Transport of carbon, major and trace element by rivers in permafrost-affected regions is one of the key factor of circumpolar aquatic ecosystem response to climate warming and permafrost thaw. While seasonal and annual export fluxes (yields) of carbon (C) and inorganic solutes are fairly well known for all large Arctic rivers, spatial variations in elementary concentration along the river length and among its tributaries remain poorly understood. Moreover, the landscape factors controlling riverine element concentration in permafrost-affected regions are still poorly constrained. This is especially true for the largest river of Eastern Siberia, the Lena River, which drains through continuous permafrost zones with highly variable lithology and vegetation. Here we present the results of C, major and trace element measurements over a 2600-km transect of the Lena River main stem (upper and middle reaches) including its 30 tributaries, conducted at the peak of the spring flood. There were two main group of solutes in the main stem depending on their spatial pattern: i) elements that decreased their concentrations downstream, from SW to NE (Cl, SO4, DIC, Li, B, Na, Mg, K, Ca, As, Sr, Mo, Sb, Ba and U), which probably reflected a decrease in the proportion of carbonate rocks in the watershed and the degree of groundwater feeding, and ii) elements that increased their concentrations downstream (Al, Ti, Cr, Fe, Ga, Rb, Y, Zr, Nb, Cs, REEs, Hf and Th), which was tentatively linked to an increase in organic C stock in soils, larch forest coverage and enhanced mobilization of lithogenic elements from silicate soil minerals. Based on landscape parameters of Lena tributaries, we tested the impact of major environmental factors on major and trace element spatial pattern. Among all the variables, the proportion of sporadic permafrost on the watershed strongly controlled concentrations of soluble highly mobile elements (Cl, B, DIC, Li, Na, K, Mg, Ca, Sr, Mo, As and U). Another important factor of element concentration control in the Lena River tributaries was the coverage of watershed by light (B, Cl, Na, K, U) and deciduous (Fe, Ni, Zn, Ge, Rb, Zr, La, Th) needle-leaf forest (pine and larch). The latter, however, could also reflect the DOC-enhanced transport of low-soluble trace elements in the NW part of the basin. This part of the basin is dominated by silicate rocks and continuous permafrost, as compared to carbonate rock-dominated and groundwater-affected SW part of the Lena River basin. Overall, the impact of rock lithology and permafrost on major and trace solutes of the Lena River basin during the peak of spring flood was mostly detected at the scale of the main stem. Such an impact for tributaries was much less pronounced, because of the dominance of surface flow and lower hydrological connectivity with deep groundwater in the latter. Future changes in the river water chemistry linked to climate warming and permafrost thaw at the scale of the whole river basin are likely to be linked to changes in spatial pattern of dominant vegetation, rather than to the permafrost regime. We argue that comparable studies of large, permafrost-impacted rivers during most contrasting seasons, including winter baseflow, should allow efficient prediction of future changes in riverine ‘inorganic’ hydrochemistry induced by permafrost thaw.

Calcium carbonate cements have been synthesized by mixing amorphous calcium carbonate and vaterite powders with water to form a cement paste and study how mechanical strength is created during the setting reaction. In-situ XRD was used to monitor the transformation of ACC and vaterite phases into calcite and a rotational rheometer was used to monitor the strength evolution. There are two characteristic time scales of the strengthening of the cement paste. The short timescale of the order 1 hour is controlled by smoothening of the vaterite grains, allowing closer and therefore adhesive contacts between the grains. The long timescale of the order 10-50 hours is controlled by the phase transformation of vaterite into calcite. This transformation is, unlike in previous studies using stirred reactors, found to be mainly controlled by diffusion in the liquid phase. The evolution of shear strength with solid volume fraction is best explained by a fractal model of the paste structure.

The present study showcases a series of crystallization experiments using a specially designed double diffusion system to grow crystals belonging to the calcium carbonate-phosphate system. The experimental U-shaped device comprised two vertical solution containers, separated by a horizontal column of silica hydrogel. Each container was filled with 0.5 M CaCl2 and 0.5 M Na2CO3 solutions, which diffused through the gel column over time. Na3PO4 solutions, with 50 and 500 ppm concentrations, were incorporated into the gel in different experiments, resulting in a homogeneous distribution of phosphate concentrations within the diffusion column. After 15 and 30 days incubation period post-nucleation, the crystals formed in different sections of the gel were carefully extracted and studied with scanning electron microscopy and electron microprobe. Additionally, Raman spectra were collected from the samples using a confocal Raman microscope, providing further insights into their molecular composition and structural properties. The obtained results show that under the induced experimental conditions (i) phosphate incorporates into calcite´s structure, and (ii) the growth of calcium phosphates in the presence of carbonate ions involves the sequential, heterogeneous nucleation of CO3-bearing OCP/HAP-like phases with Raman spectral characteristics very similar to those of bioapatites.

The crystal structure of quintinite, Mg4Al2(OH)12(CO3)·3H2O, from Jacupiranga alkaline complex (Cajati, São Paulo, Brazil) has been refined for two samples (91002 and C7029) using single-crystal X-ray diffraction data. The mineral crystallizes in the P-3c1 space group, a = 5.246/5.298, c = 15.110/15.199 Å for the samples 91002/C7029. The crystal structure consists of octahedral sheets with Mg and Al ordering according to the 3 × 3 superstructure. The Mg and Al atoms are coordinated by six hydroxylated oxygen atoms each with the average <Mg–O> and <Al–O> bond distances being in the ranges 2.022–2.053 Å and 1.974–1.978 Å, respectively. The interlayer structures are identical (in contradiction to the previous assumptions) and compose from disordered (CO3)2- groups and (H2O)0 molecules. The samples from Jacupiranga can be identified as quintinite-2T that is the second find of the polytype after the Kovdor alkaline complex (Kola peninsula, Russia). The powder X-ray diffraction pattern of quintinite-2T contains weak superstructure reflection at 4.57 Å (010) indicative of Mg and Al ordering. An important crystal-chemical criterion of quintinite is the interlayer distance (d00n-value) of ~ 7.56 Å, which is steady for natural specimens from various findings worldwide.

Calcium (Ca) is an essential element constituting sedimentary carbonate in subducting sediments. Ca isotopic characteristics of subduction-related rocks could provide insight into the behavior and budget of carbonate and carbon cycles in subduction zones, due to the distinctive δ^44/40Ca ranges of sedimentary carbonate with respect to the mantle. Here, we studied the Ca isotopic compositions of arc magmas from the Northern Luzon arc (NLA), which are evolved from a depleted mantle metasomatized by slab-derived fluids and sediment melts. The δ^44/40Ca values range from 0.76 ± 0.04‰ to 1.01 ± 0.03‰ and cover the typical ranges for bulk silica earth (BSE, ~ 0.94‰) and fresh mid-ocean ridge basalt (MORB, ~ 0.83‰). The Ca isotopes of NLA volcanics are not dominantly determined by the effects of mantle partial melting or fractional crystallization, nor significantly modified by secondary alteration. Instead, the δ^44/40Ca values of NLA volcanics are controlled by the subduction-related metasomatism. The metasomatism by slab-derived fluids (mainly expelled from altered oceanic crust, AOC) dramatically elevated the contents of fluid-mobile elements (e.g., Ba and Pb) with respect to fluid-immobile elements (e.g., Ce). This process, however, rarely modified the Ca isotopes, possibly ascribed to the δ^44/40Ca similarity between AOC and the depleted mantle. The δ^44/40Ca values significantly correlated with subduction indicators (e.g., Sr-Nd isotopes, Ba/Nb, Ce/Pb, and Nb/La), demonstrating the Ca isotopes of NLA volcanics are mainly controlled by the metasomatism of sediment melts subducting from the South China Sea (SCS). Based on the thermal structures and chemical compositions of sediments subducting into global trenches, we propose that carbonate Ca isotopic signals can only be observed in the arcs with high sedimentary Ca fluxes and temperature-pressure conditions well beyond the solidus of H₂O-saturated sediment melting, e.g., NLA, Nicaragua, Guatemala, Colombia, Peru, South Chile, North Vanuatu, New Zealand, and Kermadec. The absence of such signals in other arcs suggests either limited sedimentary fluxes or much of the subducting sedimentary carbonate has been survived during plate subduction to enter the deep mantle.

The dissolution of CO₂ in seawater in the form of bicarbonate ions is an attractive alternative to the storage in geological formations, on the conditions that the storage is stable over long times and does not harm the marine environment. In this work, we focus on the long-term chemical stability of CO₂ absorbed in seawater as bicarbonate, by monitoring the physico-chemical properties of the solutions (pH, dissolved inorganic carbon and alkalinity), in six different sets of experiments on both natural and artificial seawater lasting up to three months. The bicarbonate treatment of natural seawater consists in pouring pre-equilibrated solutions obtained from the reaction of CO₂ and Ca(OH)₂. If the pre-equilibrated mixture does not exceed a critical threshold (ca. 1000-1500 mmol/L), the resulting bicarbonate-rich solutions can be stable for over three months.

The thermal decomposition of siderite and its decomposition products in a vacuum atmosphere was investigated for the first time using in situ high-temperature transmission Mössbauer spectroscopy. These measurements were supported by X-ray diffraction, Raman spectroscopy, X-ray fluorescence, and magnetic measurements. In situ Mössbauer spectra were collected from room temperature (RT) to 750 oC with a temperature step of 50 oC. After that, the sample was cooled down to RT with step 100 oC. Raw siderite samples contain siderite as the only iron-bearing mineral, and after heating the samples at high temperatures, hematite and magnetite are only Fe-bearing phases. In the temperature range of 300 oC - 500 oC, siderite decomposition occurs. The analysis shows that siderite transforms directly into magnetite, and then hematite generation occurs as long as siderite is present in the sample. Changing hyperfine parameters like isomer shift, quadrupole splitting, or hyperfine magnetic field versus temperature were obtained for siderite and iron oxides (hematite, magnetite). The measurements also show that magnetite formed during the decomposition of siderite is a composition of particles of various sizes and a low degree of crystallization.

This study aims to investigate utilizing Precipitated Calcium Carbonate (PCC), a by-product of sugar beet, as a soil stabilizer for addressing settlement issues beneath pavements. Various tests were conducted to assess the engineering properties of PCC-stabilized subgrades using PCC obtained from Amalgamated Sugar Cooperation in Twin Falls, Idaho. Local loess samples, like those found beneath pavements, were collected for testing purposes. Initial tests involved evaluating the unconfined compressive strength of compacted loess samples, followed by tests on samples mixed with different weight percentages of PCC. The results revealed a significant average increase of 10% to 28% in the strength of loess samples stabilized with 5% PCC compared to the strength of the native soil. The chemical composition and microstructure of PCC were further analyzed through X-ray Diffraction (XRD), Energy Dispersive X-ray Spectrometer (EDX), and Scanning Electron Microscopy (SEM) Tests conducted at the Idaho National Laboratory (INL). XRD analysis indicates the presence of calcium carbonate and silica. EDX analysis unveiled a carbon content of 9% by weight in PCC, which could contribute to the carbon footprint when it breaks down. Additionally, SEM images displayed an irregular microstructure and particle shape of PCC. Furthermore, the inclusion of PCC improved the resistance of loess to saturation collapse.

Manganese sludge, an industrial waste in the ferroalloy industry, contains various components and holds significant importance for sustainable development through its valorization. This study focuses on characterizing a manganese sludge and investigating its behavior during sulfuric acid leaching. The influence of process conditions, including temperature, acid concentration, liquid to solid ratio, and leaching duration, was examined. The results revealed that Mn, Zn, and K are the main leachable components, and their leaching rates increase with increasing temperature, liquid to solid ratio, and time. However, acid concentration requires optimization. High leaching rates of 90% for Mn, 90% for Zn, and 100% for K were achieved. Moreover, it was found that Pb in the sludge is converted to sulfate during the leaching which yields a sulfate concentrate rich in PbSO4. The leaching process for Mn and Zn species appears to follow a second or -third order reaction, and the calculation of rate constants indicated that Mn leaching kinetics are two to five times higher than those for Zn. Thermodynamic calculations were employed to evaluate the main chemical reactions occurring during leaching.

In this work, the influence of catalyst reuse and reaction time on the yield and quality of organic liquid products (OLP) obtained in a cracking pilot plant at 450 °C and 1.0 atm has been systematically investigated. The distillation of OLP produced 04 (four) distilled fractions. The quality of the biofuels was certified by physical-chemical analysis, as well as FT-IR and GC-MS analysis. The experimental results showed the feasibility of applying the spent sodium carbonate twice in catalytic cracking of vegetable oils. The physical-chemical properties (density, viscosity, acid value, saponification value, and flash point) of OLP decrease as the reaction time increases. The distillation of OLP yields 62.35% (wt.), producing green-like gasoline, kerosene, and diesel fractions rich in hydrocarbons. Therefore, biofuels-like fractions produced by distillation of OLP have a great potential for replacing partially petroleum derived fuels.

Cold-water coral reefs are rich, yet fragile ecosystems found in colder oceanic waters. Knowledge of their spatial distribution on continental shelves, slopes, seamounts and ridge systems is vital for marine spatial planning and conservation. Cold-water corals frequently form conspicuous carbonate mounds of varying sizes, which are identifiable from multibeam echosounder bathymetry and derived geomorphometric attributes. However, the often large number of mounds makes manual interpretation and mapping a tedious process. We present a methodology that combines image segmentation and random forest spatial prediction with the aim to derive maps of carbonate mounds and an associated measure of confidence. We demonstrate our method based on multibeam echosounder data from Iverryggen on the mid-Norwegian shelf. We identified the image-object mean planar curvature as the most important predictor. The presence and absence of carbonate mounds is mapped with high accuracy (overall accuracy = 84.4%, sensitivity = 0.827 and specificity = 0.866). Spatially-explicit confidence in the predictions is derived from the predicted probability and whether the predictions are within or outside the modelled range of values and is generally high. We plan to apply the showcased method to other areas of the Norwegian continental shelf and slope where MBES data have been collected with the aim to provide crucial information for marine spatial planning.

Waste biogenic materials from seafood exploitation are valuable resources of new compounds exploitation within the blue bioeconomy concept. Here, we describe the effectiveness of Raman technology implementation as an in-line tool for demineralization process control of crustaceans or gastropods. We produced transparent chitin polymer foils from three waste crustacean shells (C. sapidus, S. mantis and M. squinado) using a slow, green chemical approach employing acetic acid, and showed the progressive process of biogenic carbonate dissolution and increasing the Raman characteristic signal of chitin, in a time dependence manner. It turned that chitin foils obtaining is species-specific, and the demineralization bath of waste shell mixture can be effectively tracked by Raman spectroscopy, for solvent control and the recovery of the calcium acetate as valuable by-product. Comparatively, calcium acetate drug, a compound widely used in kidney failure diseases, or as additive in nutraceuticals and food industry, has been obtained here, following a green demineralization path of the sea snail Rapana venosa intact shell, assisted by Raman tech-nology, using 9% acetic acid (vinegar) solution for 14 days. To validate the final products identity and quality, The process of waste shells demineralization and the final products of the treatment were investigated using various Raman techniques and technologies, cross-validating the results with FT-IR, XRD and SEM-EDX techniques. NIR Raman spectroscopy revealed chitin bands in a time-dependent manner, while Resonance Raman spectroscopy showed the preservation of ca-rotenoids after two weeks of acetic acid treatment. A hand-held flexible TacticID Raman system with a 1064 nm excitation demonstrated its effectiveness as a rapid, in-line decision making tool during process control and revealed excellent reproducibility of the lab-based instrument signal, suitable for in situ evaluation of the demineralization status and solvent saturation control. The calcium acetate recovered from residual treatment solutions was assessed regarding its hydration status, purity, and suitability as recrystallized material for further use as pharmaceutical product or ingredient in complex formulations.

The possibility of deep radiochemical purification of Li2CO3 has been examined in the frame of the purification program of AMoRE collaboration. In this experiment, commercial Li2CO3 was converted into LiNO3. Co-precipitation with inorganic salt-based carriers followed by membrane filtration and sorption using MDM inorganic sorbent methods were tested for the removal of alkaline-earth and transition metals, potassium, magnesium, aluminum, uranium, thorium, and radium. The calcium molybdate-based carrier was the most efficient for removing Th, U, and K. Subsequently, the radium, calcium, and barium contaminations were removed with MDM sorbent. After the impurities’ removal, the final Li2CO3 product was synthesized with NH4HCO3 sludge. The separation factors were derived by means of ICP-MS and HPGe analyses of the initial material, intermediate and final products. The study showed the optimum conditions of co-precipitation and sorption to reach a high yield and radiopurity of lithium carbonate used for low radioactive background experiments.

The use of the commercial simulator Aspen Plus® could bring an amelioration in the accuracy of the predictions of the chemical species composition in the output streams of the anaerobic digestion process, due to availability of a broad library of thermodynamic and phenomena transport properties in this commercial package. In the present investigation, the process simulation model for anaerobic digestion, which was originally developed by Rajendran et al. [1], has been modified by including a stoichiometric-equilibria reactor to calculate the extent of the ionization of the molecules present in the anaerobic digestate. The refined model offers a more accurate prediction of the composition of the biogas because it delves on the chemical equilibrium of the gaseous stream and the anaerobic digestate. Additionally, the refined model allows to assess the possibility of upgrading the gaseous stream to biomethane degree via manufacturing of ammonium bicarbonate. This processing pathway relies on the stabilization of the anaerobic digestate by means of biomass ash-based treatment. First of all, the titration of the manure digestate with the hydrochloric acid showed that a dose of 3.18 mEq/g would be required to attain the targeted pH of zero-point charge, upon addition of the sewage sludge ash in a ratio to the manure digestate of 0.6 ± 0.2 %. Secondly, the profiles of ammonia, carbon dioxide, and methane found in the biogas agree with both the pH of the treated digestate and the processes described in for the simultaneously upgrading the biogas and the production of ammonium bicarbonate. The refined Aspen Plus® model presented in this article needs to be further developed to ensure the standards are attained in all output streams of stabilized anaerobic digestate, biomethane, and isolated added-value chemical fertilizers.

Bacterial Calcium-carbonate Precipitation (BCP) has been studied for multiple applications such as remediation, consolidation and cementation. Isolation and screening of strong calcifying bacteria is the main task of BCP-technique. In this paper we studied CaCO₃ precipitation by different bacteria isolated from a rhizospheric soil in both solid and liquid media. It has been found, through culture-depending studies, that bacteria belonging to Actinobacteria, Gammaproteobacteria and Alphaproteobacteria are the dominant bacteria involved in CaCO₃ precipitation in this environment. Pure and mixed cultures of selected strains were applied for sand biocementation experiments. Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) analyses of the biotreated samples revealed the biological nature of the cementation and the effectiveness of the biodeposition treatment by mixed cultures. X-ray diffraction (XRD) analysis confirmed that all the calcifying strains selected for sand biocementation precipitated CaCO₃, mostly in the form of calcite. In this study Biolog® Eco-plate is evaluated as a useful method for a more targeted choice of the sampling site with the purpose of obtaining interesting candidates for BCP applications. Furthermore, ImageJ software was investigated, for the first time to our knowledge, as a potential method to screen high CaCO₃ producer strains.

It remains unclear in the literature what is the cause of the so-called alkali-carbonate reaction (ACR) damage to concrete yet, a consensus is reached when considering dedolimitization as non-expansive. However, expansion and cracks as distress features are often attributed to alkali-silica reaction (ASR) when evidence of a reactive mineral is found in the aggregate. Evidently, different types of aggregates may produce different types and degrees of damage. Therefore, this work aims to assess the damage to concrete generated and propagated by the so-called ACR susceptible reactive Kingston coarse aggregate through mechanical testing (i.e., direct shear test), microscopy (the damage rating index – DRI), and other techniques. Distinct induced expansion levels (i.e., 0%, 0.05%, 0.12%, and 0.20%) were selected to compare the distress caused by ACR to concrete affected by ASR. Result show that the behaviour of ACR, namely as captured through the DRI, is inconsistent with that of ASR thus attesting to ACR being a distinct distress mechanism.

Mesozoic-Palaeozoic marine carbonate rocks are important hydrocarbon reservoirs in the Central Uplift area of the South Yellow Sea Basin (SYSB). Due to the lack of boreholes and the great heterogeneity of carbonate reservoirs, the distribution of porous carbonate reservoirs and their related key controlling factors remain unclear. Based on seismic inversion and isotope analysis, this study explores the factors affecting the distribution of porous Carboniferous-Early Permian carbonate reservoirs in the SYSB. In this study, the log-seismic characteristics of porous carbonate reservoirs, sensitive lithology parameters, and physical property parameters are extracted and analyzed. The pre-stack simultaneous inversion technique is applied to predict the lithology properties and physical properties of the porous carbonate reservoirs. Moreover, the sedimentary of carbonate is analyzed using isotopes of carbon, oxygen, and strontium. The results indicate that porous carbonate reservoirs with porosities of 3%~5% mainly occur at the paleo-highland (Huanglong Formation and Chuanshan Formation) and the slope of paleo-highland (Hezhou Formation). The porous carbonate reservoirs of the Qixia Formation are only locally developed. In addition, the study area was dominated by a warm and humid tropical climate from the Carboniferous to Early Permian, with four sea-level eustatic fluctuation indicated by the negative and positive δ13C excursions. When the sea level fell, the study area was exposed and denuded, and the supply of terrigenous detrital was dominated, which significantly influenced the carbonate deposit and diagenesis. This study highlights that sedimentation was a key factor in controlling the quality of Carboniferous-Early Permian carbonate reservoirs. The methods proposed in this study can be used in other carbonate-dominated strata worldwide.

The hydrochemical composition of the Upper Jurassic groundwaters in the South German Mo-lasse Basin (SGMB) indicates a heterogeneous and varying hydrogeochemical evolution, which contradicts previous flow model concepts. For this study, the data of 88 Tertiary, Cretaceous and Upper Jurassic groundwater samples were investigated for hydrochemical elements, 2H/18O-H2O isotopes, 87Sr/86Sr ratios as well as δ11B values. In addition, the geochemical composition, 87Sr/86Sr and δ11B values were analysed from depth-oriented Upper Jurassic rock samples to delineate water-rock interactions in the aquifer systems. Slightly elevated 87Sr/86Sr ratios of the carbonates compared to the typical signatures of marine Upper Jurassic carbonates indicate a synsedimentary radiogenic influence due to the erosion of the adjacent Bohemian Massif. However, these values cannot explain the significant higher Sr-isotope fingerprint of the groundwaters in the central SGMB. Different water types occur in the Upper Jurassic aquifer, primarily distinguished by the dominant cations, calcium or sodium with subclasses of the major anions. The calcium-dominated groundwaters occur mainly at the western and northern margins of the SGMB. The sodi-um-dominated ion exchange groundwaters instead dominate in the central and eastern SGMB. With increasing strontium content, the 87Sr/86Sr ratios of the Upper Jurassic groundwater samples either indicate a strontium uptake by carbonate of the host rocks, or a prevailing radiogenic sig-nature. This implies a basic interaction with terrestrial or marine Tertiary sediments. The results illustrate a downward transformational fluid flow systematic via the thick Tertiary sediment cover into the Upper Jurassic carbonate formation in the SGMB, highlighting a new understanding on the evolution of the Upper Jurassic groundwaters and a basin-wide recharge mechanism.

Modified structure along latent tracks and track formation process have been investigated in poly(allyl diglycol carbonate), PADC, which is well recognized as a sensitive etched track detector. This knowledge is essential to develop novel detectors with improved track registration property. The track structures of protons and heavy ions (He, C, Ne, Ar, Fe, Kr and Xe) have been examined by means of FT-IR spectrometry, covering the stopping power region between 1.2 to 12,000 eV/nm. Through a set of experiments on low-LET radiations – such as gamma ray -, multi-step damage process by electron hits was confirmed in the radiation-sensitive parts of the PADC repeat-unit. From this result, we unveiled for the first-time the layered structure in tracks, in relation with the number of secondary electrons. We also proved that etch pit was formed when at least two repeat-units were destroyed along the track radial direction. To evaluate the number of secondary electrons around tracks, a series of numerical simulations were performed with Geant4-DNA. Therefore, we are proposing new physical criterions to describe the detection thresholds. Futhermore, we propose a present issue of the definition of detection threshold for semi-relativistic C ions. And as a possible chemical criterion, formation density of hydroxyl group is suggested to express the response of PADC.

Planktonic foraminiferal biomineralization intensity, reflected by their shell calcite mass, affects global carbonate deposition and is known to follow the climate cycles by being increased during glacial stages and decreased during interglacial ones. Here we measure the dissolution state and the mass of the shells of the planktonic foraminifera species Globigerina bulloides from a Tropical Eastern North Atlantic site over the last two glacial-interglacial climatic transitions and we report no major changes in plankton calcite production with the atmospheric pCO2 variations. We attribute this consistency in foraminifera calcification to the climatic and hydrological stability of the tropical regions. We however recorded increased shell masses midway through the penultimate deglaciation (Termination II). In order to elucidate the cause of the increased shell weights we performed δ18O, Mg/Ca and μCT measurements on the same shells from a number of samples surrounding this event. We find that shells of increased mass are internally contaminated by sediment infilling and that shell weights are responding to local hydrographic changes.

Concrete contributes 8% of all global carbon emissions making the need to find substitute critical for environmental sustainability. Research has indicated the potential for recycled plastics to be used as concrete substitutes. This study extends existing research by investigating the use of polycarbonate (PC) in plastic sand bricks as a mechanical equivalent to concrete. PC has high compressive strength, durability, impact strength, thermal resistivity, clarity, fatigue resistance, and UV resistance. This work provides a method and mold to produce a matrix of sand-plastic sample compositions with dimensions adhering to ASTM D695 standard for compressive properties of rigid-plastic. Compositions of 0% (control), 20%, 30%, 40%, and 50% sand by weight were tested. Samples were tested for compressive strength until yield and stress-strain behaviors plotted. The results for 100% PC demonstrated an average and maximum compressive strength of 71 MPa and 72 MPa, respectively. The 50% PC and 50% sand composition yielded an average and maximum compressive strength of 71 MPa and 73 MPa respectively with an increase in compressive stiffness, and transition to shear failure resembling cement. With a composite density of 1.86 g/cm3 against concrete’s average 2.4 g/cm3, and a compressive strength exceeding commercial concrete demands of 23.3 MPa to 30.2 MPa, this lightweight alternative meets the strength demands of concrete, reduces the need for new construction materials, and provides an additional recycling opportunity for nonbiodegradable waste plastic.

Brine-dependent recovery process has seen much global research efforts in the past two decades because of their benefits over other oil recovery methods. The process involves the tweaking of the ionic composition and strength of the injected water to improve oil production. In recent years, several studies ranging from laboratory coreflood experiments by many researchers to field trials by several companies admit to the potential of recovering additional oil in sandstone and carbonate reservoirs. Sandstone and carbonate rocks are composed of completely different minerals, with varying degree of complexity and heterogeneity, but wettability alteration has been widely considered as the consequence rather than the cause of brine-dependent recovery. However, there is no consensus on the cause as several mechanisms have been proposed to relate the wettability changes to the improved recovery. This review paper aims to provide a state-of-the-art development in published research and various efforts of the industry. This review outlines an overview of laboratory and field observations, descriptions of underlying mechanisms and their validity, the complexity of the oil-brine-rock interactions, modelling works, and comparison between sandstone and carbonate rocks. The provided information is intended to provide the reader with up-to-date information, point to relevant studies for those who are new and those implementing either laboratory- or field-scale projects to speed up the process of further investigations in this research area. Overall, the outcome of this review would potentially be of immense benefit to the oil industry.

A testable hypothesis with quantitative predictions is put forward, proposing that strong acids produced on land are a major cause of increasing atmospheric pCO2. Our modelling analysis of reactions by dissolved inorganic carbon shows that increasing atmospheric CO2 could be caused thermodynamically by falling land surface pH values. This hypothesis challenges the imbalance assumed between the global uptake of CO2 by photosynthesis and emissions of CO2 from all sources, including the combustion of fossil fuels. Strong acids generated by oxygen from reduced nitrogen and sulphur emits CO2 almost stoichiometrically from dissolved bicarbonate in the pH range of most global soils from pH 6.5 to above 8. Each general decrease of aqueous pH value of 0.01 units from acidification of surface water potentially increases the pCO2 in the atmosphere by about 7 ppmv. Contrary to prevailing assumptions that CO2 emissions from combusting fossil fuels can remain in the atmosphere for more than a millennium, such emissions may be partly nullified by global greening from enhanced rates of photosynthesis as well as oceanic absorption. The surface pH value of the ocean has been shown to decrease as atmospheric pCO2 rises. Therefore, our qualitative estimates of increasing atmospheric CO2 driven by irreversible acidification on land are critical and need broad scale validation. To the extent that significant acidification of the land is occurring, through export of alkaline produce, the use of artificial nitrogen fertilisation and possible other causes, the prevailing methods of reducing CO2 emissions will fail. However, these acidifying processes on land have not been considered by previous biogeochemical reviews. Despite counter measures, including carbon capture and geological storage, the increasing Keeling curve for pCO2 may continue to rise because zero carbon policies do not address such a major cause. This hypothesis can be tested by in situ experiments in neutral soils and water, designed to compare CO2 emissions under the acidifying conditions described in this article with those when corrective counter measures are applied.

Carbon dioxide capture and storage (CCS) is a necessary requirement for high-emitting CO2 industries to significantly reduce volumes of greenhouse gases released to the atmosphere and mitigate the climate change. Geological CO2 storage into depleted oil and gas fields is the fastest and most accessible option for CCS deployment allowing for re-purposing of existing infrastructure and utilizing the significant knowledge about the subsurface acquired during the field production operations. Location of such depleted fields in neighbourhood of high-emitting CO2 industries is additional advantage available for matured on-shore Europe fields. Considering these advantages, the oil and gas operators are now evaluating different possibilities for CO2 sequestration projects for the fields approaching end of production. This article describes an integrated approach to reservoir simulations focused on evaluating CO2 injection pilot at one of such matured fields operated by MND and located in the Czech Republic. The potential CO2 injection site in focus is a naturally fractured carbonate reservoir. This oil-bearing formation has a gas cap at the top and a limited aquifer at the bottom of the reservoir and was produced mainly by pressure depletion with quite limited pressure support from water injection. The article summarizes results of efforts taken by the multi-disciplinary team to develop and apply an integrated approach to reservoir simulation started from geological modelling of the naturally fractured reservoir and integrating results of laboratory studies and their interpretation (geomechanical and geochemistry laboratory experiments) and dynamic field data analysis (pressure transient analysis including time-lapse) into the history matching of the reservoir model and simulations of pilot CO2 injection. Attention is given to evaluating and modelling stress-sensitive fracture properties and safe injection envelope preventing induced fracturing as well as impact of potential salt precipitation in the near wellbore area. These effects are considered in the context of pilot CO2 injection and addressed in reservoir simulations of the injection scenarios. Single porosity and permeability reservoir simulations with dominating fracture flow and black-oil formulation with CO2 simulated as a solvent were used in this study and arguments for such choice of the simulation approach for the site in focus are shortly discussed. The reservoir simulations have indicated larger site injection capacity than required for the pilot injection and allowed to evaluate CO2 migration pathway within the reservoir. The application of the approach to the site in focus has also revealed large uncertainties, related to fracture description and geomechanical evaluations, resulted in an uncertain safe injection envelope. These uncertainties should be addressed in further studies in preparation to the pilot. The article concludes with an overview of the outcomes of the integrated approach and its application to the field in focus including discussion of issues and uncertainties revealed.

Melting phase relations of the diamond-forming system olivine (Ol) – jadeite (Jd) – diopside (Di) – (Mg, Fe, Ca, Na)-carbonates (Carb*) – (C-O-H-fluid) are studied in experiments at 6.0 GPa in the polythermal section Ol74Carb*18.5(C-O-H)7.5 - Omp74Carb*18.5(C-O-H)7.5, where Ol = Fo80Fa20, Omp (omphacite) = Jd62Di38 and Carb* = (MgCO3)25(FeCO3)25(CaCO3)25(Na2CO3)25. Peritectic reaction of olivine and jadeite-bearing melt with formation of garnet has been determined as a physico-chemical mechanism of ultrabasiс-basiс evolution of the diamond-forming system. In the process CO2-component of the supercritical C-O-H-fluid can react with silicate components to form additional carbonates of Mg, Fe, Ca and Na. Solidus temperature of the diamond-forming system is depressed to 1000-1020°C by joint effect of the H2O-fluid and carbonate constituents thereof. The experimentally recognized peritectic mechanism of ultrabasiс-basiс evolution of the diamond-forming system explains the origin of the associated paragenetic inclusions of peridotite and eclogite minerals in diamonds as well as the xenoliths of diamond-bearing peridotites and eclogites of the kimberlitic deposits of diamond. The diamond-forming systems have formed with the use of material of the upper mantle native peridotite rocks. In this case the capacity of the rocks to run the peritectic reaction of olivine was transmitted with silicate components to the diamond-forming systems.

The increasing use of energy resources recovered from the subsurface environments and the resulting carbon imbalance in the environment has motivated the need to develop thermodynamically downhill pathways to convert and store CO₂ as water insoluble calcium or magnesium carbonates. While previous studies extensively explored aqueous routes to produce calcium and magnesium carbonates from CO₂, there has been a limited scientific understanding of the phase evolution and textural changes during the direct gas-solid conversion routes to produce calcium carbonate from calcium hydroxide, which is one of the abundant constituents of alkaline industrial residues. With increasing interest in developing integrated pathways for capturing, converting and storing CO₂ from dilute flue gases, understanding the compositions of the product phases as they evolve is essential for evaluating the efficacy of a given processing route. Therefore, in this study, we investigate the phase evolution and the corresponding textural changes as calcium hydroxide is converted to calcium carbonate under the continuous flow of CO₂ at an ambient pressure of 1 atm and on heating continuously from 30 °C to 500 °C using in-operando wide angle X-ray scattering (WAXS), small angle X-ray scattering (SAXS), and ultra-small angle X-ray scattering (USAXS) measurements.