A new vacuum line to extract CO2 from carbonate and dissolved inorganic carbon (DIC) in water was established at Guangxi Normal University. The vacuum line consisted of two main components: a CO2 bubble circulation region and a CO2 purification collection region, both of which were made of quartz glass and metal pipelines. To validate its reliability, a series of carbonate samples were prepared using this system. The total recovery rate of CO2 extraction and graphitization exceeded 80%. Furthermore, the carbon content in calcium carbonate exhibited a linear relationship with the CO2 pressure within the system, demonstrating its stability and reliability. The system was also employed to prepare and analyze various samples, including calcium carbonate blanks, foraminiferal, shell, groundwater, and subsurface oil-water samples. The accelerator mass spectrometry (AMS) results indicated that the average beam current for 12C- in the samples exceeded 40 μA. Additionally, the contamination introduced during the liquid sample preparation process was approximately (1.77 ± 0.57) × 10−14. Overall, the graphitized preparation system for carbonate and DIC in water exhibited high efficiency and recovery, meeting the requirements for samples dating back to approximately 30,000 years.

Several new minerals, structurally and chemically similar to the hydrotalcite-manasseite group, have been found in the saline deposits of the central pre-Caspian depression and in those of Middle Asia. Their structures consist of layers of (Mg1-xAlx)(OH)2 plus interlayers of anions and molecular water. In addition to manasseite itself, [(Mg4Al2)(OH)12][(CO3)-3H2O], having unit-cell parameters of a = 3.042, c = 2 × 7.56= 15.12 Å and a calculated density of Dc = 2.15 g/cm3, other varieties were identified whose interlayers contain alternately SO42− or SO42− and CO32− anions. The following new phases were recognized: (1) an 8.85-Å phase having the composition [(Mg4Al2)(OH)12][(SO4)·3H2O], subcell dimensions of a' = 3.04, c' = 8.85 Å, and Dc = 1.96 g/cm3; (2) an 11-Å phase having the composition [(Mg3.96Fe0.06Al1.98)(OH)12][Na0.56(SO4)1.30·7.3H2O], hexagonal unit-cell parameters of a = √3 · 3.042 = 5.28 Å, c = 11.16 Å, and Dc = 1.90 g/cm3; (3) a 16.5-Å mixed-layer phase having the composition [(Mg4Al2)(OH)12][(SO4)0.5(CO3)0.5·3H2O] and an ordered ABAB... alternation of 7.56-Å layers (i.e., a brucite-like layer + a CO32−-containing interlayer) and 8.94-Å layers containing SO42− anions in interlayers; this phase has unit-cell dimensions of a' = 3.05, c' = 16.5 Å and Dc = 2.06 g/cm3; and (4) an 18.5-Å ordered mixed-layer phase having the ideal composition [(Mg8Al4)(OH)24][M+0.5(SO4)1.25(CO3)1.0·9H2O] and an alternation of 7.56-Å, CO3-containing layers and 11-Å layers having SO42− anions and Na and Mg cations in interlayers (M+0.5 corresponds to interlayer cations). This last phase has unit-cell dimensions of a = 3.046, c = 3 × 18.54 = 55.62 Å and Dc = 1.99 g/cm3. Some of the varieties containing SO42− in the interlayers swelled with ethylene glycol or glycerol.

For this diverse family of minerals whose structures are based on brucite-like layers of the composition (R2+1-xR3+x)(OH)2, a unifying system of nomenclature is offered for consideration. In describing these brucite-like structures intercalated with anion- and cation-containing interlayers, the composition of the hydroxide sheet and the interlayers, the periodicity of the layers, and the mixed-layer nature of the material should be described. By means of symbols, a single term might be used to describe the crystal chemistry of any member of the group having a given cation composition for the brucite-like layers, for example, manasseite, a 2H polytype of hydrotalcite that has a repeat distance of 7.56 Å and CO3-containing interlayers, might be designated as 7.56-Å CO3-hydrotalcite-2H.

Škáchaite (IMA2022–143) is a new mineral species discovered in samples from the hydrothermal vein B117, shaft No. 6 at the Brod deposit of the uranium and base-metal Příbram ore district, central Bohemia, Czech Republic. Škáchaite is a Co-dominant member of the dolomite group and forms anhedral grains up to 50 μm in size and as 20–100 μm thick growth zones in škáchaite–dolomite crystals as a part of carbonate (dolomite, calcite, siderite, spherocobaltite, ankerite, kutnohorite and minrecordite) gangue, associated with native silver, sulfides and arsenides. Škáchaite is pale to bright pink with vitreous lustre. The Mohs hardness is ca. 3½–4, similar to other members of the dolomite group. The calculated density is 3.140 g.cm–3. Škáchaite is optically uniaxial (–); the indices of refraction are ω = 1.741(3) and ɛ = 1.535(3). On the basis of electron-microprobe analyses, its empirical formula is Ca1.00(Co0.45Mg0.38Ca0.08Fe0.05Mn0.03Zn0.01)Σ1.00(CO3)2. The ideal formula is CaCo(CO3)2, which requires (in wt.%) CaO 25.60, CoO 34.21, CO2 40.19, a total of 100.00. Škáchaite is trigonal, R$\bar{3}$, with unit-cell parameters a = 4.8177(18), c = 16.093(7) Å, V = 323.5(2) Å3 and Z = 3. The strongest reflections of the calculated powder X-ray diffraction pattern [d, Å, (Irel, %) hkl] are: 3.704 (13) 10$\bar{2}$; 2.896 (100) 104; 2.409 (15) 110; 2.019 (17) 202; 1.812 (19) 10$\bar{8}$; and 1.792 (16) 11$\bar{6}$. According to the single-crystal X-ray diffraction data (R1 = 0.0304 for 94 reflections with [I > 3σ(I)]), the crystal structure of škáchaite is isotypic with its Mg-analogue, dolomite. The Raman spectrum of škáchaite, as well as the tentative assignment of observed bands, are given in this paper. The mineral is named in honour of Pavel Škácha, a Czech mineralogist and curator of the mineralogical collection of the Mining Museum Příbram, Czech Republic.

The chemistry of Al transformation has been well documented, though little is known about the mechanisms of structural perturbation of Al precipitates by carbonates at a molecular level. The purpose of the present study was to investigate the structural perturbation of Al precipitates formed under the influence of carbonates. Initial carbonate/Al molar ratios (MRs) used were 0, 0.1, and 0.5 after aging for 32 days, then the samples were analyzed by X-ray absorption near edge structure spectroscopy (XANES), X-ray diffraction (XRD), Fourier-transform infrared absorption spectroscopy (FTIR), and chemical analysis. The XRD data were in accord with the FTIR results, which revealed that as the carbonate/Al MR was increased from 0 to 0.1, carbonate preferentially retarded the formation of gibbsite and had relatively little effect on the formation of bayerite. As the carbonate/Al MR was increased to 0.5, however, the crystallization of both gibbsite and bayerite was completely inhibited. The impact of carbonate on the nature of Al precipitates was also evident in the increase of adsorbed water and inorganic C contents with increasing carbonate/Al MR. The Al K- and L- edge XANES data provide the first evidence illustrating the change in the coordination number of Al from 6-fold to mixed 6- and 4-fold coordination in the structural network of short-range ordered (SRO) Al precipitates formed under the increasing perturbation of carbonate. The fluorescence yield spectra of the O K-edge show that the intensity of the peak at 534.5 eV assigned to σ* transitions of Al-O and O-H bonding decreased with increasing carbonate/Al MR. The XANES data, along with the evidence from XRD, FTIR, and chemical analysis showed clearly that carbonate caused the alteration of the coordination nature of the Al-O bonding through perturbation of the atomic bonding and structural configuration of Al hydroxides by complexation with Al in the SRO network of Al precipitates. The surface reactivity of an Al-O bond is related to its covalency and coordination geometry. The present findings were, therefore, of fundamental significance in understanding the low-temperature geochemistry of Al and its impacts on the transformation, transport, and fate of nutrients and pollutants in the ecosystem.

Fire resistance performance is one of the most important requirements in geological storage conditions in order to improve the resistance of storage packages to high thermal constraints (in the case of a fire for example). With the need to develop new fire-resistant materials, the aim of the present study was to develop fire-resistant geopolymer binders based on Callovo-Oxfordian (COx) argillite. Two types of kaolin with different degrees of purity were mixed with argillite in various proportions. These mixtures were calcined at 600 or 750°C. In order to assess the fire resistance of activated materials, thermal treatment at 1000°C was performed. The compressive strength and mineralogical composition of the samples were investigated before and after heat treatment. The results showed that the addition of argillite improved significantly the thermomechanical properties of kaolin-based geopolymers containing impurities, especially the mixture containing 67% argillite and calcined at 750°C. This phenomenon was not observed for the pure-kaolin geopolymer. Improvement of fire resistance was due to the formation in situ of leucite and zeolite-type phases (KAlSi2O6 and KAlSiO4) and of wollastonite (CaSiO3) at high temperature, which is linked to the Ca available in the raw materials.

The sediments of closed-basin lakes on the margin of the East Asian summer monsoon (EASM) are valuable archives of past changes in hydroclimate and dust activity and thus potentially can help us to understand future climate changes. We present high-resolution, well-dated records of the grain size and carbonate mineralogy from Lake Bayanchagan, northern China, spanning the last 11.5 ka. Grain-size endmember (EM) analysis distinguished four EMs, each linked to different sediment transport processes. EM1 (0.4–0.6 μm) and EM3 (14–102 μm) reflect the strength of regional dust activity, whereas EM2 (1.3–31 μm) represents variations in local hydrodynamic conditions related to lake-level changes and EM4 (68–500 μm) is associated with local dust activity. Our results show that a high lake level and weakened dust activity occurred during 10–5.8 ka, as indicated by increased EM2 and decreased EM3, respectively. After 5.8 ka, EM2 decreased as the three other EMs increased, and dolomite appeared in the sediments while calcite decreased—indicating both a decline in lake level and strengthened dust activity. The fluctuations in lake level and dust activity are in good agreement with precipitation variations reconstructed from other records, which are in turn correlated to movement of the EASM rainfall belt, in response to temperature changes.

The appraisal and development of fractured reservoirs are challenging tasks because of the combined variations in reservoir quality and natural fracture distribution. Fracture models are built routinely to support both appraisal and development decisions for such reservoirs. One of the key objectives of these models is to generate three-dimensional (3D) fracture properties for dynamic flow simulations. In this paper, we illustrate the discrepancy between the scale of observation required to build a thorough geological understanding of the subsurface and the simplification imposed by modelling. We use a case study carried out in the context of an exploration campaign of a Cretaceous carbonate reservoir in Egypt. After describing the regional geological setting of the area, we share a series of detailed observations on open-hole logs, cores, thin-sections and borehole images. These observations are focused on reservoir architecture, fracture typology and fracture connectivity. Observations are then integrated with the regional geological context to build a conceptual fracture model and to characterize the uncertainty affecting the essential parameters of this model. The conceptual model, combined with 3D seismic data, is used to define a fracture modelling strategy. This strategy includes a drastic simplification of the conceptual model to generate 3D discrete fracture network scenarios that are calibrated using pressure communication data from the exploration wells. Another extreme simplification is then necessary to populate 3D simulation grids. In the case study presented, the key tuning parameters to obtain a dynamic match are the grid cell orientation and the width of the modelled fault damage zone.

Calcification within breast cancer is a diagnostically significant radiological feature that generally consists of hydroxylapatite. Samples from 30 cases of breast carcinoma with calcification were investigated using optical microscopy, energy-dispersive X-ray analysis, transmission-electron microscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, synchrotron radiation X-ray diffraction and X-ray fluorescence. Under optical microscopy, the calcifications were found to consist of either irregular aggregates with widths > 200 μm or spherical aggregates similar to psammoma bodies with an average diameter of 30 μm. Transmission-electron microscopy showed that short columnar or dumbbell-shaped crystals with widths of 10–15 nm and lengths of 20–50 nm were the most common morphology; spherical aggregates (~1 μm in diameter) with amorphous coatings of fibrous nanocrystals were also observed. Results indicated that hydroxylapatite was the dominant mineral phase in the calcifications, and both CO32– and cation substitutions (Na, Mg, Zn, Fe, Sr, Cu and Mn) were present in the hydroxylapatite structure. Fourier-transform infrared spectra show peaks at 872 and 880 cm–1 indicating that CO32– substituted both the OH– (A type) and PO43– (B type) sites of hydroxylapatite, making it an A and B mixed type. The ratio of B- to A-type substitution was estimated in the range of 1.1–18.7 from the ratio of peak intensities (I872/I880), accompanied with CO32– contents from 1.1% to 14.5%. Trace arsenic, detected in situ by synchrotron radiation X-ray fluorescence was found to be distributed uniformly in the calcifications in the form of AsO43– substituting for PO43–. It is therefore proposed that identifying these trace elements in breast cancer calcifications may be promising for future clinical diagnostics.

Alstonite, BaCa(CO3)2, is a mineral described almost two centuries ago. It is widespread in Nature and forms magnificent cm-sized crystals. Notwithstanding, its crystal structure was still unknown. Here, we report the crystal-structure determination of the mineral and discuss it in relationship to other polymorphs of BaCa(CO3)2. Alstonite is trigonal, space group P31m, with unit-cell parameters a = 17.4360(6), c = 6.1295(2) Å, V = 1613.80(9) Å3 and Z = 12. The crystal structure was solved and refined to R1 = 0.0727 on the basis of 4515 reflections with Fo > 4σ(Fo) and 195 refined parameters. Alstonite is formed by the alternation, along c, of Ba-dominant and Ca-dominant layers, separated by CO3 groups parallel to {0001}. The main take-home message is to show that not all structure determinations of minerals/compounds can be solved routinely. Some crystals, even large ones displaying excellent diffraction quality, can be twinned in complex ways, thus making their study a crystallographic challenge.

Radiocarbon (14C) dating of anthropogenic carbonates (CaCO3) such as ash, lime plaster and lime mortar, has proven a difficult task due to the occurrence of a number of contaminants embedded within the CaCO3 pyrogenic binder. These include 14C-free geologic components and/or secondary phases bearing an unknown amount of 14C, and thus the alteration of the original pyrogenic isotopic signature of the material results in major age offsets when carbon recovery is performed through acid hydrolysis. Here we present a characterization/quantification approach to anthropogenic carbonates that includes Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, thin section petrography, thermogravimetric analysis and scanning electron microscopy coupled with high-resolution cathodoluminescence, with which we identified the pyrogenic CaCO3 fraction in an aerial lime plaster and two hydraulic mortars. The preserved pyrogenic component was then isolated by density separation and its purity checked again using FTIR. Carbon was recovered through thermal decomposition in vacuum. The resulting 14C age matches the expected age of the lime plaster, whereas hydraulic mortars are slightly offset due to the carbonation of calcium hydroxide lumps. This approach highlights the importance of a dedicated characterization strategy prior to dating and may be applied to aerial lime plasters to obtain accurate ages.

Akopovaite, ideally Li2Al4(OH)12(CO3)(H2O)3, is a new hydrotalcite-supergroup mineral from the Karasu–Karavshinskoye Sn deposit, Turkestan Range, Kyrgyzstan. It occurs as white or pale yellowish rosette-like aggregates that are composed of tiny curved plates up to 20–30 μm. Akopovaite is associated with gibbsite, quartz, albite, microcline, muscovite, montebrasite, siderite, schorl and birnessite-like Fe–Mn oxides. Akopovaite has a perfect cleavage along {001}, the mineral is transparent and very soft (VHN = 24 that corresponds to Mohs hardness of ca. 1). Dmeas = 2.12(2) g/cm3 and Dcalc = 2.106 g/cm3. The Raman spectra contain bands of carbonate groups and bands of O–H stretching vibrations. The chemical composition (wt.%, electron microprobe for Al and Fe; ICP-OES for Li; CHN method for CO2 and H2O) is Li2O 6.43, Al2O3 45.79, Fe2O3 0.27, CO2 10.09, H2O 36.1, total 98.68. The empirical formula based on (Li + Al + Fe) = 6 apfu is Li1.94(Al4.05Fe0.02)Σ4.07(OH)12(CO3)1.03(H2O)3.03. The crystal structure was refined by the Rietveld method with RB = 0.006 and Rwp = 0.014. Akopovaite is monoclinic, C2/m, a = 5.0953(6), b = 8.877(1), c = 7.806(1) Å, β = 102.572(6)°, V = 344.61(8) Å3 and Z = 1. The polytype should be denoted as 1M. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 7.66(100)(001), 4.397(27)(020), 3.821(45)(002,021), 2.4881(27)(200), 2.2273(16)(201) and 1.9027(18)(202). Akopovaite is the first naturally occurring hydrotalcite-supergroup carbonate species of Al and Li; its synthetic analogue is known.

Research on the biogenic-specific polymorphism and morphology of carbonate has been gaining momentum in the fields of biomineralization and industrial engineering in recent years. We report the nucleation of carbonate particles on bacterial cell templates to produce a novel dumbbell-like morphology which was assembled by needle-like crystals of magnesium calcite or aragonite radiating out from both ends of the template bacterium. Mature dumbbell-like structures had a tendency to break apart in the central template region, which was made up mostly of weak amorphous carbonate. Further crystal growth, especially at the template region, transformed the broken pieces into spherulites. Rod-like cell templates were essential for the formation of dumbbell-like morphologies, and we propose a possible formation mechanism of the dumbbell-like morphology. Our findings provide new perspectives on the morphological formation mechanism in biomineralization systems and may have a potential significance in assembling composite materials suitable for industrial applications.

We have investigated the possibility of direct accelerator mass spectrometry radiocarbon (AMS 14C) measurement of carbonate samples at ANSTO using the STAR 2 MV tandem accelerator. Each carbonate sample was powdered, mixed with metal powder and pressed into an aluminum cathode for direct carbonate measurement by AMS 14C. Of the three high-purity metal powders (Fe, Nb, and Ag) used in our investigation, Nb was found to be the best metal, which delivered higher carbon beam currents and lower background. Beam currents for targets containing the optimal carbonate mass of 1.5–2.0 mg were ∼8% of those obtained from graphite targets of standard size (>0.5 mg C). Typical measured blank for Carrara marble (IAEA-C1) of ∼40 ka was obtained. Background-corrected 14C values of carbonate targets agreed well with their associated values obtained from high-precision analysis of graphite targets within 2σ uncertainties. Typical precision of this rapid AMS analysis was ∼1% for samples <8 ka. Despite lower precision for carbonate target ages (compared to standard graphite target ages), these ages are useful for palaeobiological applications where a large number of dates are required, such as time-averaging studies.