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

The formation of calcium carbonate scale in pipes and devices in water supply networks poses serious problems. Electromagnetic treatment (EMT) is a technology that can prevent the formation of these scales without the need to add chemical reagents, reducing maintenance costs in the installations. In this work, the types of crystals commonly found in water distribution systems are studied, with emphasis on the different techniques that allow their characterization (TGA, XRD, SEM), and the effects that EMT produces on their morphology. Laboratory trials have been carried out with synthetic water prepared from a calcium carbonate solution to study the crystals obtained at different temperatures, with and without EMT. High temperatures cause the production of aragonite instead of the stable form (calcite), as was observed in the samples from the heater resistors. In contrast, in the samples taken in lower temperature zones, a majority presence of calcite was observed. These results have been corroborated with a laboratory-scale evaporation trial, obtaining an increase in the aragonite/calcite ratio with increasing temperature and with the treatment applied, generating crystalline phases that exceed 70% aragonite (needle shape). It is highlighted that the EMT limits the reversion of aragonite to calcite and decreases the formation of scale.

Stable isotope, trace element, and cathodoluminescence analyses were performed on gastropods and matrix from rock cores of the Middle to Upper McMurray Formation (Lower Cretaceous/Aptian, Northwestern Alberta, Canada) to characterize the extent to which pristine material remained from which depositional environmental conditions could be estimated. Aragonitic gastropod shells retain their original depositional chemistry, and along with other closely associated authigenic carbonate components, indicate that the Middle to Upper McMurray Formation was deposited in a freshwater environment that was part of a continent-scale river system.

Crystalline calcium carbonates (CCCs) are among the most widespread minerals on the Earth’s surface and play a crucial role in the global carbon cycle, heavy metal sorption and incorporation. Among the numerous factors that influence the precipitation of CCCs from solution, the most determinant are the presence of additives in the mineral-forming medium, temperature, and crystallization time (aging time). The current work fills the gaps in the study of calcium carbonate crystallization from heavy metal (Me2+ = Co, Ni, Cu Fe)-containing solutions (Me2+/Ca 0.005–1.600) at different temperatures (3 and 23 °C) and aging times (21–158 days). The resulting precipitates were studied using optical and scanning electron microscopy, powder X-ray diffraction and energy-dispersive X-ray spectroscopy. Three crystalline calcium carbonates (synthetic analogues of calcite, aragonite and monohydrocalcite), as well as amorphous carbonate (AC), were found in the resulting precipitates. Temperature and aging time have a considerable effect on the phase composition, morphology and heavy metal content in CCCs. Low temperature (3 °C) and short aging times are generally favorable for the formation of monohydrocalcite and amorphous carbonate, while calcite tends to form at a higher temperature (23 °C) and in long-term experiments. Heavy metals can be incorporated into the calcite/monohydrocalcite crystal lattice in sufficient amounts, while aragonite can host a very small amount of Me2+ (or none). Calcite can concentrate Co (up to ~0.25 atoms per formula unit (apfu)) and Ni/Cu (up to ~0.05 apfu), while its Fe content is very close to the detection limits. Calcite precipitated at a higher Me2+/Ca ratio and temperature (23 °C) contains less Me2+ compared to calcite precipitated at a lower Me2+/Ca ratio and temperature (3 °C). Monohydrocalcite can host up to ~0.1 apfu of Co/Ni/Cu with no detectable preference for Me2+. The amount of Me2+ in monohydrocalcite decreases as aging time or temperature increases. It is worth noting that AC is the main carrier of heavy metals in the system being investigated and it should be considered the main host phase in heavy metal adsorption from aqueous solutions. The results obtained can be used to solve environmental issues and in mineral resource management.

This work presents a new discussion about the vibrational properties of the carbonate ion displayed in several different environments. The microparameters introduced by cation substitution and different crystal lattices in addition to the crystal aggregation are present in the discussion. The work comments on how the Raman modes are affected by these changes by using data obtained with four different laser excitation sources. Raman spectra excited at 1064 nm are reported at 1 cm−1 resolution. New observations and approaches based on the Raman modes highlight the differences observed in the relative intensity and width of the bands. The new data contribute to the understanding of these materials and their spectra, bringing new observations based on the Raman modes. This work presents a new approach highlighting the differences observed in the relative intensity and width of the Raman bands. The results indicate some evidence of the influence of the crystal habit and/or the growth of the mineral itself on the Raman spectrum. In addition, the data show the influence of cation substitution upon Raman bandwidth and the interference of the size of the spot of the laser in the measurement.

Composite powders were synthesized from the water solutions of sodium silicate and different calcium salts (nitrate, chloride, and acetate) at a Ca/Si molar ratio of 1.0. According to the XRD data, all the synthesized powders included hydrated calcium silicate Ca1,5SiO3,5·xH2O (Ca/Si molar ratio = 1.5) and calcium carbonate CaCO3 (Ca/Si molar ratio = ∞). The presence of H2SiO3 or SiO2·xH2O in the synthesized powders was assumed to be due to the difference between the Ca/Si molar ratio of 1.0 specified by the synthesis protocol and the molar ratio of the detected products. Reaction by-products (sodium nitrate NaNO3, sodium chloride NaCl, and sodium acetate NaCH3COO) were also found in the synthesized powders after filtration and drying. According to the XRD data phase composition of all powders after washing four times consisted of the quasi-amorphous phase and calcium carbonate in the form of calcite. Calcium carbonate in the form of aragonite was detected in powders synthesized from calcium chloride CaCl2 and calcium nitrate Ca(NO3)2 before and after washing. Synthesized powders containing reaction by-products and washed powders were used for the preparation of ceramics at 900, 1000, and 1100 °C. The phase composition of the ceramic samples prepared from the washed powders and powder containing NaCl after firing at 900 and 1000 °C consisted of β-wollastonite β-CaSiO3, and, after firing at 1100 °C, consisted of both β-wollastonite β-CaSiO3 and pseudo-wollastonite α-CaSiO3. The phase composition of the ceramic samples prepared from powders containing sodium nitrate NaNO3 and sodium acetate NaCH3COO after firing at 900, 1000, and 1100 °C consisted of calcium sodium silicates, i.e., Na2Ca2Si3O9 (combeite) and Na2Ca3Si2O8. Synthesized and washed composite powders can be used for the preparation of biocompatible materials, in the technology of construction materials, and as components of lunar soil simulants.

Sixteenth century wall paintings were analyzed from a church in an advanced state of decay in the Apennines of central Italy, now a remote area but once located along the salt routes from the Po Valley to the Ligurian Sea. Infrared spectroscopy (FTIR-ATR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) with a microprobe were used to identify the painting materials, as input for possible future restoration. Together with the pigments traditionally used for wall painting, such as ochre, ultramarine blue, bianco di Sangiovanni, cinnabar/vermilion, azurite, some colors were also found to have only been used since the 18th century. This thus suggests that a series of decorative cycles occurred after the church was built, confirmed by the multilayer stratigraphy of the fragments. Some of these colors were also unusual, such as clinochlore, Brunswick green, and ultramarine yellow. The most notable result of the analytical campaign however, was the ubiquitous determination of aragonite, the mineralogical form of calcium carbonate, mainly of biogenic origin. Sources report its use in Roman times as an aggregate in mortars, and in the literature it has only been shown in Roman wall paintings. Its use in 16th century wall paintings is thus surprising.

The non-natural mineralization of CaCO3 with special structures or morphologies is generated during the migration of crude oil and is the main form of scale in alkaline/surfactant/polymer (ASP) flooding in oilfields, adversely affecting oil recovery and causing environmental pollution. To date, the mineralization of aragonite superstructures and the role of heavy alkyl-benzene sulfonate (HABS) in mineralization are still unclear. In this work, aragonite-based superstructures of CaCO3 crystals were obtained in an O/W emulsion with HABS to help deepen the understanding of the diversified growth of CaCO3 scaling in oilfields. As a result, rosette-like, bouquet-like, and dumbbell-shaped CaCO3 crystals with vaterite–aragonite, aragonite, and calcite–aragonite phases were formed with 200 mg/L HABS concentration at 45 °C for 60 min and spherical vaterite phase stabilized at a high HABS concentration (800 mg/L and 1000 mg/L). Rhombohedral calcite content experienced a fluctuation of about 40% as the HABS concentration varied. Needle-like and bundle-like aragonite precipitates were generated with increasing temperatures from 65 °C to 85 °C. Thus, HABS affects the nucleation and growth of the precipitated CaCO3 solid, leading to modifications in the structure and morphology of the crystals. The synergistic effect between HABS and temperature can regulate ion pairs with the calcium ions and block sites that are essential to the incorporation of new solutes into the crystal lattice, which leads to the heterogeneous nucleation of vaterite and aragonite on calcite, forming aragonite-based superstructures in kerosene emulsion. This work may enrich the understanding of CaCO3 mineralization in oilfields, and also provide a novel strategy for manufacturing organic–inorganic composites.

Caudofoveates are benthic organisms that reside in the deep waters of continental slopes in the world. They are considered to be a group that is of phylogenetic and ecological importance for the phylum Mollusca. However, they remain poorly studied. In this work, we revealed the structure of the spicules of Caudofoveatan mollusks Falcidens sp. The spicules presented a hierarchical organization pattern across different length scales. Various imaging and analytical methods related to light and electron microscopy were employed to characterize the samples. The primary imaging methods utilized included: low voltage field emission scanning electron microscopy (FEG-SEM), focused ion beam-scanning electron microscopy (FIB-SEM), high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), and electron diffraction. In addition, we performed a physicochemical analysis by electron energy loss spectroscopy (EELS) and energy dispersive X-ray spectroscopy (EDS). A crucial factor for successfully obtaining the results was the preparation of lamellae from the spicules without damaging the original structures, achieved using FIB-SEM. This allowed us to obtain diffraction patterns of significant areas of well-preserved sections (lamellae) of the spicules in specific directions and demonstrate for the first time that the bulk of these structures is organized as a single crystal of calcium carbonate aragonite. On the other hand, AFM imaging of the spicules’ dorsal surface revealed a wavy appearance, composed of myriads of small, pointed crystallites oriented along the spicules’ longer axis (i.e., the c-axis of the aragonite). The organization pattern of these small crystallites, the possible presence of twins, the relationship between confinement conditions and accessory ions in the preference for mineral polymorphs, and the single crystalline appearance of the entire spicule, along with the observation of growth lines, provide support for further studies employing Caudofoveata spicules as a model for biomineralization studies.

We analyze 214 freshly laid eggs belonging to 16 species across three orders of Class Reptilia. Using mechanical compression tests, we measure each egg’s absolute stiffness (K, unit: N m−1) and relative stiffness (C number). The effective Young’s modulus, E, was obtained by combining experimental and numerical methods. The mineral (CaCO3) content was measured by acid–base titration, the microstructures by scanning electron microscopy (SEM), and the crystallography by electron backscatter diffraction (EBSD). We find that the C number of reptilian eggs is, on average, higher than that of bird eggs, indicating that reptilian eggs are stiffer with respect to the egg mass than birds. However, Young’s moduli of the reptilian eggshells (32.85 ± 3.48 GPa) are similar to those of avian eggshells (32.07 ± 5.95 GPa), even though those eggshells have different crystal forms, microstructures, and crystallography. Titration measurement shows that the reptilian eggshells are highly mineralized (>89% for nine Testudines species and 96% for Caiman crocodilus). Comparing the species with aragonite and calcite crystals, we find that calcite shells, including those of the Kwangsi gecko (inner part) and spectacled caiman (outer part), generally have larger grains than the aragonite ones. However, the grain size is not correlated to the effective Young’s modulus. Also, as measured by the C number, the aragonite shells are, on average, stiffer than the calcite ones (except for the Kwangsi gecko), primarily due to their thicker shells.

Anthropogenic carbonates are pyrotechnological products composed of calcium carbonate, and include wood ash, lime plaster/mortar, and hydraulic mortar. These synthetic materials are among the first produced by humans, and greatly influenced their biological and cultural evolution. Therefore, they are an important component of the archeological record that can provide invaluable information about past lifeways. One major aspect that has been long investigated is the possibility of obtaining accurate radiocarbon dates from the pyrogenic calcium carbonate that makes up most of these materials. This is based on the fact that anthropogenic carbonates incorporate atmospheric carbon dioxide upon the carbonation of hydrated lime, and thus bear the radiocarbon signature of the atmosphere at a given point in time. Since plaster, mortar, and ash are highly heterogeneous materials comprising several carbon contaminants, and considering that calcium carbonate is prone to dissolution and recrystallization, accurate dating depends on the effectiveness of protocols aimed at removing contaminants and on the ability to correctly identify a mineral fraction that survived unaltered through time. This article reviews the formation and dissolution processes of pyrogenic calcium carbonate, and mineralogical approaches to the definition of a ‘dateable fraction’ based on its structural properties.

We prepared solution-precipitated amorphous calcium carbonate by two similar methods and tracked structural changes over time as they crystallized. By cross-referencing mid-range infrared (400–4000 cm−1) with far-infrared (100–400 cm−1) spectral features, and by comparing with powder X-ray diffraction data for the aged crystallized products, we provide guidelines for—and potential limitations of—using far-infrared spectroscopy to assess multi-phase Mg-containing calcium carbonate samples that include amorphous or poorly crystallized components.

Carbonate ooids are a significant component of shallow water carbonate deposits in the present and geologic past, yet their origin and formation mechanism have been the subject of continuing debate. This study focuses on the well-preserved Holocene aragonitic ooids collected from the west Qaidam Basin, Qinghai-Tibetan Plateau (QTP). The mineralogical and chemical compositions, and stable (δ13C and δ18O), and radiocarbon isotopes of the ooids were analyzed to investigate their formation and develop a depositional model. The ooids formed approximately 5377±61 cal BP, and their cortices were composed of microcrystalline aragonite, with most nuclei being quartz grains. Stable carbon and oxygen isotopes indicate that authigenic aragonite precipitation is driven by evaporation and associated degassing of CO2 under turbulence conditions in a shallow alkaline lakes. Furthermore, eletron microscopy showed no presence of microfossils in ooid cortices or other evidence of microbial activity. Therefore, we propose that aragonite precipitation during ooid formation is most likely induced abiotically by increasing alkalinity due to evapoconcentration of lake waters based on an absence of an efficient carbonate-inducing metabolic pathway. New observations and detailed analyses of aragonitic ooid samples in the Qaidam Basin provide an improved understanding of the origin and formation processes of carbonate ooid in modern environment and the geologic past.

Microbial mats represented the earliest complex ecosystems on Earth, since fossil mineralized examples (i.e., microbialites) date back to the Archean Eon. Some microbialites contain putative remains of organic matter (OM), however the processes and pathways that lead to the preservation of OM within microbialite minerals are still poorly understood. Here, a multidisciplinary study is presented (including petrographic, mineralogical and organic geochemical analyses), focusing on a modern calcifying mat from a hypersaline lake in the Kiritimati atoll (Central Pacific). The results show that this mat has a complex history, with two main growth phases under hypersaline conditions, separated by an interruption caused by desiccation and/or freshening of the lake. The mineral precipitates of the mat are predominantly aragonitic and two contrasting precipitation modes are observed: the main growth phases of the mat were characterized by the slow formation of irregular micritic particles with micropeloidal textures and subspherical particles, linked to the degradation of the exopolymer (EPS) matrix of the mat; whereas the interruption period was characterized by the rapid development of a thin but laterally continuous crust composed of superposed fibrous aragonite botryoids that entombed their contemporaneous benthic microbial community. These two precipitation modes triggered different preservation pathways for the OM of the mat as the thin crust shows a particular lipid biomarker signature, different from that of other layers and the relatively rapid precipitation of the crust protecting the underlying lipids from degradation, causing them to show a preservation equivalent to that of a modern active microbial community, despite them being >1100 years old. Equivalent thin mineral crusts occur in other microbialite examples and, thus, this study highlights them as excellent targets for the search of well-preserved biomarker signatures in fossil microbialites. Nevertheless, the results of this work warn for extreme caution when interpreting complex microbialite biomarker signatures, advising combined petrographic, mineralogical and geochemical investigations for the different microbialite layers and mineral microfabrics.

Aragonite plays an important role in the biomineralization of serpulid polychaetes. Aragonitic structures are present in a wide range of serpulid species, but they mostly belong to one clade. Aragonitic structures are present in a wide range of marine environments, including the deep ocean. Aragonitic tube microstructures were studied using a scanning electron microscope. X-ray powder diffraction was used to identify the aragonite. Aragonite is used to build five different types of microstructures in serpulid tubes. The most common aragonitic irregularly oriented prismatic structure (AIOP) is also, evolutionarily, the most primitive. Some aragonitic microstructures, such as the spherulitic prismatic (SPHP) structure, have likely evolved from the AIOP structure. Aragonitic microstructures in serpulids are far less numerous than calcitic microstructures, and they lack the complexity of advanced calcitic microstructures. The reason why aragonitic microstructures have remained less evolvable than calcitic microstructures is currently unknown, considering their fit with the current aragonite sea conditions (Paleogene–recent).

Polychaete annelids are a very important group of calcifiers in the modern oceans. They can produce calcite, aragonite, and amorphous phosphates. Serpulids possess very diverse tube ultra-structures, several unique to them. Serpulid tubes are composed of aragonite or calcite or a mixture of both polymorphs. The serpulid tubes with complex oriented microstructures, such as lamello fibrillar, are exclusively calcitic, whereas tubes with prismatic structures can be composed either of calcite or aragonite. In serpulids, the calcareous opercula also have complex microstructures. Evolutionarily, calcitic serpulid taxa belong to one clade and the aragonitic taxa belong to another clade. Modern ocean acidification affects serpulid biomineralization. Serpulids are capable of biomineralization in extreme environments, such as the deepest part (hadal zone) of the ocean. The tubes of calcareous sabellids are aragonitic and have two layers, the inner irregular spherulitic prismatic layer and the outer spherulitic layer. The tube wall of cirratulids is composed of aragonitic lamellae with a spherulitic prismatic structure. In some other polychaetes, biominerals are formed in different parts of the animal body, such as chaetae or body shields, or occur within the body as granule-shaped or rod-shaped inclusions.

Using the density functional theory with the hybrid functional B3LYP and the basis of localized orbitals of the CRYSTAL17 program code, the dependences of the wavenumbers of normal long-wave ν vibrations on the P(GPa) pressure ν(cm−1) = ν0 + (dv/dP)·P + (d2v/dP2)·P and structural parameters R(Å) (R: a, b, c, RM-O, RC-O): ν(cm−1) = ν0 + (dv/dR) − (R − R0) were calculated. Calculations were made for crystals with the structure of calcite (MgCO3, ZnCO3, CdCO3), dolomite (CaMg(CO3)2, CdMg(CO3)2, CaZn(CO3)2) and aragonite (SrCO3, BaCO3, PbCO3). A comparison with the experimental data showed that the derivatives can be used to determine the P pressures, a, b, c lattice constants and the RM-O metal-oxygen, and the RC-O carbon-oxygen interatomic distances from the known Δν shifts. It was found that, with the increasing pressure, the lattice constants and distances R decrease, and the wavenumbers increase with velocities the more, the higher the ν0 is. The exceptions were individual low-frequency lattice modes and out-of-plane vibrations of the v2-type carbonate ion, for which the dependences are either nonlinear or have negative dv/dP (positive dv/dR) derivatives. The reason for this lies in the properties of chemical bonding and the nature of atomic displacements during these vibrations, which cause a decrease in RM-O and an increase in RC-O.

Biomaterials, especially when coated with adhesive polymers, are a key tool for restorative medicine, being biocompatible and supportive for cell adherence, growth, and function. Aragonite skeletons of corals are biomaterials that support survival and growth of a range of cell types, including neurons and glia. However, it is not known if this scaffold affects neural cell migration or elongation of neuronal and astrocytic processes, prerequisites for initiating repair of damage in the nervous system. To address this, hippocampal cells were aggregated into neurospheres and cultivated on aragonite skeleton of the coral Trachyphyllia geoffroyi (Coral Skeleton (CS)), on naturally occurring aragonite (Geological Aragonite (GA)), and on glass, all pre-coated with the oligomer poly-D-lysine (PDL). The two aragonite matrices promoted equally strong cell migration (4.8 and 4.3-fold above glass-PDL, respectively) and axonal sprouting (1.96 and 1.95-fold above glass-PDL, respectively). However, CS-PDL had a stronger effect than GA-PDL on the promotion of astrocytic processes elongation (1.7 vs. 1.2-fold above glass-PDL, respectively) and expression of the glial fibrillary acidic protein (3.8 vs. and 1.8-fold above glass-PDL, respectively). These differences are likely to emerge from a reaction of astrocytes to the degree of roughness of the surface of the scaffold, which is higher on CS than on GA. Hence, CS-PDL and GA-PDL are scaffolds of strong capacity to derive neural cell movements and growth required for regeneration, while controlling the extent of astrocytic involvement. As such, implants of PDL-aragonites have significant potential as tools for damage repair and the reduction of scar formation in the brain following trauma or disease.

Lake Qinghai is sensitive to climatic changes because of its pivotal location between mid-latitude Westerlies and the low-latitude East Asian monsoon. An 18.6 m long drilling core (1Fs) from Lake Qinghai provides new information on the hydroclimatic dynamics since the last glacial period. Here, we present the results of bulk mineral assemblages of this core. X-ray diffraction (XRD) results showed that the bulk minerals of the core sediments consist of major clastic minerals (e.g., quartz, feldspar, muscovite), carbonates (e.g., calcite, aragonite, dolomite), and minor clay minerals (e.g., chlorite). Quartz as an exogenous detrital mineral in lake sediments, its abundance is related to lake level changes resulting from regional climate changes via fluvial/aeolian transportation. Aragonite was precipitated from water solutions or chemical alteration of pre-existing minerals or biogenic mediation, closely related to lake hydroclimate change. Mineral assemblages revealed remarkable stepwise hydroclimatic changes. High quartz content and low calcite without aragonite suggested a cold-wet climate condition under predominant westerlies during the last glacial period from 35 to 25.3 ka. Afterward, quartz decreased and aragonite occasionally appeared, indicating an unstable hydroclimatic condition during the last deglaciation. Since the Early Holocene (11.9–8.2 ka), predominant minerals shifted from terrigenous quartz to authigenic carbonates, suggesting an increasing lake level, possibly due to intensified Asian summer monsoon with increased effective moisture. Aragonite became the primary carbonate mineral, implying a warming and humid hydroclimate environment with a relatively higher lake-level. During the Middle Holocene (8.2–4.2 ka), aragonite showed a decreasing trend indicating a higher lake level with weak evaporation. During the Late Holocene since 4.2 ka, there were lower quartz and aragonite, suggesting a deep lake with a weak summer monsoon. Our quartz and carbonate minerals record provided essential clues to reconstruct hydroclimate change in Lake Qinghai since the last glacial period.

The preferential incorporation of carboxylic acids into aragonite and its effects on the crystal growth and physicochemical properties of aragonite were systematically investigated using a seeded co-precipitation system with different carboxylic acids (citric, malic, acetic, glutamic, and phthalic). Aragonite synthesized in the presence of citric and malic acids showed a remarkable decrease in the crystallinity and size of crystallite, and the retardation of crystal growth distinctively changed the crystal morphology. The contents of citric acid and malic acid in the aragonite samples were 0.65 wt % and 0.19 wt %, respectively, revealing that the changes in the physicochemical properties of aragonite were due to the preferential incorporation of such carboxylic acids. Speciation modeling further confirmed that citric acid with three carboxyl groups dominantly existed as a metal–ligand, (Ca–citrate)−, which could have a strong affinity toward the partially positively charged surface of aragonite. This indicates why citric acid was most favorably incorporated among other carboxylic acids. Our results demonstrate that the number of carboxyl functional groups strongly affects the preferential incorporation of carboxylic acids into aragonite; however, it could be suppressed by the presence of other functional groups or the structural complexity of organic molecules.

Ten distinct microstructures occur in fossil serpulids and serpulid tubes can contain several layers with different microstructures. Diversity and complexity of serpulid skeletal structures has greatly increased throughout their evolution. In general, Cenozoic serpulid skeletal structures are better preserved than Mesozoic ones. The first complex serpulid microstructures comparable to those of complex structures of molluscs appeared in the Eocene. The evolution of serpulid tube microstructures can be explained by the importance of calcareous tubes for serpulids as protection against predators and environmental disturbances. Both fossil cirratulids and sabellids are single layered and have only spherulitic prismatic tube microstructures. Microstructures of sabellids and cirratulids have not evolved since the appearance of calcareous species in the Jurassic and Oligocene, respectively. The lack of evolution in sabellids and cirratulids may result from the unimportance of biomineralization for these groups as only few species of sabellids and cirratulids have ever built calcareous tubes.

There are few research reports on the relationship between fish habitats and the periodicity of the fishes’ incremental lines of otolith fossils. The present study examines this relationship through histological and analytical studies on otolith fossils from Nobori Formation, Pliocene, Japan. The specimens were observed and analyzed using light microscopy, polarizing microscopy, Miniscopy, Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) analysis, electron probe X-ray microanalyzer (EPMA), Raman spectroscopy, and XRD. The otolith crystals were aragonite according to XRD and Raman analysis. The incremental lines contained C, O, and Ca, with Si as a trace element. In the layer between the incremental lines, Si was not detected. The circadian incremental lines were unclear and irregularly observed in both Lobianchia gemellarii and Diaphus gigas. Their behavioral pattern included a diurnal vertical movement. By comparison, for Cetonurus noboriensis, Ventrifossa sp., Sebastes scythropus, and Congriscus megastomus, the circadian incremental lines were evident. The habitat of the fishes that live exclusively on the continental slope is kept constant, and the circadian incremental lines are formed regularly. However, for fishes that spend the day in the deep sea and ascend to the shallow sea at night, the ecosystem, such as seawater temperature and pressure, fluctuates, and the circadian incremental lines become unclear and irregular. The period of the circadian incremental lines of otolith may vary due to differences in the ecosystems.

A block of sandstone retrieved by divers from near Rathlin Island, Co. Antrim, Northern Ireland, represents an aragonite cemented sand formed during the Quaternary. Strongly negative δ13C of the aragonite cement (−50 to −60‰ δ13C) indicates that the hardground was formed by the anaerobic oxidation of methane (AOM), resulting in the formation of a methane-derived authigenic carbonate (MDAC) hardground. Such hardgrounds have previously been recorded as forming extensive pavements in deeper waters in the mid Irish Sea (e.g., Croker Carbonate Slabs), although the latter also contains high-magnesium calcite. Sand was initially deposited as part of a storm lag deposit, with a reworked bivalve and gastropod fauna. This sand was then colonised by a probable crustacean fauna, producing horizontal open dwelling burrows (Thalassinoides). After aragonite cementation, the hardground was colonised by boring bivalves, with slightly negatively elevated levels of δ13C. Finally, the hardground was colonised by an encrusting fauna (bryozoans, calcareous algae and serpulids), by then in warmer seas. Continued depleted levels of δ13C present within the encrusting fauna (−1 to −5‰ δ13C) indicate continued methane generation and seepage, which may still be active to the present day, and to the possibility of shallow gas reserves. The δ18O values change between macro-infauna vs. encrusters, indicating a warming in water temperature, reflecting glacial and post-glacial environments. The aragonite cemented sandstone has a highly variable porosity, with large vugs (open burrows and borings), smaller mouldic porosity within gastropods and bivalves and complex micro-porosity associated with acicular aragonite cements. Overall permeability was recorded at the 2.5 to 23 Darcies level, reflecting the highly variable vuggy porosity, although matrix permeability was around 100 mD and controlled by the MDAC fabric. Actual permeability will likely be controlled by the extent to which larger pores are interconnected. The sea around the Rathlin Island area contains a diverse fauna, which is worthy of future study in the context of cold seep and MDAC pavement formation.

Polycrystalline carbonate minerals (including calcite, Mg-calcite, and aragonite) can show distinctive variations in their far-infrared (FIR) spectra. We describe how to identify mixed-phase samples by correlating FIR spectral changes with mid-infrared spectra, X-ray diffraction data, and simple peak overlap simulations. Furthermore, we show how to distinguish portlandite-containing (Ca(OH) 2 ) mixtures that are common in heated calcium carbonate samples. Ultimately, these results could be used for tracking how minerals are formed and how they change during environmental exposure or processing after extraction.

We studied 46 small, drainless lakes in various landscape types: The sub-taiga (Vasyugan plain), forest–steppe (Baraba lowland), and steppe and subzone of ribbon forests (Kulunda plain). Sampling of lake components (sediments, water, and biota) was performed. The materials were analyzed via a combination of modern analytical methods (atomic absorption spectroscopy, X-ray fluorescence, scanning electron microscopy and X-ray diffractometry). It was found that in the south of Western Siberia, lakes with a bicarbonate-sodium water composition are widespread against the background of general landscape zoning. This composition contributes to the abundant growth of biota in the lakes, which leads to the processes of authigenic carbonate formation from calcite–dolomite series and aragonite on geochemical barriers, i.e., drifting biota–water, submerged biota–water, and water–bottom sediments against a background of terrigenous demolition and organic matter accumulation. The article shows the differences in the composition and structure of low-temperature carbonate minerals formed on various geochemical barriers. It was found that low-magnesium calcite and aragonite are the most common authigenic carbonates in small lakes in the south of Western Siberia and are formed on all three geochemical barriers in lakes. High-magnesium calcites and Ca-excess dolomites are formed only at the water–bottom sediment barrier in lakes with HCO3–Na and Cl–HCO3–Na water composition at pH > 9 and with a total dissolved solids > 3 g·L−1 (in some lakes of HCO3-Na composition with a TDS < 3 g·L−1 and pH > 9).

Although biomineralization of minerals induced by microorganisms has been widely reported, the mechanisms of biomineralization and the characteristics of the biominerals precipitated needs to be studied further. In this study, Staphylococcus warneri YXY2, a moderate halophile, was used to induce the precipitation of carbonate minerals at various Mg/Ca molar ratios. To investigate the biomineralization mechanism, the growth curve, pH changes, ammonia test, the concentration of bicarbonate and carbonate ions, and the activity of carbonic anhydrase (CA) and alkaline phosphatase (ALP) were determined. X-ray powder diffraction (XRD), scanning electron microscopy - energy disperse spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and stable carbon isotope analyses were used to characterize the minerals. The obtained biotic minerals were calcite, vaterite, Mg-rich calcite, and aragonite crystals. The crystallinity of aragonite decreased with increasing Mg/Ca ratios. The preferred orientation, diverse morphologies, organic substances, and more negative stable carbon isotope values proved the biogenesis of these carbonate minerals. The presence of Mg in the biotic aragonite crystals was likely related to the acidic amino acids which also facilitated the nucleation of minerals on/in the extracellular polymeric substances (EPS). Mg2+ and Ca2+ ions were able to enter into the YXY2 bacteria to induce intracellular biomineralization. Dynamics simulation using Material Studio software proved that different adsorption energies of Glutamic acid (Glu) adsorbed onto different crystal planes of aragonite led to the preferred orientation of aragonite. This study helps to deepen our understanding of biomineralization mechanisms and may be helpful to distinguish biotic minerals from abiotic minerals.

Marine invertebrates produce a plethora of bioactive compounds, which serve as inspiration for marine biotechnology, particularly in drug discovery programs and biomaterials development. This review aims to summarize the potential of drugs derived from marine invertebrates in the field of neuroscience. Therefore, some examples of neuroprotective drugs and neurotoxins will be discussed. Their role in neuroscience research and development of new therapies targeting the central nervous system will be addressed, with particular focus on neuroinflammation and neurodegeneration. In addition, the neuronal growth promoted by marine drugs, as well as the recent advances in neural tissue engineering, will be highlighted.

Cockle shell is an external covering of small, salt water edible clams (Anadara granosa) that dwells in coastal area. This abundant biomaterial is hard, cheap and readily available with high content of calcium carbonate in aragonite polymorphic form. At present, cockle shell-derived calcium carbonate nanoparticles (CSCaCO3NPs) with dual applications has remarkably drawn significant attention of researchers in nanotechnology as a nanocarrier for delivery of different categories of drugs and as bone scaffold due to its beneficial potentials such as biocompatibility, osteoconductivity, pH sensitivity, slow biodegradation, hydrophilic nature and a wide safety margin. In addition, CSCaCO3NP possesses structural porosity, a large surface area and functional group endings for electrostatic ion bonds with high loading capacity. Thus, it maintains great potential in the drug delivery system and a large number of biomedical utilisations. The pioneering researchers adopted a non-hazardous top-down method for the synthesis of CSCaCO3NP with subsequent improvements that led to the better spherical diameter size obtained recently which is suitable for drug delivery. The method is therefore a simple, low cost and environmentally friendly, which involves little procedural steps without stringent temperature management and expensive hazardous chemicals or any carbonation methods. This paper presents a review on a few different types of nanoparticles with emphasis on the versatile most recent advancements and achievements on the synthesis and developments of CSCaCO3NP aragonite with its applications as a nanocarrier for drug delivery in nanomedicine.

The Semyenov-2 hydrothermal field located at 13°31′N of the Mid-Atlantic Ridge (MAR) is associated with an oceanic core complex (OCC) and hosted by peridotites and basalts with minor amounts of gabbro and plagiogranites. Seafloor massive sulphides (SMS) are represented by chimneys with zonality, massive sulphides without zonality and sulphide breccia cemented by opal and aragonite. The mean value of Au (20.6 ppm) and Te (40 ppm) is much higher than average for the MAR SMS deposits (3.2 ppm and 8.0 ppm, respectively). Generally, these high concentrations reflect the presence of a wide diversity of Au and Te minerals associated with major mineral paragenesis: primary native gold, melonite (NiTe2) and tellurobismuthite (Bi2Te3) are related to high-temperature chalcopyrite (~350 °C); electrum (AuAg)1, hessite (Ag2Te) and altaite (PbTe) are related to medium- and low-temperature Zn-sulphide and opal assemblages (260–230 °C). Calaverite (AuTe2) and Te-rich “fahlore„ Cu12(Sb,As,Te)4S13 are texturally related to the chalcopyrite-bornite-covellite. Enrichment of Au in sulphide breccia with opal and aragonite cement is driven by the re-deposition and the process of hydrothermal reworking of sulphide. The low-temperature fluid mobilizes gold from primary sulphide, along with Au and Te minerals. As a result, the secondary gold re-precipitate in cement of sulphide breccia. An additional contribution of Au enrichment is the presence of aragonite in the Cu-Zn breccia where the maximal Au content (188 ppm) is reached.

In this work, we aimed to experimentally study the nucleation and growth of CaCO3 phases precipitated from supersaturated aqueous solutions in the presence of varying concentrations of sulphate oxyanion. The experiments were conducted under pH conditions close to neutral (7.6) and by considering a wide range of initial (SO42−)/(CO32−) ratios (0 to approx. 68) in the aqueous solution. We paid special attention to the evolution of the precipitates during ageing within a time framework of 14 days. The mineralogy, morphology, and composition of the precipitates were studied by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and EDX microanalysis. The concentration of sulphate ions in the reacted aqueous solution was studied by ICPs. The experimental results showed that the mineral composition of the precipitate recovered in each run varied with the (SO42−)/(CO32−) ratio in the parental solution, which influenced the mineral evolution of the precipitates during ageing. We observed that high concentrations of sulphate in the aqueous solution stabilized the vaterite precipitates and inhibited calcite formation. Furthermore, aragonite never precipitated directly from the solution, and it was only formed via a dissolution-precipitation process in solutions with a high (SO42−)/(CO32−) ratio after long reaction times. Finally, gypsum only precipitated after long ageing in those aqueous solutions with the highest concentration of sulphate. The reaction pathways during ageing, the morphology of the calcite crystals, and the composition of vaterite and calcite were discussed considering both kinetic and thermodynamic factors. These results showed a considerably more complex behavior of the system than that observed in experiments conducted under higher pHs and supersaturation levels and lower (SO42−)/(CO32−) ratios in the aqueous phase.

Lime plaster and mortar are pyrotechnological materials that have been employed in constructions since prehistoric times. They may nucleate as calcite and/or aragonite under different environmental settings. In nature, aragonite and calcite form through biogenic and geogenic processes that lead to different degrees of atomic order. The latter is a result of defects in the crystal lattice, which affect the properties of crystals, including their interaction with infrared light. Using Fourier transform infrared spectrometry (FTIR) with the KBr pellet method, it is possible to exploit these differences and assess the degree of atomic order of aragonite and calcite crystals and thus their mechanisms of formation. Here we use FTIR to characterize the degree of short-range atomic order of a pyrogenic form of aragonite recently observed in experimental and archaeological lime binders. We show that pyrogenic aragonite has a unique signature that allows its identification in archaeological sediments and lime binders of unknown origin. Based on these results, we developed a new FTIR-based method to assess the integrity and degree of preservation of aragonite and calcite when they occur together in the same material. This method allowed a better assessment of the diagenetic history of an archaeological plaster and finds application in the characterization of present-day conservation materials, such as lime plaster and mortar, where different polymorphs may nucleate and undergo recrystallization processes that can alter the mechanical properties of binders.

This study is focused on mineralogical and chemical characterization of an authigenic carbonate rock (crust) collected at a recently discovered cold seep on the US North Atlantic continental margin. X-ray diffraction (XRD) and scanning electron microscopy (SEM) indicate that the carbonate rock is composed of microcrystalline aragonite cement, white acicular aragonite crystals (AcAr), equant quartz crystals, small microcrystalline aluminosilicates, and trace amounts of iron sulfide microcrystals. Element/calcium ratios were measured with laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) using a calcite standard, which was prepared by annealing USGS certified carbonate powder (MACS-3). The occurrence of microscopic, non-carbonate inclusions precluded evaluation of trace elements in the aragonite cement, but allowed for in situ analysis of AcAr crystals. Carbon and oxygen isotopes were analyzed via isotope ratio mass spectrometry (IRMS) and expressed as δ13C and δ18O. Low δ13C values suggest that aragonite grew as a result of anaerobic oxidation of methane and observed δ18O values indicate that the temperature of aragonite crystallization was 1.7–1.9 °C.

To better predict long-term performance of a remediation system, parameters of a numerical model should be constrained with care by calibrating with reliable experimental data. This study conducted sensitivity analyses for model parameters, which were shown to represent reasonably well the observed geochemical behaviors for the column experiments that evaluated evolving reactivity of granular iron for the treatment of trichloroethylene (TCE) resulting from precipitation of secondary minerals. The particular model parameters tested include iron corrosion rate, aragonite and Fe2(OH)2CO3 precipitation rates, and proportionality constants for each mineral. For sensitivity analyses, a specific parameter was systematically changed, while other parameters were fixed at the values for the base case. The ranges of parameters tested were determined based on the previous modeling study. The results showed that the most important and sensitive model parameters were secondary mineral precipitation rates. Also, not only absolute precipitation rate for each mineral but also relative precipitation rates among different minerals were important for system performance. With help of sensitivity analysis, the numerical model can be used as a predictive tool for designing an iron permeable reactive barrier (PRB) and can provide implications for the long-term changes in reactivity and permeability of the system.

Natural resources such as plants, animals and minerals have always been used by mankind to develop drugs and marine world is no exception. Marine by-products like conches, pearls, mother of pearl shells, corals and so forth have been used by traditional Ayurvedic practitioners for centuries. The unique methods of these preparations are scientifically designed to eliminate unwanted impurities and convert them into bioavailable form. In this study, Conch (Xanchus pyrum) was used as a marine resource of calcium carbonate and was converted pharmaceutically from its aragonite form to calcite. All the steps of preparations and changes in the properties therein were documented and validated. Further, traditional as well as modern analytical tools were used to study its physical and chemical characters to develop a monograph. The physical characterization included particle size, X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Thermogravimetric Analysis (TGA) and Fourier Transform Infra-red (FTIR). Metal composition and heavy metal limits were determined using Inductively Coupled Plasma Optical Emission Spectrometry (ICPOES). This study revealed the rearrangement of aragonite crystals into calcite form by grinding, trituration with aloe vera juice and incineration under controlled conditions. Moreover, the finished product was found to be devoid of organic matrix that is nacre. This study creates a foundation for the development of a master formula for commonly used Shankha Bhasma in Ayurvedic medicines.

Bioinspired self-assembled composite materials are appealing both for their industrial applications and importance in natural sciences, and represent a stimulating topic in the area of materials science, biology, and medicine. The function of the organic matrix has been studied from the biological, chemical, crystallographic, and engineering point of view. Little attention has been paid to the effect of one of the two main components of the organic matrix, the sericin fraction, on the growth morphology of calcium carbonate polymorphs. In the present work, we address this issue experimentally, emphasizing the morphological effects of sericin on calcite and aragonite crystals, and on the formation of a sericin-aragonite-calcite self-assembled composite with a hierarchic structure comparable to that of natural nacre.

We have investigated dissolution and surface reaction of calcite and aragonite in amino acid solutions of L-glutamic (L-glu) and L-aspartic acid (L-asp) at weak acidity of above pH 3. The surface reactions of calcite and aragonite were related with the dissolution. Calcite was dissolved in both solutions but the dissolution was limited by an adsorption of Ca-carboxylate salt. Aragonite was neither dissolved nor reacted in amino acid solutions because the crystal surface consisted of a hard to dissolve structure.

Wt% of aragonite, a CaCO3 polymorph, increased with higher hydraulic activity (°C) of limestone in precipitated calcium carbonate (PCC) from the lime-soda process (Ca(OH)2-NaOH-Na2CO3). Only calcite, the most stable polymorph, was crystallized at hydraulic activity under 10 °C, whereas aragonite also started to crystallize over 10 °C. The crystallization of PCC is more dependent on the hydraulic activity of limestone than CaO content, a factor commonly used to classify limestone ores according to quality. The results could be effectively applied to the determination of polymorphs in synthetic PCC for eco-friendly paper manufacture.

The effectiveness of magnesium as a substitute material in enzyme-mediated calcite precipitation was evaluated. Magnesium sulfate was added to the injecting solution composed of urea, urease, and calcium chloride. The effect of the substitution on the amount of precipitated materials was evaluated through precipitation tests. X-ray powder diffraction and scanning electron microscopy analyses were conducted to examine the mineralogical morphology of the precipitated minerals and to determine the effect of magnesium on the composition of the precipitated materials. In addition to calcite, aragonite and gypsum were formed as the precipitated materials. The effect of the presence of aragonite and gypsum, in addition to calcite, as a soil-improvement technique was evaluated through unconfined compressive strength tests. Soil specimens were prepared in polyvinyl chloride cylinders and treated with concentration-controlled solutions, which produced calcite, aragonite, and gypsum. The mineralogical analysis revealed that the low and high concentrations of magnesium sulfate effectively promoted the formation of aragonite and gypsum, respectively. The injecting solutions which produced aragonite and calcite brought about a significant improvement in soil strength. The presence of the precipitated materials, comprising 10% of the soil mass within a treated sand, generated a strength of 0.6 MPa.