Calcite Crystal Growth Research Articles

Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic-Inorganic Hybrid Materials with Controlled Internal Structures.

Efficient occlusion of particulate additives into a single crystal has garnered an ever-increasing attention in materials science because it offers a counter-intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization-induced self-assembly is employed to synthesize well-defined and highly anionic poly(3-sulfopropyl methacrylate potassium)41-block-poly(benzyl methacrylate)500 [PSPMA41-PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic‐Inorganic Hybrid Materials with Controlled Internal Structures

AbstractEfficient occlusion of particulate additives into a single crystal has garnered an ever‐increasing attention in materials science because it offers a counter‐intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization‐induced self‐assembly is employed to synthesize well‐defined and highly anionic poly(3‐sulfopropyl methacrylate potassium)41‐block‐poly(benzyl methacrylate)500 [PSPMA41‐PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

Exploring calcite Coprecipitation: Synthesis, Crystal Growth, and pH effect

In this study, the synthesis and crystal growth of calcite (CaCO3) was examined with a focus on the coprecipitation and hydrothermal methods; additionally, crystal nucleation and growth was monitored under acidic and alkaline conditions. In the experiments, different Ca2+ solutions (pH 1.4 and 8.1) were mixed with Na2CO3 (pH 11.6), and the rates for the addition of the reactants were adjusted. Using an acidic Ca2+ solution as the calcium source and the rapid addition of carbonate, larger crystals were precipitated and grown in a single-step coprecipitation process. The fast addition of carbonate in an initially alkaline calcium solution produced intermediate crystal sizes. However, the slow dropwise addition of carbonate led to smaller crystals due to localized supersaturation and rapid nucleation. Coprecipitation followed by hydrothermal treatment produced larger crystals with the best-defined morphology. Structural and compositional analyses were conducted using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results showed the formation of calcite with different crystal sizes and provided insight into the controlled synthesis of CaCO3 crystals; our study has relevance for various industrial applications and for the investigation of natural sources.

Epitaxial Calcite Morphology Modified in the Presence of Magnesium and Sulfate Ions

AbstractMagnesium and sulfate are a determinant key in CaCO3 mineralization. However, the works of the literature have failed to provide a clear understanding of how these ions influence the nucleation‐growth of CaCO3 precipitation. Our study uses an electrochemical method, having for principle to impose a dissolved oxygen reduction potential on gold (111) films. This technique that allows the exclusive and controlled crystallization of epitaxial calcite established an ideal system for the study of foreign ions influence. The polymorph, composition and morphology of crystals are characterized using scanning electron microscopy (SEM) coupled with X‐ray energy dispersive spectroscopy (EDS) and Raman spectroscopy. The results demonstrate that the increase of calcium concentration in calcocarbonic pure solution enhances the nucleation and then the growth of calcite crystals without affecting their morphology and their orientation. However, the magnesium directly modifies the surface morphology of calcite as a consequence of Mg substitution to calcium ions and the inhibitive effect of magnesium is assured by an incorporation mechanism. In the matter of sulfate ions influence, the experimental results indicate that SO42− slows down the epitaxial calcite nucleation by substituting itself to carbonate ions preferentially in the center of the crystals facets causing an enlargement of the lattice parameter.

Environmentally-friendly calcite scale mitigation: encapsulation of CDs@ MS composite within membranes framework for nanofiltration

Scale formation caused by the precipitation of sparingly soluble salts such as CaCO3 is a major challenge in membrane-based desalination technologies, leading to flux decline and increased energy costs. Surface modification using nanoscale coatings is a promising approach to mitigate membrane fouling. In this work, we demonstrate the antiscalant properties of a MoS2-carbon quantum dot (CDs@MS-NF) composite with a nanoflower-like structure coating for suppressing calcite scale formation. The CDs@ MS-NF coating was synthesized via a solvothermal method and applied to a polyamide reverse osmosis membrane surface using an in-situ growth technique. Characterization revealed uniform coverage of MoS2 nanosheets decorated with CDs@MS-NF on the membrane surface. Static fouling tests simulating calcium sulfate scaling conditions were conducted to evaluate the antifouling performance. The CDs@MS-NF coated membrane exhibited a flux reduction of only 11 %, compared to 34 % for the unmodified membrane after 24 hours. Further analyses showed a calcite nucleation induction time of 5.2 hours and a critical scaling threshold of 1.8 times the solubility for the CDs@ MS-NF coated membrane, indicating significant inhibition of scale formation. We hypothesize that the CDs@ MS-NF nanocomposite layer alters surface charge and wettability while also catalyzing redox reactions to hinder calcite crystal growth. This work demonstrates that multifunctional two-dimensional nanocomposite coatings can effectively mitigate membrane scaling through multiple synergistic mechanisms.

Carbonate diagenesis: A celebration of the work of John Anthony Dawson (Tony) Dickson

Carbonate diagenesis: A celebration of the work of John Anthony Dawson (Tony) Dickson

Experimental study on calcium carbonate phase transition from amorphous to crystalline forms in a reverse emulsion

Calcium carbonate (CaCO3) nanoparticles for lubricant additives are typically manufactured in reverse emulsion. The amorphous form is sterically stabilised in oil to create the so-called, ‘overbased detergents’, for motor engine oils, whilst crystalline CaCO3 nanoparticles are produced for specific applications, like lubricating greases. Here, the phase transition of amorphous calcium carbonate to crystalline forms in a reverse water/oil emulsion was studied in a 23L jacketed batch reactor equipped with agitator, temperature and pressure control. During the process, several acids, such as acetic, alkylaryl and 12-hydroxystearic (HSA), were added. The impact of acid type and HSA quantity were studied with all other aspects constant. The amorphous to crystalline phase transition kinetics were measured, the crystal habits were observed and the solid forms were characterized. With no HSA, a more acidic environment resulted in faster transition kinetics from amorphous CaCO3 to calcite. However, the presence of HSA tended to slow down the transition kinetics. Indeed, calcite crystal growth was asymmetrically inhibited by HSA, leading to elongated rod-shaped crystals. Finally, a very high HSA concentration leads to the formation of vaterite crystals, vaterite being a less stable phase than calcite.

The combined effects of Mg2+ and Sr2+ incorporation during CaCO3 precipitation and crystal growth

Calcite (CaCO3) composition and properties are defined by the chemical environment in which CaCO3 forms. However, a complete understanding of the relationship between aqueous chemistry during calcite precipitation and resulting chemical and physical CaCO3 properties remains elusive; therefore, we present an investigation into the coupled effects of divalent cations Sr2+ and Mg2+ on CaCO3 precipitation and subsequent crystal growth. Through chemical analysis of the aqueous phases and microscopy of the resulting calcite phases in compliment with density functional theory calculations, we elucidate the relationship between crystal growth and the resulting composition (elemental and isotopic) of calcite. The results of this experimental and modeling work suggest that Mg2+ and Sr2+ have cation-specific impacts that inhibit calcite crystal growth, including: (1) Sr2+ incorporates more readily into calcite than Mg2+ (DSr > DMg), and increasing [Sr2+]tor [Mg2+]t increases DSr; (2) the inclusion of Mg2+ into structure leads to a reduction in the calcite unit cell volume, whereas Sr2+ leads to an expansion; (3) the inclusion of both Mg2+ and Sr2+ results in a distribution of unit cell impacts based on the relative positions of the Sr2+ and Mg2+ in the lattice. These experiments were conducted at saturation indices of CaCO3 of ∼4.1, favoring rapid precipitation. This rapid precipitation resulted in observed Sr isotope fractionation confirming Sr isotopic fractionation is dependent upon the precipitation rate. We further note that the precipitation and growth of calcite favors the incorporation of the lighter 86Sr isotope over the heavier 87Sr isotope, regardless of the initial solution conditions, and the degree of fractionation increases with DSr. In sum, these results demonstrate the impact of solution environment to influence the incorporation behavior and crystal growth behavior of calcite. These factors are important to understand in order to effectively use geochemical signatures resulting from calcite precipitation or dissolution to gain specific information.

Naturally Derived Cements Learned from the Wisdom of Ancestors: A Literature Review Based on the Experiences of Ancient China, India and Rome.

For over a thousand years, many ancient cements have remained durable despite long-term exposure to atmospheric or humid agents. This review paper summarizes technologies of worldwide ancient architectures which have shown remarkable durability that has preserved them over thousands of years of constant erosion. We aim to identify the influence of organic and inorganic additions in altering cement properties and take these lost and forgotten technologies to the production frontline. The types of additions were usually decided based on the local environment and purpose of the structure. The ancient Romans built magnificent structures by making hydraulic cement using volcanic ash. The ancient Chinese introduced sticky rice and other local materials to improve the properties of pure lime cement. A variety of organic and inorganic additions used in traditional lime cement not only changes its properties but also improves its durability for centuries. The benefits they bring to cement may also be useful in enzyme-induced carbonate precipitation (EICP) and microbially induced carbonate precipitation (MICP) fields. For instance, sticky rice has been confirmed to play a crucial role in regulating calcite crystal growth and providing interior hydrophobic conditions, which contribute to improving the strength and durability of EICP- and MICP-treated samples in a sustainable way.

Direct Pore‐Scale Numerical Simulation of Microbially Induced Calcium Carbonate Precipitation

AbstractMicrobially induced calcium carbonate precipitation (MICP) is a promising method for eco‐friendly solutions in geotechincal engineering. MICP involves highly coupled processes in geochemistry and bacterial metabolism that take place in a porous medium. Advancement of these processes drives calcite crystal growth which leads to a decrease in porosity and permeability of the medium. Mathematical models are being developed and used to predict the fate of system at different conditions. Micro‐scale and local bio‐geochemical evolution and its role on the overall macroscopic fate of MICP needs further investigation. In this work, a pore‐scale reactive transport model of MICP for biocementation is developed in a closed system. MICP is simulated in a sample porous geometry in 2D using a native geochemical solver and a lattice Boltzmann solver that handles diffusive transport. We present reactive‐transport factors to up‐scale pore‐scale effects and quantify the efficiency of MICP at different stages of the process. Our results show that pore‐scale effects on the average concentration of urea and calcium are not significant after the initial 20% of urea have been consumed. On the other hand, the pH evolution in the system is significantly affected by pore‐scale effects. We also explored effects of biomass density and biomass distribution on the reactive transport factors, as well as the effect of the urea to calcium ratio on the resulting crystallization patterns. We found that a higher ratio of rate of ureolysis to rate of precipitation leads to more nucleation sites and more uniform calcite precipitation in the geometry.

Calcium Carbonate Mineralization of Microalgae.

Biological substrates catalyze the nucleation and growth of sparingly soluble salts however, the underlying mechanism is largely unknown. In the present study, the growth of calcium carbonate (CaCO3), on Acutodesmus obliquus (AO) microalgae was investigated. The test microalgae favored the growth of CaCO3 from solutions supersaturated with respect to calcite (7.94 < SRcalcite < 104.71). The precipitation of calcite on AO was not preceded by measurable induction times, and the rates of calcite crystal growth were higher for higher microalgae cell concentrations. The presence of the microalgae cultivation medium and illumination of the supersaturated solutions accelerated the precipitation of CaCO3, increasing the rate by 75% in comparison with the respective value in its absence. AO cultures, air dried at 25 °C yielded higher precipitation rates, in comparison with the respective rates in the presence of active AO cultures. At 70 °C, nucleation and growth were suppressed, due to the destruction of the molecular structure of the microalgae. The CaCO3 precipitation rates on calcite precipitated on air-dried AO culture, were doubled in comparison with the respective rates obtained with the respective quantities of each component of the composite substrate.

Insight into evolution of chemical structure and mineralogy to reveal the mechanism of temperature-dependent phosphorus release from hydrochars

Shrimp shell (SS) is sustainable biomass with abundant minerals and developable phosphorus (P) resource. Hydrothermal carbonization of SS can solve the shortage of P resources and the utilization of waste. However, few studies on the application of SS hydrochar as fertilizer have been conducted. Having an insight into the evolution of chemical structure and mineralogy could understand the mechanism of P release. In this study, Olsen method was employed to determine the available P (AP) release, and the temperature-dependent evolution of crystalline phase, carbon skeleton structures and surface functionalities were characterized by XRD, XPS, FTIR and TG. The results of AP release from SS hydrochar showed the following temperature (120−280 °C in 20 °C intervals) dependence: 120 °C derived hydrochars (2.30 mg/g) >feedstock (1.51 mg/g) > 160−280 °C derived hydrochars. In addition, AP dissolution kinetic data were well fitted to pseudo-second-order equation (R2 >0.999). Two-dimensional correlation spectroscopy revealed that phosphate crystallinity degree was negatively corresponding to release behavior. Meanwhile, calcite crystal growth and the transformation of P species influence the P bioavailability of SS hydrochar. Therefore, hydrochar with lower phosphate crystalline could benefit the P fertilizing efficiency.

Air nanobubbles retard calcite crystal growth

Demands for “green” additives that control the crystal growth and inhibit the scale formation in industrial processes are growing as never before. Nanobubbles can be the green additive for inhibiting and/or promoting the crystal growth of calcium carbonate, given their well-known unique physicochemical properties. This paper reports for the first time the changes in the crystal growth rate of calcite in liquid in the presence of air nanobubbles. We injected the air nanobubbles into the solution and studied the calcite crystal growth for the first 4 h in a static condition at 20 °C and 88 °C. We found that air nanobubbles retarded the growth rate of calcite crystal by up to 53 % and 33 % at 20 °C and 88 °C, respectively. The retardation of calcite crystal growth could differ with different number densities of air nanobubbles added to the solution. A higher number density of nanobubbles generally showed slightly greater retardation throughout the tested 4 h. Air nanobubbles may influence the crystal growth either by changing solid-liquid interfacial tension on the crystal surface, reducing the free growth sites, adsorbing Ca2+ ions, playing roles in bubble mattress and thermal buffering on the crystal surface, or combinations of them. Our findings suggest that air nanobubbles can be utilized as a green inhibitor of calcite crystal growth and calcium carbonate scale in broad industrial areas.

Conservation paleobiology on Minami-Daito Island, Okinawa, Japan: anthropogenic extinction of cave-dwelling bats on a tropical oceanic island.

BackgroundWith strong environmental and geographic filtration, vertebrates incapable of flying and swimming are often extirpated from island ecosystems. Minami-Daito Island is an oceanic island in Okinawa, Japan that harbors the Daito flying fox (Pteropus dasymallus daitoensis), a subspecies of the fruit bat and the only extant mammal endemic to the island. However, the skeleton of a cave-dwelling bat Rhinolophus sp. and fossil guano were briefly reported in a previous study.MethodsHere, we present evidence for the anthropogenic extirpation of two species of cave-dwelling bats (Miniopterus sp. & Rhinolophus sp.) from Minami-Daito Island. Our goal is to reliably constrain the ages of the extirpated bat species by a multiproxy approach. Because skeletal materials did not preserve sufficient bone collagen for direct radiocarbon dating, we alternatively examined guano-like deposits based on SEM observation and Fourier-transform infrared spectroscopy (FTIR) along with stable carbon and nitrogen isotope analyses for possible indirect dating. We also examined stable carbon isotopes in bone apatite, assuming that an isotopic signal of C4 plants on the bat bones links to sugarcane plantation on the island based on the historical knowledge that early human settlers quickly replaced the island’s native C3 forests with sugarcane (C4 perennial grass) plantation from 1900 onward.ResultsOur cave survey documents the remains of Miniopterus sp. from the island for the first time. Based on the unique taphonomic conditions (unpermineralized bones, disarticulated skeletons closely scattered without sediment cover, various degrees of calcite crystal growth around bones) and a radiocarbon age of a humic sample, we suggest that the maximum age constraint of Miniopterus sp. and Rhinolophus sp. is 4,640 calBP. Based on a series of analyses, we conclude that the guano-like deposits are composed not of bat guano but mainly of humic substances; however, a hydroxyapatite crust associated with bat-lying stalagmites may be derived from bat feces. Stable carbon isotope analysis of bone apatite revealed C4 signals in various degrees, confirming that small populations of cave-dwelling bats persisted on Minami-Daito Island after 1900.ConclusionsThe results of this study indicate that these populations remained rather small and did not leave many generations and that the estimated ages can be bracketed from 4,640 calBP to the post-1900 (perhaps, until the 1950s). They likely faced a continuously high mortality risk due to severe anthropogenic stresses on the island, where most of the forests were turned into sugarcane plantations within a few decades in the early 20th century. A result of hearing surveys to local residents suggests the latest remnants most likely disappeared on the island concurrently with the introduction of chemical pesticides after World War II.

Microplastics impact shell and pearl biomineralization of the pearl oyster Pinctada fucata

Microplastics are extremely widespread aquatic pollutants that severely detriment marine life. In this study, the influence of microplastics on biomineralization was investigated. For the first time, multiple forms and types of microplastics were detected and isolated from the shells and pearls of Pinctada fucata. According to the present study, the abundance of microplastics in shells and pearls was estimated at 1.95 ± 1.43 items/g and 0.53 ± 0.37 items/g respectively. Interestingly, microplastics were less abundant in high-quality round pearls. Microplastics may hinder the growth of calcite and aragonite crystals, which are crucial components required for shell formation. During the process of biomineralization microplastics became embedded in shells, suggesting the existence of a novel pathway by which microplastics accumulate in bivalves. After a 96-h exposure to microplastics, the expression level of typical biomineralization-related genes increased, including amorphous calcium carbonate binding protein (ACCBP) gene which experienced a significant increase. ACCBP promotes the formation of amorphous calcium carbonate (ACC), which is the pivotal precursor of shell formation-related biominerals. ACCBP is highly expressed during the developmental stage of juvenile oysters and the shell-damage repair process. The increased expression of ACCBP suggests biomineralization is enhanced as a result of microplastics exposure. These results provide important evidence that microplastics exposure may impact the appearance of biominerals and the expression of biomineralization-related genes, posing a new potential threat to aquatic organisms.

The role of phosphate on non-skeletal carbonate production in a Cretaceous alkaline lake

Alkaline carbonate-rich systems may, under some circumstances, result in significant accumulation of aqueous phosphorus. Additionally, the geochemistry of modern alkaline lakes, combined with current understanding of CaCO3 precipitation kinetics, indicates that the establishment of high alkalinity, high dissolved inorganic carbon (DIC), and CaCO3 supersaturation require compounds that inhibit or interfere with CaCO3 precipitation. Furthermore, the interplay between these factors may potentially affect fabric development in non-skeletal carbonates. In order to understand how these interlinked processes may have regulated PO4 concentrations and the processes and products of non-skeletal CaCO3 precipitation in the distant past, we conducted a detailed geological and geochemical study in two cores drilled in different portions of the Santos Basin, offshore southeastern Brazil, consisting of lacustrine carbonate rocks from the Lower Cretaceous Barra Velha Formation. We find that phosphorus in the sediments comes from two main products, phosphatic bioclasts and authigenic phosphate (of both primary and diagenetic origins). We also find that phosphorus occurs in concentrations of up to several thousand ppm in some intervals and is preferentially associated with some calcite textures potentially reflecting the primary sedimentary depositional conditions (e.g., upward-radiating aggregates of fibrous calcite, or “shrubs” and spherulitic aggregates of fibrous calcite, or “spherulites”). Microanalytical data from selected samples and high-Mg CaCO3 textures show median P values can be particularly high in crusts, shrubs and spherulitic calcite minerals interpreted here to have formed as primary to early diagenetic deposits, and roughly vary between 1000 and 2000 ppm (10.5–21.1 mmol/kg). The average P/(Ca + Mg) molar ratio values based on the same data for these three calcite textures are 1.45 ± 0.98, 1.13 ± 0.97 and 1.09 ± 0.90 mmol/mol, respectively, being as high as 4.80 mmol/mol in specific spots in “shrubby” textures. Although multiple source-to-sink mechanisms were likely involved in the P budget in lake waters and in the sediments, such as recycling and remobilisation of skeletal- and organic-bound phosphate, high alkalinity may have enhanced its accumulation in the lake’s waters. In light of current understanding of CaCO3 precipitation kinetics, we hypothesise that phosphate may have played a central role in maintaining high calcium carbonate saturation (14–45 < Ωcalcite ≤ 100–180). These conditions would have favoured growth of calcite crystals on pre-existing substrates over nucleation of finely particulate carbonate sediment. By combining these observations with theoretical geochemical considerations, we propose that phosphate inhibition of calcium carbonate precipitation was enhanced by high alkalinity, further sustaining CaCO3 supersaturation and favouring distinctive carbonate growth textures. This unique and relatively well-preserved example of non-skeletal carbonate production implies that similar regulation of CaCO3 precipitation kinetics and PO4 concentrations may have operated across other intervals of time in Earth’s history, both in non-marine and marine environments that pre-date the emergence of skeletal calcification.

Uterine Metabolomic Analysis for the Regulation of Eggshell Calcification in Chickens.

Eggshell quality is economically important for table eggs and functionally indispensable for hatching eggs. During the formation of eggshell in the uterus, organic matrixes in uterine fluid can control and modify the formation of calcified eggshell. At present, there are limited studies focusing on the effect of uterine organic metabolites on eggshell quality. In this study, an LC-MS-based metabolomic technology was performed to identify the crucial uterine metabolites that differently presented in hens producing eggs with divergent eggshell quality (eggshell strength, thickness, and weight). More than 1000 metabolites were identified in uterine fluid, and six putative metabolites, including phosphatidylcholine, diacylglycerol, verapamil, risedronate, coproporphyrinogen III, and biliverdin, were screened to play crucial roles in eggshell calcification. Then, two trials for oral administration and in vitro calcite crystal growth were conducted to verify the effect of potential different metabolites on the eggshell quality. Verapamil has a temporary effect on decreasing eggshell strength and eggshell thickness. Coproporphyrinogen III could induce smaller calcite crystals to improve eggshell strength while biliverdin could modify crystal morphology by forming rougher faces and rounder edges to strengthen the eggshell. The present study gives us new insight to understand the role of uterine fluid matrixes in eggshell calcification.

The temperature - pressure phase diagram of the calcite I - calcite II phase transition: A first-principles investigation

In this work, we use first-principles atomistic calculations based on density functional theory to investigate the first phase transition that occurs when pressure and temperature are applied to calcite I, the stable polymorph at standard temperature and pressure. The mechanism of this phase transition is identified as phonon softening, and the specific phonon mode is documented. The phase boundary is computed with the framework of the quasi-harmonic approximation (QHA) and compared to available experiments. The computed phase boundary is sensitive to the approximations adopted to describe electronic exchange and correlation. To explore this sensitivity a range of approximation with the framework of modern density functional theory have been used, namely; global hybrid exchange, the generalized gradient approximation and the inclusion of ad hoc corrections describing van der Waals interactions. The latter prove to be significant in improving the agreement with the available observations of phase stability. The phonon mediated nature of the transition suggests mechanisms for controlling the growth of calcite crystals, for example, via the inclusion of amino acids or partial substitution of ions, to frustrate displacements along the soft phonon modes.

Forming Anisotropic Crystal Composites: Assessing the Mechanical Translation of Gel Network Anisotropy to Calcite Crystal Form.

The promise of crystal composites with direction-specific properties is an attractive prospect for diverse applications; however, synthetic strategies for realizing such composites remain elusive. Here, we demonstrate that anisotropic agarose gel networks can mechanically "mold" calcite crystal growth, yielding anisotropically structured, single-crystal composites. Drying and rehydration of agarose gel films result in the affine deformation of their fibrous networks to yield fiber alignment parallel to the drying plane. Precipitation of calcium carbonate within these anisotropic networks results in the formation of calcite crystal composite disks oriented parallel to the fibers. The morphology of the disks, revealed by nanocomputed tomography imaging, evolves with time and can be described by linear-elastic fracture mechanics theory, which depends on the ratio between the length of the crystal and the elastoadhesive length of the gel. Precipitation of calcite in uniaxially deformed agarose gel cylinders results in the formation of rice-grain-shaped crystals, suggesting the broad applicability of the approach. These results demonstrate how the anisotropy of compliant networks can translate into the desired crystal composite morphologies. This work highlights the important role organic matrices can play in mechanically "molding" biominerals and provides an exciting platform for fabricating crystal composites with direction-specific and emergent functional properties.

Epitaxy of Rhodochrosite (MnCO3) on Muscovite Mica and Its Relation with Calcite (CaCO3).

The flatness of muscovite mica makes it a convenient substrate to study epitaxy. We have analyzed the growth of rhodochrosite (MnCO3) crystals in solution and on muscovite mica. Growth at high supersaturations occurs via the formation of amorphous MnCO3, which over time transforms into the crystalline form. In the presence of muscovite mica, epitaxial rhodochrosite crystals with a size of approximately 1 μm form. These crystals are kinetically roughened, because of the high supersaturation. The lattice match between MnCO3 and muscovite was found not to be the main reason for epitaxy. If the growth experiment is performed twice, the original epitaxial MnCO3 crystals are overgrown by many small crystallites. Similarly, spherical MnCO3 crystals with many overgrown facets can be formed on a muscovite surface that is exposed to humidity or by using a higher MnCO3 supersaturation. A comparison with calcite shows that epitaxy strongly depends on initial supersaturation for both carbonates. In contrast to previous studies, we find that at the right supersaturation, epitaxial calcite crystal growth is possible on freshly cleaved muscovite.