Showing papers in "American Mineralogist in 2009"

Thermal decomposition of calcite: Mechanisms of formation and textural evolution of CaO nanocrystals

Abstract: Field emission scanning electron microscopy (FESEM), two-dimensional X-ray diffraction (2D-XRD), and transmission electron microscopy coupled with selected area electron diffraction (TEM-SAED) analyses of the reactant/product textural relationship show that the thermal decomposition of Iceland spar single crystals according to the reaction CaCO3(s) → CaO(s) + CO2(g) is pseudomorphic and topotactic. This reaction begins with the formation of a mesoporous structure made up of up to four sets of oriented rod-shaped CaO nanocrystals on each rhombohedral cleavage face of the calcite pseudomorph. The four sets formed on (1014)calcite display the following topotactic relationships: (1) (1210)calcite//(110)CaO; (2) (1104)calcite⊥ (110)CaO; (3) (1018)calcite//(110)CaO; and (4) (0114)calcite⊥(110)CaO; with [841]calcite//[110]CaO in all four cases. At this stage, the reaction mechanism is independent of P CO2 (i.e., air or high vacuum). Strain accumulation leads to the collapse of the mesoporous structure, resulting in the oriented aggregation of metastable CaO nanocrystals (~5 nm in thickness) that form crystal bundles up to ~1 μm in cross-section. Finally, sintering progresses up to the maximum T reached (1150 °C). Oriented aggregation and sintering (plus associated shrinking) reduce surface area and porosity (from 79.2 to 0.6 m2/g and from 53 to 47%, respectively) by loss of mesopores and growth of micrometer-sized pores. An isoconversional kinetic analysis of non-isothermal thermogravimetric data of the decomposition of calcite in air yields an overall effective activation energy E α = 176 ± 9 kJ/mol (for α > 0.2), a value which approaches the equilibrium enthalpy for calcite thermal decomposition (177.8 kJ/mol). The overall good kinetic fit with the F1 model (chemical reaction, first order) is in agreement with a homogeneous transformation. These analytical and kinetic results enable us to propose a novel model for the thermal decomposition of calcite that explains how decarbonation occurs at the atomic scale via a topotactic mechanism, which is independent of the experimental conditions. This new mechanistic model may help reinterpret previous results on the calcite/CaO transformation, having important geological and technological implications.

A thermodynamic model for the plagioclase-liquid hygrometer/thermometer

Abstract: A new thermodynamic model for the plagioclase-liquid exchange reaction between the albite (NaAlSi 3 O 8 ) and anorthite (CaAl 2 Si 2 O 8 ) components is presented, which can be used as a plagioclaseliquid hygrometer or thermometer. The model incorporates calorimetric and volumetric data for the pure liquid and crystalline components, which permits the effect of temperature and pressure on the exchange reaction to be calculated independently from the effect of composition. This allows a more accurate assessment of the effect of melt composition (including dissolved water concentration) on the exchange reaction from plagioclase-liquid equilibrium experiments. Activity-composition relations for the plagioclase solid solution are taken from Holland and Powell (1992). The new hygrometer is calibrated on 71 plagioclase-liquid experiments, of which 45 are hydrous and 26 are anhydrous. Three filters were applied to the phase-equilibrium data: (1) crystallanities <30%; (2) pure H 2 O fluidsaturated; and (3) compositional totals (including H 2 O component) of 97‐101% for hydrous quenched glasses. The final data set spans a wide range of liquid compositions (46‐74 wt% SiO 2 ), plagioclase compositions (An 93 -An 37 ), temperatures (825‐1230 °C), pressures (0‐300 MPa), and dissolved melt water concentrations (0‐7 wt% H 2 O). The standard error of estimate (SEE) for the model is ±0.32 wt% H 2 O, and all liquid compositions are fitted equally well. When the model is used as a thermometer, all measured temperatures are recovered equally well within ±14 °C on average. The model is only recommended for applications that fall within the compositional bounds of the calibration data set (i.e., metaluminous basalts through rhyolites in equilibrium with An 95 -An 35 ). It is not yet calibrated for rhyolites crystallizing plagioclase more sodic than An 30 , owing to an absence of phase-equilibrium experiments on rhyolites that pass the required filters. The new plagioclase-liquid hygrometer/thermometer is available as a Visual Basic program that runs on Excel 2004.

Microbe-clay mineral interactions

Abstract: Clays and clay minerals are common components in soils, sediments, and sedimentary rocks, and they play an important role in many environmental processes. Iron is ubiquitous in clays and clay minerals and its oxidation state, in part, controls the physical and chemical properties of these fine-grained minerals. The structural ferric iron in clay minerals can be reduced either chemically or biologically. Biological reductants include mesophilic and thermophilic microorganisms from diverse environments such as soils, sediments, sedimentary rocks, and hydrothermal hot springs. Multiple clay minerals have been used for microbial reduction studies, including dioctahedral smectiteillite series, palygorskite, chlorite, and their various mixtures in natural soils and sediments. All of these clay minerals are reducible by microorganisms under various conditions with smectite (nontronite) being the most reducible and illite the least. The rate and extent of bioreduction depends on many experimental factors, such as the type of microorganisms and clay minerals, solution chemistry, and temperature. Despite significant efforts, current understanding of the mechanisms of microbial reduction of ferric iron in clay minerals is still limited. Whereas some studies have presented evidence for a solid-state reduction mechanism, others argue that the clay mineral structure partially dissolves when the extent of reduction is high. This inconsistency may be related to several experimental conditions, and their specific effects are discussed in this paper. Whereas past experiments have been largely conducted in well-controlled laboratory systems, recent efforts have attempted to transfer knowledge to the field to improve our understanding of more complex soil systems for better agricultural practices. Biologically reduced clay minerals are also important agents in remediating inorganic and organic contaminants in soil and groundwater systems. This paper reviews the most recent developments and suggests some directions for future research.

Heat capacities and thermodynamic functions of TiO2 anatase and rutile: Analysis of phase stability

Abstract: At high temperature, coarse-grained (bulk) rutile is well established as the stable phase of TiO2, and nanophase anatase, thermodynamically stable relative to nanophase rutile, transforms irreversibly to rutile as it coarsens. The lack of experimental heat-capacity data for bulk anatase below 52 K lends uncertainty to its standard entropy and leaves open a slight possibility that anatase may have a thermodynamic stability field at low temperature, as suggested by some theoretical calculations. In the present study, the molar heat capacities of rutile and anatase were measured from 0.5 K to about 380 K. These data were combined with previously measured high-temperature heat capacities, and fits of the resulting data set were used to generate C P ,m°, ΔT S m°, ΔT H m°, and ΔT G m ° values at smoothed temperatures between 0.5 and 1300 K for anatase and 0.5 and 1800 K for rutile. Using these new data and the enthalpy of transformation between anatase and rutile at 298 K, the change in Gibbs free energy for the transition between anatase and rutile from 0 to 1300 K was calculated. These calculations reveal that the transformation from bulk anatase to bulk rutile is thermodynamically favorable at all temperatures between 0 and 1300 K, confirming that bulk anatase does not have a thermodynamic stability field. Implications for the natural occurrence of these two minerals in terrestrial, lunar, and planetary settings are discussed. In particular, anatase requires low-temperature aqueous conditions for its formation and may be a reliable indicator of such conditions in both terrestrial and extraterrestrial settings.

Advances in understanding the structure of borosilicate glasses: A Raman spectroscopy study

Abstract: This study is focused on the behavior of ternary SiO2-Na2O-B2O3 borosilicate glasses at temperatures between 298 and 1800 K. Unpolarized Raman spectra were measured up to high temperature. SiO2-Na2O-B2O3 glass samples were prepared with different values of the ratio R = [Na2O]/[B2O3], while the ratio K = [SiO2]/[B2O3] was kept constant and equal to 2.12. Spectra were measured at room temperature in samples with 0.43 ≤ R ≤ 1.68, and the effect of the modifier content was clearly observed in these glasses, only in partial agreement with previous literature results. In particular, the formation in the glass of sodium-danburite units Na2O·B2O3·2SiO2 was postulated. This feature led to a new assessment of R* , the critical value of R above which every new alkali atom added to the system breaks a Fo-O-Fo (Fo = glass former) bridge causing depolymerization of the glass. A revised formula is proposed to obtain the value of R * as a function of K . Raman spectra measured at high temperature yielded important information about the temperature-dependent evolution of the borosilicate system. In particular, borate and borosilicate units including tetra-coordinated boron seem to be unstable at high temperature, where the formation of metaborate chains or rings is fostered. Above 1500 °C, evaporation of borate compounds is clearly observed, stemming from the small sample size.

Evolution of uranium and thorium minerals

Abstract: The origins and near-surface distributions of the ~250 known uranium and/or thorium minerals elucidate principles of mineral evolution. This history can be divided into four phases. The first, from ~4.5 to 3.5 Ga, involved successive concentrations of uranium and thorium from their initial uniform trace distribution into magmatic-related fluids from which the first U4+ and Th4+ minerals, uraninite (ideally UO2), thorianite (ThO2), and coffinite (USiO4), precipitated in the crust. The second period, from ~3.5 to 2.2 Ga, saw the formation of large low-grade concentrations of detrital uraninite (containing several wt% Th) in the Witwatersrand-type quartz-pebble conglomerates deposited in a highly anoxic fluvial environment. Abiotic alteration of uraninite and coffinite, including radiolysis and auto-oxidation caused by radioactive decay and the formation of helium from alpha particles, may have resulted in the formation of a limited suite of uranyl oxide-hydroxides. Earth’s third phase of uranium mineral evolution, during which most known U minerals first precipitated from reactions of soluble uranyl (U6+O2)2+ complexes, followed the Great Oxidation Event (GOE) at ~2.2 Ga and thus was mediated indirectly by biologic activity. Most uraninite deposited during this phase was low in Th and precipitated from saline and oxidizing hydrothermal solutions (100 to 300 °C) transporting (UO2)2+-chloride complexes. Examples include the unconformity- and vein-type U deposits (Australia and Canada) and the unique Oklo natural nuclear reactors in Gabon. The onset of hydrothermal transport of (UO2)2+ complexes in the upper crust may reflect the availability of CaSO4- bearing evaporites after the GOE. During this phase, most uranyl minerals would have been able to form in the O2-bearing near-surface environment for the first time through weathering processes. The fourth phase of uranium mineralization began ~400 million years ago, as the rise of land plants led to non-marine organic-rich sediments that promoted new sandstone-type ore deposits. The modes of accumulation and even the compositions of uraninite, as well as the multiple oxidation states of U (4+, 5+, and 6+), are a sensitive indicator of global redox conditions. In contrast, the behavior of thorium, which has only a single oxidation state (4+) that has a very low solubility in the absence of aqueous F-complexes, cannot reflect changing redox conditions. Geochemical concentration of Th relative to U at high temperatures is therefore limited to special magmatic-related environments, where U4+ is preferentially removed by chloride or carbonate complexes, and at low temperatures by mineral surface reactions. The near-surface mineralogy of uranium and thorium provide a measure of a planet’s geotectonic and geobiological history. In the absence of extensive magmatic-related fluid reworking of the crust and upper mantle, uranium and thorium will not become sufficiently concentrated to form their own minerals or ore deposits. Furthermore, in the absence of surface oxidation, all but a handful of the known uranium minerals are unlikely to have formed.

Structure and carbonate orientation of vaterite (CaCO3)

Abstract: First-principles calculations and molecular-dynamics simulations are employed in this study to further our understanding of the crystal structure and orientational order of carbonate ions in vaterite, which is the least stable polymorph of calcium carbonate. The structural details of vaterite have been controversial but they are prerequisite for investigating and understanding the processes involving vaterite crystal nucleation, growth, and stabilization at a molecular level. The first-principles calculations, using density functional theory with the plane-wave pseudopotential method, are carried out to calculate relative thermodynamic stabilities of proposed structures. Molecular-dynamics simulations with classical empirical potentials, larger computational cells, and fully flexible models at different temperatures are performed to investigate the orientation and order-disorder of the carbonate ions. The results show that the previously accepted structure with disordered CO 3 ions, which are randomly distributed over three orientations parallel to the c axis, is only metastable. By applying a temperature annealing technique to the molecular dynamics simulations, a more stable structure with fully ordered carbonate ions is found that has a hexagonal superstructure. The space group of this newly derived vaterite structure is P 6 5 22 (no. 179) with Z = 18 and cell dimensions of √3 times in a , and 3 times in c of the previous suggested disordered structure. Comparison of experimental observations of X-ray diffraction patterns, enthalpies of transformation to calcite, and volume change by heat treatment with our theoretical calculations indicates that freshly made vaterite is often carbonate-disordered and metastable and can fully or partially transform to a carbonate-ordered structure by aging and heating.

Solubility of H2O and CO2 in ultrapotassic melts at 1200 and 1250 °C and pressure from 50 to 500 MPa

Abstract: The solubility of H2O-CO2 fluids in a synthetic analogue of a phono-tephritic lava composition from Alban Hills (Central Italy) was experimentally determined from 50 to 500 MPa, at 1200 and 1250 °C. Contents of H2O and CO2in experimental glasses were determined by bulk-analytical methods and FTIR spectroscopy. For the quantification of volatile concentrations by IR spectroscopy, we calibrated the absorption coefficients of water-related and carbon-related bands for phono-tephritic compositions. The determined absorption coefficients are 0.62 ± 0.06 L/(mol·cm) for the band at ~4500 cm−1 (OH groups) and 1.02 ± 0.03 L/(mol·cm) for the band at ~5200 cm−1 (H2O molecules). The coefficient for the fundamental OH-stretching vibration at 3550 cm−1 is 63.9 ± 5.4 L/(mol·cm). CO2 is bound in the phono-tephritic glass as CO32− exclusively; its concentration was quantified by the peak height of the doublet near the 1500 cm−1 band with the calibrated absorption coefficient of 308 ± 110 L/(mol·cm). Quench crystals were observed in glasses with water contents exceeding 6 wt% even when using a rapid-quench device, limiting the application of IR spectroscopy for water-rich glasses. H2O solubility in the ultrapotassic melts (7.52 wt% K2O) as a function of pressure is similar to the solubility in basaltic melts up to 400 MPa (~8 wt%) but is higher at 500 MPa (up to 10.71 wt%). At 500 MPa and 1200 °C, the CO2 capacity of the phono-tephritic melt is about 0.82 wt%. The high CO2 capacity is probably related to the high K2O content of the melt. At both 200 and 500 MPa, the H2O solubility shows a non linear dependence on XH2Of in the whole XH2Of range. The variation of CO2 solubility with XCO2f displays a pronounced convex shape especially at 500 MPa, implying that dissolved H2O promotes the solubility of CO2. Our experimental data on CO2 solubility indicate that the interaction between phono-tephritic magma and carbonate rocks occurring in the Alban Hills magmatic system may result in partial dissolution of CO2 from limestone into the magma. However, although the CO2 solubility in phono-tephritic melts is relatively high compared to that in silicic to basaltic melts, the capacity for assimilation of limestone without degassing is nevertheless limited to <1 wt% at the P - T conditions of the magma chamber below Alban Hills.

Mechanism of wollastonite carbonation deduced from micro- to nanometer length scale observations

Abstract: The microstructural evolution of CaSiO3 wollastonite subjected to carbonation reactions at T = 90 °C and pCO2 = 25 MPa was studied at three different starting conditions: (1) pure water; (2) aqueous alkaline solution (0.44 M NaOH); and (3) supercritical CO2. Scanning and transmission electron microscopy on reacted grains prepared in cross-section always revealed unaltered wollastonite cores surrounded by micrometer-thick pseudomorphic silica rims that were amorphous, highly porous, and fractured. The fractures were occasionally filled with nanometer-sized crystals of calcite and Ca-phyllosilicates. Nanoscale chemical profiles measured across the wollastonite-silica interfacial region always revealed sharp, step-like decreases in Ca concentration. Comparison of the Ca profiles with diffusion modeling suggests that the silica rims were not formed by preferential cation leaching (leached layer), but rather by interfacial dissolution-precipitation. Extents of carbonation as a function of time were determined by quantitative Rietveld refinement of X-ray diffractograms performed on the reacted powders. Comparing the measured extents of carbonation in water (condition 1) with kinetic modeling suggests that carbonation was rate-controlled by chemical reactions at the wollastonite interface, and not by transport limitations within the silica layers. However, at conditions 2 and 3, calcite crystals occurred as a uniform surface coating covering the silica layers, and also within pores and cracks, thereby blocking the connectivity of the originally open nanoscale porosity. These crystals ultimately may have been responsible for controlling transport of solutes through the silica layers. Therefore, this study suggests that pure silica layers were intrinsically non-passivating, whereas silica layers became partially passivating due to the presence of calcite crystallites.

Crystal chemistry of the magnetite-ulvöspinel series

Abstract: Spinel single crystals of 19 compositions along the magnetite-ulvospinel join were synthesized by use of a flux-growth method. To obtain quantitative site populations, the crystals were analyzed by single-crystal X-ray diffraction, electron-microprobe techniques, and Mossbauer spectroscopy. All results were processed by using an optimization model. The unit-cell parameter, oxygen fractional coordinate, and tetrahedral bond length increase with increasing ulvospinel component, whereas the octahedral bond length decreases marginally. These changes result in sigmoidal crystal-chemical relationships consistent with cation substitutions in fully occupied sites. As a first approximation, the Akimoto model T (Fe 1− X 3+ Fe X 2 + ) M (Fe 2+ Fe 1− X 3+ Ti X )O 4 describes the cation substitutions. Deviations from this model can be explained by an electron exchange reaction T Fe 2+ + M Fe 3+ = T Fe 3+ + M Fe 2+ , which causes M Fe 2+ ≠ 1 and T Fe 2+ /Ti ≠ 1. The resultant S-shaped trends may be related to a directional change in the electron exchange reaction at Ti ≈ 0.7 apfu. In general, variations in structural parameters over the whole compositional range can be split into two contributions: (1) a linear variation due to the T Fe 3+ + M Fe 3+ = T Fe 2+ + M Ti 4+ chemical substitution and (2) non-linear variations caused by the internal electron exchange reaction. In accordance with bond-valence theory, strained bonds ascribable to steric effects characterize the structure of magnetite-ulvospinel crystals. To relax the bonds and thereby minimize the internal strain under retained spinel space group symmetry, the electron exchange reaction occurs.

Primitive oxygen-isotope ratio recorded in magmatic zircon from the Mid-Atlantic Ridge

Abstract: The oxygen-isotope composition of the Earth’s upper mantle is an important reference for understanding mantle and crust geochemical cycles. Olivine is the most commonly used mineral for determining the influence of crustal processes on the oxygen-isotope ratio (δ 18 O) of primitive rocks, however it is an uncommon mineral in continental crust and readily alters at or near Earth’s surface. Here we report the first measurements of oxygen-isotope ratios in zircon from oceanic crust exposed at a mid-ocean ridge. Measurements of δ 18 O and trace elements were made by ion microprobe on zircon in polished rock chips of gabbro and veins in serpentinized peridotite drilled from the Mid-Atlantic Ridge. The zircon grains contain both oscillatory and sector growth zoning, features characteristic of magmatic zircon. Values of δ 18 O (zircon) = 5.3 ± 0.8‰ (2 st. dev., n = 68) for the population are consistent with the interpretation that these grains are igneous in origin and formed in high-temperature isotopic equilibrium with mantle oxygen. The δ 18 O values demonstrate that zircon in oceanic crust preserves primitive δ 18 O in spite of sub-solidus alteration of the whole rock. The fact that the primitive δ 18 O (zircon) values fall in a narrow range (5.3 ± 0.8‰) strengthens the use of oxygen isotopes in zircon as a tracer to identify processes of exchange in a wide range of modern and ancient crustal environments, including subducted oceanic crust (eclogite), and also in the oldest known pieces of Earth, >3900 million-year-old detrital zircon grains from Western Australia.

Ferritchromite and chromian-chlorite formation in mélange-hosted Kalkan chromitite (Southern Urals, Russia)

Abstract: Spinel is often used as a magmatic indicator of crystallization processes, without considering the effects of metamorphic alteration on spinel geochemical features. Serpentinized melanges in the southern Urals host different kinds of disseminated to massive chromitite mineralization. In melange environments, intense metamorphic alteration above 300 °C leads to major changes in chromite chemistry and to the growth of secondary phases such as ferritchromite and chromian-chlorite. Based on textural and chemical analyses, melange-hosted Kalkan chromitites exhibit a hydration and oxidation reaction that can explain the formation of ferritchromite and chromian-chlorite from chromite and serpentine: \begin{eqnarray*}&&{2(Mg_{0.60}Fe_{0.40})(Cr_{1.30}Al_{0.70})O_{4}_{Chr}^{}}\ +\ {3/2(Mg_{2.57}\ Al_{0.32}Fe_{0.11})Si_{2}O_{5}(OH)_{4}_{Atg}^{}}\ +\ H_{2}O\ +\ 1/12O_{2}\ {\rightarrow}\\&&{7/6(Mg_{0.40}Fe_{0.60})(Cr_{1.85}Fe_{0.08}Al_{0.07})O_{4}_{Fe-Chr}^{}}\ +\ {1/2(Mg_{9.18}Fe_{0.34}Al_{1.60}Cr_{0.88})(Al_{2}Si_{6})O_{20}(OH)_{16}_{Cr-Chl}^{}}.\end{eqnarray*} Textural analyses fit well with the proposed reaction and show that it usually proceeds very close to completion. The degree of alteration of chromite into ferritchromite is controlled by the initial chromite to serpentine ratio. In chromitites, high ratios prevent complete transformation of chromite into ferritchromite. The most likely environment for such reaction is a prograde metamorphic event post-dating serpentinization of the Kalkan ophiolite, possibly related to emplacement within an accretionary wedge.

High-pressure ammonium-bearing silicates : Implications for nitrogen and hydrogen storage in the Earth's mantle

Abstract: The ammonium analogues of the high-pressure potassium-bearing silicate phases K-hollandite, K-Si-wadeite, K-cymrite, and phengite were synthesized in the system (NH 4 ) 2 O(-MgO)-Al 2 O 3 -SiO 2 -H 2 O [N(M)ASH] using multi-anvil and piston-cylinder equipment. Syntheses included NH 4 -hollandite (NH 4 AlSi 3 O 8 ) at 12.3 GPa, 700 °C; NH 4 -Si-wadeite [(NH 4 ) 2 Si 4 O 9 ] at 10 GPa, 700 °C; NH 4 -cymrite (NH 4 AlSi 3 O 8 ·H 2 O) at 7.8 GPa, 800 °C; and NH 4 -phengite [NH 4 (Mg 0.5 Al 1.5 )(Al 0.5 Si 3.5 )O 10 (OH) 2 ] at 4 GPa, 700 °C. Run products were characterized by SEM, FTIR, and powder XRD with Rietveld refinements. Cell parameters of the new NH 4 end-members are: a = 9.4234(9) A, c = 2.7244(3) A, V = 241.93(5) A 3 (NH 4 -hollandite); a = 6.726(1) A, c = 9.502(3) A, V = 372.3(1) A 3 (NH 4 -Si-wadeite); a = 5.3595(3) A, c = 7.835(1) A, V = 194.93(5) A 3 (NH 4 -cymrite). NH 4 -phengite consisted of a mixture of 1 M , 2 M 1 , 2 M 2 , 3 T , and 2 Or polytypes. The most abundant polytype, 2 M 1 , has cell dimensions a = 5.2195(9) A, b = 9.049(3) A, c = 20.414(8) A, β = 95.65(3)°, V = 959.5(5) A 3 . All unit-cell volumes are enlarged in comparison to the potassium analogues. Substitution of NH 4 for K does not cause changes in space group. NH 4 incorporation was confirmed by the appearance of NH 4 -vibration modes ν 4 and ν 3 occurring in the ranges of 1397–1459 and 3223–3333 cm −1 , respectively. Ammonium in eclogite facies metasediments is mainly bound in micas and concentrations may reach up to a few thousand parts per million. It can be stored to greater depths in high-pressure potassium silicates during ongoing subduction. This possibly provides an important mechanism for nitrogen and hydrogen transport into the deeper mantle.

Change in compressibility of δ-AlOOH and δ-AlOOD at high pressure: A study of isotope effect and hydrogen-bond symmetrization

Abstract: The compression behaviors of δ-AlOOH and δ-AlOOD were investigated under quasi-hydrostatic conditions at pressures up to 63.5 and 34.9 GPa, respectively, using results from synchrotron X-ray diffraction experiments conducted at ambient temperature. Because of the geometric isotope effect, at ambient pressure, the a and b axes of δ-AlOOD, which define the plane in which the hydrogen bond lies, are longer than those of δ-AOOH. Under increasing pressure, the a and b axes of δ-AlOOH stiffen at 10 GPa, although the c axis shows no marked change. Identical behavior was found in δ-AlOOD, but the change in compressibility was observed at a slightly higher pressure of 12 GPa. Axial ratios a / c and b / c first decrease rapidly with increasing pressure, then begin to increase at pressures >10 GPa in δ-AlOOH and >12 GPa in δ-AlOOD. At these pressures, the pressure dependence of a / b also changes from increasing to decreasing. The unit-cell volumes of δ-AlOOH and δ-AlOOD become slightly less compressible at high pressures. Assuming K ′ = 4, the calculated bulk moduli of δ-AlOOH below and above 10 GPa are 152(2) and 219(3) GPa, respectively. Those of δ-AlOOD below and above 12 GPa are 151(1) and 207(2) GPa, respectively.

Formation of aragonite mesocrystals and implication for biomineralization

Abstract: Highly oriented aragonite tablets have been found in the nacre layers of molluscan shell (or mother of pearl). In this article, we show that highly organized aragonite rods can be prepared over a broad range of pH values (1.5 to 6.9) and in the absence of any bio- or organic macromolecules. The organized rods were characterized by XRD, FTIR, FESEM, TEM, SAED, and EDX techniques. FESEM results reveal that the mesoscale aragonite rods are not only assembled with aragonite microrods end-to-end, and side-to-side, but are also partially fused to one another, forming flat, faceted surfaces, i.e., mesocrystal structure. TEM and SAED analyses confirm that the organized rods have the same crystallographic symmetry as single-crystal aragonite, and thus the self-assembly process is energetically favorable. Similar assembly processes also occur for the mineral strontianite of the aragonite group, revealing the occurrence of a general self-assembly process. The driving force controlling the self-assembly process may originate from the inherent anisotropic dipole-dipole interactions between the assembled units. Such dipole interaction may generally occur in biomineralization of nacre layers in molluscan shell, and orchestrate aragonite nanocrystals in an aragonite tablet to coherently orient and array. Furthermore, the dipole-dipole interactions may also contribute to the co-orientation of the aragonite tablets in the same nacreous column. Therefore, our experimental results may provide insight into biomineralization mechanisms. It appears that biological genetic and crystallochemical factors may synergistically operate in biomineralization.

U-Pb age, trace-element, and Hf-isotope compositions of zircon in a quartz vein from eclogite in the western Dabie Mountains : Constraints on fluid flow during early exhumation of ultrahigh-pressure rocks

Abstract: Quartz veins in high-pressure (HP) to ultrahigh-pressure (UHP) rocks are the products of fluid-rock interaction, and thus provide insight into fluid processes in subduction zones. In this paper, we report an integrated study of mineral inclusion, trace-element, U-Pb age, and Lu-Hf isotope compositions of hydrothermal zircon grains from a quartz vein within an UHP eclogite outcrop from the Hong’an area, western Dabie Mountains. These data are used to decipher the age, conditions of formation, and source of fluid for zircon formation during the exhumation of UHP rocks. Zircon grains from the vein have perfect euhedral shape, and show sector zoning or weak zoning, indicating that they precipitated from the aqueous fluid responsible for the vein formation. Raman spectroscopy analysis reveals that the zircon grains contain inclusions of garnet, omphacite, rutile, quartz, and H2O, implying that they crystallized from aqueous fluid under HP eclogite-facies conditions. The zircon grains show low Th/U and Lu/Hf ratios, nearly flat HREE patterns, absent Eu anomalies and low LREE contents. These characteristics are consistent with their precipitation in the presence of garnet and epidote, and absence of feldspar, and thus suggest that trace-element concentrations in hydrothermal zircon are controlled by co-precipitation of mineral assemblages. Crystallization temperatures of 670 to 712 °C, which were calculated using the Ti content of zircon, are consistent with their formation under eclogite-facies conditions and may correspond to the temperature of the infiltrating fluid. The weighted mean 206Pb/238U age of 224.7 ± 1.3 Ma is taken as the best estimate for the age of quartz-vein formation and records aqueous fluid flow during the early exhumation stage of UHP rocks. The zircon grains in the quartz-vein have Hf compositions similar to those in the host eclogite, which demonstrates isotopic equilibrium between fluid and rocks and that the fluid-rock ratio was likely low.

Tistarite, Ti2O3, a new refractory mineral from the Allende meteorite

Abstract: Tistarite, ideally Ti_2O_3, is a new member of the corundum-hematite group. It is found as one subhedral crystal in a cluster of micrometer-sized refractory grains along with khamrabaevite (TiC), rutile, and corundum crystals within a chondrule from the Allende meteorite. The mean chemical composition determined by electron microprobe analysis is (wt%) Ti_2O_3 94.94, MgO 2.06, Al_2O_3 1.50, ZrO_2 0.44, FeO 0.24, CaO 0.10, Cr_2O_3 0.06, sum 99.34. The empirical formula calculated on the basis of 3 O atoms is (Ti^(3+)_(1.90)Mg_(0.07)Al_(0.04)Zr_(0.01))∑_(2.02)O_3. Tistarite is rhombohedral, R3–c; a = 5.158 A, c = 13.611 A, V = 313.61 A^3, and Z = 6. Its electron back-scatter diffraction pattern matches that of synthetic Ti_2O_3 with the R3–c structure. The strongest calculated X-ray powder diffraction lines from the synthetic Ti_2O_3 data are [d spacing in A (I) hkl]: 3.734 (84) (012), 2.707 (88) (104), 2.579 (90) (110), 2.242 (38) (113), 1.867 (33) (024), 1.703 (100) (116), 1.512 (28) (214), 1.489 (46) (300), 1.121 (20) (226), 0.896 (25) (416). The mineral is named after the composition "Ti" and the word "star," implying that this new refractory mineral is among the first solids formed in the solar system.

Experimental constraints on rutile saturation during partial melting of metabasalt at the amphibolite to eclogite transition, with applications to TTG genesis

Abstract: TiO2 solubility in rutile-saturated felsic melts and coexisting minerals was determined at 1.5–3.5 GPa, 750–1250 °C, and 5–30 wt% H2O. TiO2 solubility in the melt primarily increases with temperature and melt basicity; it increases slightly with water content in the melt, and it decreases with pressure. A general TiO2 solubility model was obtained and is expressed as: ln(TiO2)melt = ln(TiO2)rutile + 1.701 − (9041/ T ) − 0.173 P + 0.348FM + 0.016H2O, where TiO2 and H2O are in wt%, T is in Kelvin, P in GPa, and FM is the melt composition parameter given by FM = (1/Si)·[Na + K + 2(Ca + Fe + Mn + Mg)]/Al, in which the chemical symbols represent cation fractions. TiO2 solubility in amphibole, garnet, and clinopyroxene also increases with temperature and empirical equations describing this temperature dependence were derived. These data were used to assess the protolith TiO2 content required for rutile saturation during partial melting of hydrous metabasalt at the amphibolite to eclogite transition. The results show that only 0.8–1.0 wt% TiO2 is required for rutile saturation during low-degree (<20%) melting. Rutile is stable up to ~1150 °C with 1.6 wt% TiO2 in the protolith and 30–40% melting for dehydration melting and up to ~1050 °C and 50–60% melting for fluid-present melting. The data also show that 0.7–0.8 wt% TiO2 in the protolith is needed for rutile saturation during subsolidus dehydration. Therefore, nearly all basaltic protoliths in deep-crustal settings and subduction zones will be saturated with rutile during subsolidus dehydration and low-degree melting at hydrous conditions. Archean tonalites-trondhjemites-granites (TTG) are widely accepted to be the products of low-degree melting of metabasalts at the amphibolite to eclogite transition, with rutile being present in the residue. Comparison of natural TTG compositions with our experimental rutile solubility data indicates that the dominant TTG magmas were produced at temperatures of 750–950 °C, which requires that the partial melting occurred at hydrous conditions. Models involving melting at the base of oceanic plateaus are inadequate to explain TTG genesis because the plateau root zones are likely dominated by anhydrous cumulates. A slab-melting model satisfies the requirement of a hydrous metabasalt, which during subduction would melt to produce voluminous TTG melts under high Archean geothermal gradients. The geothermal gradients responsible are estimated to be between 10 and 19 °C/km based on a pressure range of 1.5–2.5 GPa for the amphibolite to eclogite transition.

Spectroscopic characteristics of synthetic olivine: An integrated multi-wavelength and multi-technique approach

Abstract: Spectroscopic measurements have been made of two suites of olivine minerals synthesized under slightly different conditions in 5–10 mol% increments across the solid solution from forsterite to fayalite. Here, we present Mossbauer results for the entire Fe-Mg olivine suite, as well as the results for only the fayalite end-member as an introduction to our team’s other diverse spectral-analysis techniques and data that will be presented in forthcoming papers. Experimental methods used to synthesize both suites of samples are discussed here in detail, along with specifics of the analytical techniques used to study them. Electron microprobe data and Mossbauer spectra acquired at 293 K across the solid solution are presented first to characterize and address the presence of impurities in the broad suite of samples that may affect other spectroscopic methods. We then focus specifically on the fayalite end-member to illustrate its properties using multiple techniques. Fayalite is an especially important phase for different types of spectroscopy because, by definition, it contains an equal distribution of Fe 2+ cations between the M1 and M2 octahedral sites. Thus, features associated with each of the two sites must represent equal numbers of Fe 2+ cations, removing uncertainties associated with assumptions about order/disorder of Fe 2+ and other cations. Mossbauer, Raman, thermal emission, attenuated total reflectance (ATR), specular reflectance, and visible to mid-infrared total reflectance studies are presented for fayalite. These include calculation of mid-infrared optical constants ( n and k ) and fundamental Mossbauer parameters: intrinsic isomer shift (δ I ), Mossbauer temperature (𝛉 M ), and recoil-free fraction ( f ). Data from the different techniques are described and related, demonstrating the importance of multi-wavelength data to provide a complete characterization and understanding of the spectroscopic features in fayalite.

Solid-state NMR and IR spectroscopic investigation of the role of structural water and F in carbonate-rich fluorapatite

Abstract: We have studied the substitutions in a natural well-crystallized carbonate-containing apatite-(CaF) (var. staffelite) using infrared (IR) and solid-state nuclear magnetic resonance (NMR) spectroscopic techniques. Our results show the presence of both A- and B-type carbonate plus a large amount of structural water (0.44 pfu). This sample also contains 0.21 pfu excess F, but only weak C-F dipolar coupling is observed indicating that a tetrahedral CO3F 3– complex does not occur. 19 F NMR results indicate the presence of a second F environment in the apatite structure at a concentration similar to that of B-type carbonate but which does not differ from channel F in terms of coupling to 31 P or 1 H.

The composition of KLB-1 peridotite

Abstract: Electron microprobe analyses of major- and minor-element oxide components for two glassed samples of natural KLB-1 peridotite are presented. One glass was made with the aid of a phosphate flux, and the second glass was made by laser melting of aerodynamically levitated spheroids resulting in homogeneous silicate glass beads. For unknown reasons, the silicate-phosphate glass yields compositions that are incompatible with the composition of KLB-1 peridotite. However, analysis of the glass bead formed by laser synthesis is believed to give an accurate representation of the com-position of KLB-1 peridotite, except for minor loss of Na 2 O owing to volatilization. The new data resolve conflicting FeO, CaO, and TiO 2 values from two older measurements present in the literature. Mass-balance calculations using the new composition measurement combined with new analyses of the mineral compositions in KLB-1 result in a lower sum of squares of the residuals than those using the older measurements. There are appreciable differences in calculated modes from partial-melting experiments of KLB-1 when calculated using older KLB-1 analyses or our new analysis.

Simultaneous aluminum, silicon, and sodium coordination changes in 6 GPa sodium aluminosilicate glasses

Abstract: We present the first direct observation of high-coordinated Si and Al occurring together in a series of high-pressure sodium aluminosilicate glasses, quenched from melts at 6 GPa. Using ^(29)Si MAS NMR, we observe that a small amount of Al does not have a significant effect on the amount of ^VSi or ^(VI)Si generated, but that larger Al concentrations lead to a gradual decrease in both these species. ^(27)Al MAS NMR spectra show that samples with small amounts of Al have extremely high mean Al coordination values of up to 5.49, but that larger Al concentrations cause a gradual decrease in both ^VAl and ^(VI)Al. Although mean Al and Si coordination numbers both decrease with increasing Al contents, the weighted combined (Al+Si) coordination number increases. Silicon and Al resonances shift in frequency with increasing pressure or changing Al concentration, indicating additional structural changes, including compression of network bond angles. Increases in the ^(23)Na isotropic chemical shifts indicate decreases in the mean Na-O bond lengths with increasing pressure, which are more dramatic at higher Al contents. Recovered glass densities are about 10 to 15% greater than those of similar ambient pressure samples. However, the density increases due to the combined coordination changes of Al and Si are estimated to total only about 1 to 2%, and are roughly constant with composition despite the large effects of Al content on the individual coordinations of the two cations. Thus, effects of other structural changes must be significant to the overall densification. Apparent equilibrium constants for reactions involving the generation of high-coordinated species show systematic behavior, which suggests an internal consistency to the observed Si and Al coordination number shifts.

Mechanism and kinetics of a mineral transformation under hydrothermal conditions: Calaverite to metallic gold

Abstract: The transformation of calaverite to gold under hydrothermal conditions was studied experimentally by probing the effects of temperature (140 to 220 °C), pH (2–12), oxidant concentration, geometric specific surface area, and solid-weight to fluid-volume ratio on the sample textures and the reaction kinetics. Under all of the experimental conditions explored, calaverite transformed to various extents to metallic gold. The replacement is pseudomorphic, as gold preserves the external dimensions of calaverite. The resulting elemental gold is porous; consisting of filament-shaped aggregates with diameters ranging from 200 to 500 nm and lengths up to 25 μm. Gold crystals appear to be randomly oriented with respect to the twinned calaverite grains. The transformation proceeds via a coupled calaverite dissolution–gold precipitation mechanism, with calaverite dissolution being rate-limiting relative to gold precipitation. Tellurium is lost to the bulk solution as Te(IV) complexes, and may further precipitate away from the dissolution site (e.g., autoclave walls) as TeO2(s). In contrast, gold precipitates locally near the calaverite dissolution site. Such local gold precipitation is facilitated by fast heterogeneous nucleation onto the calaverite surface. The dissolution of calaverite and the overall reaction are oxidation reactions, and oxygen diffusion through the porous metallic gold layer probably plays an important role in sustaining the reaction. A similar dissolution-reprecipitation process may be responsible for the formation of mustard gold during the weathering of gold-telluride ores. At 220 °C, solid-state replacement of calaverite by gold is slow (months), but calaverite grains ~100 μm in size are fully replaced in <24 h under hydrothermal conditions, providing a possible alternative to roasting as a pre-treatment of telluride-rich gold ores.

Octahedral cation distribution in palygorskite

Abstract: The OH speciation of 18 palygorskite samples from various localities were evaluated by near infrared spectroscopy (NIR) and compared to the corresponding octahedral composition derived from independent, single-particle analytical electron microscopy (AEM). NIR gives evidence for dioctahedral-like (AlAlOH, AlFe3+OH, Fe3+Fe3+OH) and trioctahedral-like (Mg3OH) species. Therefore, palygorskite can be approximated by the formula yMg5 Si8O20(OH)2·(1 – y)[xMg2Fe2·(1 – x)Mg2Al2]Si8O20(OH)2, where x is the Fe content of the dioctahedral component, and y is the trioctahedral fraction. The values of x estimated from the NIR data are in excellent agreement with the Fe/(VIAl + Fe) ratio from AEM (R2 = 0.98, σ = 0.03), thus suggesting that all octahedral Al and Fe in palygorskite participate in M2M2OH (dioctahedral-like) arrangements. Furthermore, y values from AEM can be compared to NIR (R2 = 0.90 and σ = 0.05) after calibrating the relative intensity of the Mg3OH vs. (Al,Fe)2OH overtone bands using AEM data. The agreement between the spectroscopic and analytical data are excellent. The data show that Fe3+ for Al substitution varies continuously in the analyzed samples over a broad range (0 < x < 0.7), suggesting that fully ferric dioctahedral palygorskites (x = 1) may exist. On the other hand, the observed upper trioctahedral limit of y = 0.50 calls for the detailed structural comparison of Mg-rich palygorskite with sepiolite.

Growth controls in colloform pyrite

Abstract: Primary colloform textures preserved in ore deposits can be a useful tool in understanding changing conditions of ore formation due to the sequential development of the colloform layers. However, the growth controls that influence formation of these textures are poorly understood. To try to address this problem, samples from two ore deposits, Greens Creek in Alaska and Ezuri in Japan, have been systematically analyzed for grain size and shape, crystal preferred orientation (CPO), sulfur isotope composition, and trace element content. Grain size and shape varies between layers of equant, ~20 μm crystals to acicular and elongate crystals up to several millimeters in length. Electron backscatter diffraction (EBSD) reveals that both samples have an initial random orientation of crystals with CPO in subsequent layers developed either about , , or crystallographic axes. Despite similarity in texture, the sulfur isotope results from Greens Creek colloforms have a very negative, open-system bacteriogenic δ34S between –40 and –32‰, whereas the Ezuri colloform has a positive δ34S of ~+5‰, typical of hydrothermal sulfur in Kuroko ores. Trace element results indicate variability in As, Sb, and Cu distribution. Whereas trace element variability at Greens Creek appears to be related to changes in δ34S, with a heavier signature correlating with sequestration of Sb in outer layers, overall the detailed analyses reveal that in both Greens Creek and Ezuri, there is no systematic correlation between sulfur source or trace element sequestration and CPO. This suggests that the abrupt changes in CPO recorded appear most likely to be influenced by changes in degree of supersaturation.

Magmatic vs. hydrothermal origins for zircon associated with tantalum mineralization in the Tanco pegmatite, Manitoba, Canada

Abstract: Complex textures in zircon associated with Ta oxides have been used to assess the processes at the origin of zircon crystallization and associated Ta mineralization in pegmatites, in particular the role of magmatic vs. hydrothermal processes. The Tanco pegmatite is used as an example because its zircon is devoid of post-magmatic alteration and its petrogenesis is well constrained. Zircon in primary units is metamict with high U-Pb-Th contents. By contrast, in secondary assemblages affected by late-magmatic micaceous alteration, zircon is devoid of radiogenic elements, but it may contain abundant Ta2O5 (up to 4.7 wt%). The incorporation of Ta into zircon may occur through coupled substitution mechanisms involving other minor elements such as P, Al, Mn, or Li. The presence of Ta accounts for the distorted structures in the Ta-rich zircon, as revealed in high-resolution TEM images. Four zircon types occur sequentially in single zircon crystals, which permits a new model for zircon growth and evolution in rare element pegmatites to be advanced: (1) zircon (Z1) is Ta-rich and crystallized possibly before discrete Ta phases; (2) Z1 was overgrown by regularly zoned zircon Z2 and Z3, which show lower Ta and extreme Zr/Hf fractionation (HfO2 up to 38.9 wt%), suggesting crystallization from a highly fractionated melt, possibly at the onset of Ta mineralization; and (3) close to the solidus, the aqueous fluid at the origin of micaceous alteration corroded the distorted structure of Z1, and a low-Ta zircon (Z4) replaced Z1 by dissolution-reprecipitation, whereas Z2 and Z3 resisted this alteration. Tantalum was no longer stable in the zircon structure and crystallized as Ta-oxide inclusions in the reequilibrated zircon (Z4).

Calcium L2,3-edge XANES of carbonates, carbonate apatite, and oldhamite (CaS)

Abstract: The local electronic structure and stereochemistry of calcite, aragonite, dolomite, ferroan dolomite, manganoan calcite, synthetic carbonate hydroxylapatite (CHAP), and CaS (synthetic oldhamite) have been studied using Ca L 2,3 -edge X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectra of the calcite- and dolomite-structure carbonates are identical within error of measurement, confirming the local nature of X-ray absorption at the L 2,3 edge of Ca 2+ . The Ca L 2,3 -edge XANES spectrum of aragonite is distinct and indicates a weak crystal-field splitting of positive 10 Dq . Separate Ca1 and Ca2 sites are resolved in the XANES of hydroxylapatite and CHAP: Ca1 appears to have a very weak crystal field of negative 10 Dq , and Ca2 has a weak crystal field of positive 10 Dq . The Ca L 2,3 -edge XANES spectrum of CaS reflects both Ca and S unoccupied 3 d states, and is used to show progressive oxidation of the sulfide on exposure to air. The L 2,3 X-ray absorption edge of 3 d 0 cations is associated with the 2 p 5 3 d 1 excited electronic state. It is, therefore, a novel technique for studying the crystal field of K + , Ca 2+ , Sc 3+ , and Ti 4+ , which do not have populated 3 d orbitals in their ground state.

Arsenate Substitution in Hydroxylapatite: Structural Characterization of the Ca5(PxAs1-xO4)3OH Solid Solution

Abstract: Arsenate (As5+) substitution in the hydroxylapatite structure was examined using a combination of crystallographic and spectroscopic techniques. Samples of hydroxylapatite, the As5+-substituted analog (synthetic johnbaumite), and five intermediate compositions were synthesized from solution. Synchrotron X-ray diffraction data show that all samples are single-phase, confirming complete substitution. No evidence is found for lowering of symmetry below P 63/ m . Rietveld structure refinements show progressive expansion of the unit cell with increasing As substitution, which can be accounted for primarily by an average expansion of the tetrahedral site. Sizes of Ca polyhedra show little variation as a result of As substitution. NMR results show no evidence for local clustering of PO4 tetrahedra. EXAFS confirms that the size of As-centered tetrahedra remains constant across the solid-solution series.

New insights into smectite illitization: A zoned K-bentonite revisited

Abstract: The illitization reaction in a thick K-bentonite bed located in upper Cretaceous marine shale in the Montana disturbed belt was studied by X-ray diffraction, chemical analysis, and thermal gravimetric analysis. Modeling of the experimental XRD patterns from oriented clay specimens in air-dried and glycolated states shows that at each sample location in the bentonite bed a mixture of R0 illite-smectite (I-S) and R1 I-S coexist. Each of these phases in all samples consists of the same or similar content of illite and expandable layers independent on location in the bed. In particular, the illite content in the R0 I-S and the R1 I-S from the <0.5 μm fractions is equal to 30 and 62%, respectively. The main difference between the samples at different locations is the different weight concentrations of the coexisting I-S phases. The R1 I-S content decreases progressively from the lower and upper contacts of the bed to its center. The reverse trend was observed for the R0 I-S. The layer unit-cell parameter b increases from samples located near the middle of the bed toward samples near the bed margins. The DTG patterns of the samples contain two endothermic maxima at about 640 and 470 °C, corresponding to cis -vacant ( cv ) illite and trans -vacant ( tv ) smectite layers coexisting in the R1 I-S and R0 I-S. Analysis of the crystal-chemical features of the R1 I-S and R0 I-S shows that, in the middle of the bed, both phases are characterized by the lowest octahedral Mg and the highest tetrahedral Al contents. In the structural formula of the R1 I-S, the tetrahedral Al content is significantly higher than the (K+Na) content independent of sample location. In contrast, tetrahedral Al in the R0 I-S located near the bed boundaries is lower compared with (K+Na) content. To account for the crystal-chemical features of the coexisting I-S, a first assumption is that the initial volcanic ash was altered into tv smectite having a homogeneous Al-rich composition throughout the bed. Second, along with K, the active role in illitization was controlled by Mg. Mineralogical zonation of the K-bentonite is explained by the progressive migration of K from the margins toward the bed center with the associated decrease of K cations in the pore fluids. However, the decrease in K concentration was accompanied by a successive increase in R0 I-S content, but not a progressive decrease in illite layer content in a single I-S phase. The main role of Mg was to redistribute octahedral and tetrahedral Al in the 2:1 layers of the R0 I-S and R1 I-S in such a way that the amount of Al in the tetrahedral sheets increased at the expense of the substitution of Mg for Al in the octahedral sheet of the 2:1 layers in the initial smectite. These results demonstrate a new insight into mineralogical sequences of intermediate members of smectite illitization. Instead of a statistically homogeneous and continuous reaction associated with the increase of illite layers in I-S and the simultaneous increase of order of the layer stacking sequence, the illitization reaction in the thick K-bentonite consists of the formation of a physical mixture of two I-S having a contrasting content of layer types and their distribution. Factors responsible for the formation of the coexisting R0 I-S and R1 I-S are discussed.

The carbonatation of gypsum: Pathways and pseudomorph formation

Abstract: In this paper, we present an experimental study of the interaction between gypsum (010) surfaces and aqueous solutions of Na2CO3 with different concentrations. This interaction leads to the carbonatation (i.e., the transformation into carbonate minerals) of gypsum crystals, which under ambient conditions shows the characteristics of a mineral replacement and leads to the formation of pseudomorphs consisting of an aggregate of calcite crystals. Carbonatation progress was monitored by scanning electron microscopy (SEM) and glancing incidence X-ray diffraction (GIXRD). The carbonatation advances from outside to inside the gypsum crystal and occurs through a sequence of reactions, which involves the dissolution of gypsum and the simultaneous crystallization of different polymorphs of CaCO3 [amorphous calcium carbonate (ACC), vaterite, aragonite, and calcite], as well as several solvent-mediated transformations between these polymorphs. The sequence in which CaCO3 phases form is interpreted taking into consideration nucleation kinetics and the qualitative evolution of several chemical parameters in the aqueous solution. The textural characteristics of the transformed regions are described. The degree of faithfulness of the pseudomorphs obtained is related to the kinetics of the carbonatation process, which in turn depends on the initial concentration of carbonate in the aqueous solutions. Finally, changes in the rate at which the transformation front advances are discussed on the basis of both textural and physicochemical considerations.