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1.
The solid‐state reaction magnesite (MgCO3) + calcite (aragonite) (CaCO3) = dolomite (CaMg(CO3)2) has been identified in metapelites from western Tianshan, China. Petrological studies show that two metamorphic stages are recorded in the metapelites: (1) the peak mineral assemblage of magnesite and calcite pseudomorphs after aragonite which is only preserved as inclusions within dolomite; and (2) the retrograde glaucophane‐chloritoid facies mineral assemblage of glaucophane, chloritoid, dolomite, garnet, paragonite, chlorite and quartz. The peak metamorphic temperatures and pressures are calculated to be 560–600 °C, 4.95–5.07 GPa based on the calcite–dolomite geothermometer and the equilibrium calculation of the reaction dolomite = magnesite + aragonite, respectively. These give direct evidence in UHP metamorphic rocks from Tianshan, China, that carbonate sediments were subducted to greater than 150 km depth. This UHP metamorphism represents a geotherm lower than any previously estimated for subduction metamorphism (< 3.7 °C km?1) and is within what was previously considered a ‘forbidden’ condition within Earth. In terms of the carbon cycle, this demonstrates that carbonate sediments can be subducted to at least 150 km depth without releasing significant CO2 to the overlying mantle wedge.  相似文献   

2.
Eclogites from the Jæren nappe in the Caledonian orogenic belt of SW Norway contain aragonite, magnesite and dolomite in quartz‐rich layers. The carbonates comprise composite grains that occur interstitially between phases of the eclogite facies assemblage: garnet + omphacite + zoisite + clinozoisite + quartz + apatite + rutile ± dolomite ± kyanite ± phengite. Pressure and temperature conditions for the main eclogite stage are estimated to be 2.3–2.8 GPa and 585–655 °C. Published ultrahigh pressure (UHP) experiments on CaO‐, MgO‐ and CO2‐bearing systems have shown that equilibrium assemblages of aragonite and magnesite form as a result of dolomite breakdown at pressures >5 GPa. As a result, recognition of magnesite and aragonite in eclogite facies rocks has been used as an indicator for UHP conditions. However, petrological testing showed that the samples studied here have not experienced such conditions. Aragonite and magnesite show disequilibrium textures that indicate replacement of magnesite by aragonite. This process is inferred to have occurred via a coupled dissolution–precipitation reaction. The formation of aragonite is constrained to eclogite facies conditions, which implies that the studied rocks have experienced metasomatic, reactive fluid flow during their residence at high pressure (HP) conditions. During decompression, the bimineralic carbonate aggregates were overgrown by rims of dolomite, which partially reacted with aragonite to form Mg‐calcite. The well‐preserved carbonate assemblages and textures observed in the studied samples provide a detailed record of the reaction series that affected the rocks during and after their residence at P–T conditions near the coesite stability field. Recognition of the HP mechanism of magnesite replacement by aragonite provides new insight into metasomatic processes that occur in subduction zones and illustrates how fluids facilitate HP carbonate reactions that do not occur in dry systems at otherwise identical physiochemical conditions. This study documents that caution is warranted in interpreting aragonite‐magnesite associations in eclogite facies rocks as evidence for UHP metamorphic conditions.  相似文献   

3.
ABSTRACT Gravity cores of Holocene sediments from a shallow ephemeral lake in the Coorong region (Pellet Lake, southeastern coastal Australia) show a mineral assemblage and sequence particular to its hydrology. The mineralogical sequence above an initial dolomitic siliciclastic sand reflects conditions of increasing salinity in the lower portions of the core (i.e. organic-rich aragonite to magnesite + hydromagnesite + aragonite) followed by a relative decrease in salinity (i.e. magnesite + aragonite + hydromagnesite to aragonite + hydromagnesite) in the upper portions of the core. This sequence is capped by ? 0.4 m of micritic dolomite and minor amounts of hydromagnesite, with the relative abundance of dolomite increasing upwards. Three stratigraphically and spatially distinct dolomite units (upper, lower and margin) are recognized using stable carbon and oxygen isotope data, unit cell calculations and MgCO3 mole per cent data of the dolomite. Detailed X-ray diffraction (XRD) analyses of samples with more than 80% dolomite shows that the dolomite is ordered. Average unit cell parameters, calculated from the XRD patterns, indicate that the upper dolomite unit has crystal lattices expanded in the co direction (co= 16.09 Å) relative to ideal dolomite (co= 16.02 Å) and contracted in the ao direction (ao= 4.796 Å) relative to ideal dolomite (ao= 4.812 Å). The mol fraction of MgCO3 in the upper dolomite shows up to 4.0 ±M 2.0 mole per cent excess Mg in the dolomite crystal lattice (calculated from XRD). This unusual dolomite crystal chemistry is probably generated by rapid precipitation from solutions which have greatly elevated Mg/Ca ratios. Transmission electron microscopy reveals that the upper dolomite has a heterogeneous microstructure which also suggests rapid precipitation from solution. The modulated microstructure found in calcium-rich dolomite is completely lacking. Dolomite ordering reflections are present in electron diffraction patterns, but are weak. Stable oxygen and carbon isotope values of the upper dolomite are tightly grouped (ave. δ18O ～+ 7.55%o, δ13C ～+ 4.10%o), yet show three upward-lightening oxygen cycles. The oxygen cycles correlate with three upward decreases in the calculated Mg content of the dolomite zone. These cycles may indicate the increased importance of rain-water dilution of the brine at times when the water in the lake was at its shallowest levels. Analyses of the lower dolomite and the margin dolomite suggest that these units precipitated more slowly from less evaporitic brines than the upper dolomite unit. The lower dolomite is close to stoichiometric, has less evaporitic stable isotope values than the upper dolomite, and has only a slightly expanded co-axis. The margin dolomite is Ca-rich, has a more homogeneous microstructure, and has expanded ao and co axes. The abundance of relatively soluble Mg-bearing phases, such as hydromagnesite and magnesite, may supply additional magnesium for the dolomitization of aragonite and calcite during subsequent diagenesis and burial of the sediment. This process may leave a finely laminated dolomicrite deposit which retains little, if any, evidence of evaporite minerals.  相似文献   

4.
We report on high-pressure and high-temperature experiments involving carbonates and silicates at 30–80 GPa and 1,600–3,200 K, corresponding to depths within the Earth of approximately 800–2,200 km. The experiments are intended to represent the decomposition process of carbonates contained within oceanic plates subducted into the lower mantle. In basaltic composition, CaCO3 (calcite and aragonite), the major carbonate phase in marine sediments, is altered into MgCO3 (magnesite) via reactions with Mg-bearing silicates under conditions that are 200–300°C colder than the mantle geotherm. With increasing temperature and pressure, the magnesite decomposes into an assemblage of CO2 + perovskite via reactions with SiO2. Magnesite is not the only host phase for subducted carbon—solid CO2 also carries carbon in the lower mantle. Furthermore, CO2 itself breaks down to diamond and oxygen under geotherm conditions over 70 GPa, which might imply a possible mechanism for diamond formation in the lower mantle.  相似文献   

5.
Martinez et al. bracketed the decomposition reaction of dolomite to aragonite + magnesite between 5.0 and 5.5 GPa at 600 °C using in-situ XRD in a multi-anvil apparatus. They then extrapolated their results using the available thermodynamic data such that the breakdown reaction occurs at ~1,000 °C at 6 GPa. If correct, this extrapolation has implications for the type(s) of stable carbonate(s) in the mantle. For example, the reaction magnesite + diopside = dolomite + enstatite would be metastable at P >7 GPa relative to the aragonite-containing analog, and thus aragonite, rather than dolomite, might be stable near the solidus of lherzolite. This extrapolation would also imply that aragonite and magnesite would be stable in garnet + clinopyroxene assemblages at pressures in the stability field of diamond. To test this extrapolation, experiments were conducted at higher temperatures in a multiple-anvil apparatus. Results of initial experiments were consistent with the results of Martinez et al.. At higher temperatures, however, the reaction occurs at higher pressures than predicted by Martinez et al., requiring significant curvature to the reaction boundary. This curvature (increasing dP/dT with increasing T) is consistent with increasing disorder in the dolomite with increasing temperature, increasing the stability of dolomite relative to aragonite plus magnesite. The experimental results restrict aragonite + magnesite-bearing assemblages to low temperature. Aragonite will not be present in near-solidus lherzolite, and can be present in orthopyroxene-free eclogites and pyroxenites only at low temperature.  相似文献   

6.
Origin of ultramafic-hosted magnesite on Margarita Island,Venezuela   总被引：1，自引：0，他引：1  
Ultramafic-hosted deposits of magnesite (MgCO3) have been studied on Margarita Island, Venezuela, to elucidate the source of carbon and conditions of formation for this type of ore. Petrographic, mineralogic, and δ18O data indicate that magnesite precipitated on Margarita in near-surface environments at low P and T. δ13C ranges from −9 to −16‰ PDB within the magnesite and −8 to −10‰ PDB within some calcite and dolomite elsewhere on the island. The isotopically light dolomite fills karst and the calcite occurs as stock-work veins which resemble the magnesite deposits. These carbon isotopic ratios are consistent with a deep-seated source rather than an overlying source from a zone of surficial weathering. However, there is not much enrichment of precious metals and no enrichment of heavy rare-earth elements, as would be expected if the carbon had migrated upward as aqueous carbonate ions. The carbon probably has risen as a gaseous mixture of CO2 and CH4 which partially dissolved in near-surface water before leaching cations and precipitating as magnesite and other carbonates. The process probably is ongoing, given regional exhalation of carbonaceous gases.  相似文献   

7.
The pressure–temperature conditions of the reactions of the double carbonates CaM(CO3)2, where M = Mg (dolomite), Fe (ankerite) and Mn (kutnohorite), to MCO3 plus CaCO3 (aragonite) have been investigated at 5–8 GPa, 600–1,100°C, using multi-anvil apparatus. The reaction dolomite = magnesite + aragonite is in good agreement with the results of Sato and Katsura (Earth Planet Sci 184:529–534, 2001), but in poor agreement with the results of Luth (Contrib Mineral Petrol 141:222–232, 2001). The dolomite is partially disordered at 620°C, and fully disordered at 1,100°C. All ankerite and kutnohorite samples, including the synthetic starting materials, are disordered. The P–T slopes of the three reactions increase in the order M = Mg, Fe, Mn. The shallower slope for the reaction involving magnesite is due partly to its having a higher compressibility than expected from unit-cell volume considerations. At low pressures there is a preference for partitioning into the double carbonate of Mg > Fe > Mn. At high pressures the partitioning preference is reversed. Using the measured reaction positions, the P–T conditions at which dolomite solid solutions will break down on increasing P and T in subduction zones can be estimated.  相似文献   

8.
The rates of grain growth of stoichiometric dolomite [CaMg(CO3)2] and magnesite (MgCO3) have been measured at temperatures T of 700–800°C at a confining pressure P c of 300 MPa, and compared with growth rates of calcite (CaCO3). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO3)2, MgCO3, and CaCO3, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO3)2, MgCO3, and CaCO3, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (≃5 × 10−5 μm3/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.  相似文献   

9.
The results of experiments on the hydrothermal dolomitization of calcite (between 252 and 295°C) and aragonite (at 252°C) by a 2 M CaCl2-MgCl2 aqueous solution are reported and discussed. Dolomitization of calcite proceeds via an intermediate high (ca. 35 mole %) magnesian calcite, whereas that of aragonite is carried out through the conversion of the reactant into a low (5.6 mole %) magnesian calcite which in turn transforms into a high (39.6 mole %) magnesian calcite. Both the intermediate phases and dolomite crystallize through a dissolution-precipitation reaction. The intermediate phases form under local equilibrium within a reaction zone surrounding the dissolving reactant grains. The volume of the reaction zone solution can be estimated from Sr2+ and Mg2+ partitioning equations. In the case of low magnesian calcite growing at the expense of aragonite at 252°C, the total volume of these zones is in the range of 2 × 10?5 to 2 × 10?4 1., out of 5 × 10?3 1., the volume of the bulk solution.The apparent activation energies for the initial crystallization of high magnesian calcite and dolomite are 48 and 49 kcal/mole, respectively.Calcite transforms completely into dolomite within 100 hr at 252°C. The overall reaction time is reduced to approximately 4 hr at 295°C. The transformation of aragonite to dolomite at 252°C occurs within 24 hr. The nature of the reactant dictates the relative rates of crystallization of the intermediate phases and dolomite. With calcite as reactant, dolomite growth is faster than that of magnesian calcite; this situation is reversed when aragonite is dolomitized.Coprecipitation of Sr2+ with dolomite is independent of temperature (within analytical error) between 252 and 295°C. Its partitioning, with respect to calcium, between dolomite and solution results in distribution coefficients in the range of 2.31 × 10?2 to 2.78 × 10?2.  相似文献   

10.
 High-pressure and high-temperature Raman spectra of CaGeO3 tetragonal garnet have been collected to 11.5 GPa and 1225 K, respectively, in order to investigate possible intrinsic anharmonic behaviour in this phase. The Raman peak positions were observed to vary linearly with pressure and temperature within the ranges studied, with the higher-energy peaks showing larger P- and T-induced shifts than the low energy modes. The observed T-induced shifts are similar to those reported for grossular and andradite, while the observed P-induced shifts are generally larger than those of aluminosilicate and MgSiO3 majorite garnets (Gillet et al. 1992; Rauch et al. 1996) due to the larger bulk modulus of CaGeO3 garnet. The observed mode shifts of CaGeO3 garnet were used to determine the isothermal and isobaric mode Grüneisen parameters for this phase. These parameters are similar in value to those reported previously for grossular and andradite (Gillet et al. 1992). The calculated intrinsic anharmonic parameters, a i , for CaGeO3 garnet were determined to be nonzero, indicating significant anharmonic behaviour for this phase. These values, which range from −3.8 × 10−5 K−1 to −1.3 × 10−5 K−1, are also similar to those reported for andradite and grossular, but smaller than those determined for pyrope (Gillet et al. 1992). Hence, we expect MgSiO3 majorite to show greater anharmonicity than the germanate analogue studied by us. The anharmonic parameters determined for CaGeO3 tetragonal garnet may now be introduced into quasiharmonic vibrational heat capacity models to account for the observed anharmonic behaviour. Received: 21 April 1999 / Revised, accepted: 11 September 1999  相似文献   

11.
The sediment-hosted huntite-magnesite deposits are located in the Egirdir-Hoyran lake basin in the Isparta Angle (southern Turkey). The deposits occur at two different localities in the region: (1) Kemersirti huntite deposit, (2) Köytepe huntite-magnesite deposit. The huntite-magnesite occurrences are found in shallow lacustrine rocks of the Miocene-Pliocene Kizilcik Formation and formed as a result of Neogene tectonic activity. Based on X-ray diffraction and scanning electron microscopic studies, the mineral assemblage of huntite deposits contains mostly huntite, less magnesite, dolomite, very little calcite, illite, simectite, brucite, and quartz in the Kemersirti area but contain huntite, magnesite, dolomite, and calcite in the Köytepe area.In the huntite and magnesite-bearing huntite samples, MgO varies from 32.70 to 37.95 wt. %, CaO from 7.83 to 15.10 w.t. %, and SiO2 from 0.99 to 10.60 w.t. %. Ba and Sr are dominant minor elements in the deposits. Ba and Sr for huntite and magnesite bearing huntite in the study area vary from 11 to 233 ppm and from 325 to 765 ppm, respectively. As, U, Zr, V and Ce contents ranged from 11.5-146 ppm, 0.5-3.7 ppm, 1.4-13.2 ppm, 7-34 ppm, and 0.9-2.7 ppm respectively. The huntite-magnesite is characterized by relatively lower Ni (0.5-2.4 ppm) and Co (0.5-1.1 ppm) contents. The huntite and magnesite-bearing huntite occurrences have higher Ba, Sr, As, Zr, V, and U contents than those of the other elements. The d13C isotope values vary between 7.8‰ to 8.8‰ PDB for huntite+magnesite, 8.2‰ PDB for huntite, 1.4‰ PDB for magnesite+dolomite, and 4.0‰ PDB for limestone from deposits in the study area. The δ18O isotope values of the huntite deposits ranged from 30.4 to 35.5‰ SMOW for huntite+magnesite, 32.4‰ SMOW for huntite, 29.8‰ SMOW for magnesite+ dolomite, and 26.9‰ SMOW for limestone.The presence of nodular huntite and the abundance of gastropod, ostracoda and Chura shells in the carbonate units indicate that the huntite occurrences are precipitated at shallow, alkaline (8.5-9.5 pH) and lower temperature (approximately 25°C) lake conditions. The Mg++, Ca++ and Si++ ions for the huntite formation were derived from the surrounding rocks such as ultrabasic rocks, dolomite, dolomitic limestone, and limestone in the Egirdir-Hoyran lake basin. Also, the C isotope ratios indicate that the CO2 source for the huntite formations results to sedimentary basin from metamorphic CO2, carbonate rocks, fresh water carbonates, and ground water. The source of oxygen for the huntite formation may come from marine limestone, fresh water carbonates and meteoric water.  相似文献   

12.
Holocene carbonate sedimentation in Lake Manitoba, Canada   总被引：1，自引：0，他引：1  
W. M. LAST 《Sedimentology》1982,29(5):691-704
The carbonate mineral suite of the modern offshore bottom sediment of the South Basin of Lake Manitoba consists mainly of high magnesian calcite and dolomite with minor amounts of low-Mg calcite and aragonite. The high-Mg calcite is derived from inorganic precipitation within the water column in response to supersaturation brought about by high levels of organic productivity in the basin. Both dolomite and pure calcite are detrital in origin, derived from erosion of the surrounding carbonate-rich glacial deposits. Aragonite, present only in trace amounts in the offshore sediments, is bioclastic in origin. The upward increase in the amount of magnesian calcite in the post-glacial sediment record is attributed to increasing photosynthetic utilization of CO2 in the lake. Stratigraphic variation in the amount of magnesium incorporated into the calcite lattice is interpreted as reflecting a variable magnesium input to the lake from ground water and surface runoff, and possibly variable calcium removal in the precipitating lake water. The effects of long-term chemical weathering at the source and size segregation explain the changes in dolomite content throughout the section.  相似文献   

13.
We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K d (X Fe carb X Mg ol /X Fe ol X Mg carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W FeMg ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO3 a W FeMg carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K d substantially enabling us to calculate W CaMg carb -W CaFe carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO2(CMS)–CO2 system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO2. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.  相似文献   

14.
Using established methods of statistical mechanical calculation and a recent compilation of vibrational frequency data, we have computed oxygen isotope reduced partition function ratios (β values) for a large number of carbonate minerals. The oxygen isotope β values of carbonates are inversely correlated to both the mass and radius of the cation bonded to the carbonate anion but neither correlation is good enough to be used as a precise and accurate predictor of β values. There is an approximately 0.6% relative increase in the β values of aragonite per 10 kbar increase in pressure. These estimates of the pressure effect on β values are broadly similar to those deduced previously for calcite using the methods of mineral physics. In comparing the β values of our study with those derived recently from first-principles lattice dynamics calculations, we find near-perfect agreement for calcite and witherite (<0.3% deviation), reasonable agreement for dolomite (<0.9% deviation) and somewhat poorer agreement for aragonite and magnesite (1.5-2% deviation). In the system for which we have the most robust constraints, CO2-calcite, there is excellent agreement between our calculations and experimental data over a broad range of temperatures (0-900 °C). Similarly, there is good to excellent correspondence between calculation and experiment for most other low to moderate atomic mass carbonate minerals (aragonite to strontianite). The agreement is not as good for high atomic mass carbonates (witherite, cerussite, otavite). In the case of witherite and cerussite, the discrepancy may be due, in part, to our calculation methodology, which does not account for the effect of cation mass on the magnitude of vibrational frequency shifts associated with heavy isotope substitution. However, the calculations also reveal an incompatibility between the high- and low-temperature experimental datasets for witherite and cerussite. Specifically, the shapes of fractionation factor versus 1/T2 curves in the calcite-witherite and calcite-cerussite systems do not conform to the robust constraints on the basic shape of these curves provided by theory. This suggests that either the high- or low-temperature datasets for both minerals is in error. Dolomite-calcite fractionation factors derived from our calculations fall within the wide range of fractionations for this system given by previous experimental and natural sample studies. However, our compilation of available low-temperature (25-80 °C) experimental data reveal an unusual temperature dependence of fractionations in this system; namely, the data indicate an increase in the magnitude of fractionations between dolomite (or proto-dolomite) and calcite with increasing temperature. Such a trend is incompatible with theory, which stipulates that fractionations between carbonate minerals must decrease monotonically with increasing temperature. We propose that the anomalous temperature dependence seen in the low-temperature experimental data reflect changes in the crystallinity and degree of cation ordering of the dolomite phase over this temperature interval and the effect these changes have on the vibrational frequencies of dolomite. Similar effects may be present in natural systems at low-temperature and must be considered in applying experimental or theoretical fractionation data to these systems. In nearly all cases, carbonate mineral-calcite fractionation factors given by the present calculations are in as good or better agreement with experimental data than are fractionations derived from semi-empirical bond strength methods.  相似文献   

15.
The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200 °C using single inorganic aragonite crystals as a starting material. The initial saturation state and the total [Ca2+]:[CO32−] ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy.Experiments using carbonate solutions prepared with water enriched in 18O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of 18O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the 18O distribution in the calcite replacement. An activation energy of 109 kJ/mol was calculated for the exchange of oxygen isotopes between [C16O32−]aq and [H218O] and the time for oxygen isotope exchange in the fluid at 200 °C was estimated at ∼0.9 s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution-reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.  相似文献   

16.
The Raman spectra of geikielite (MgTiO3-ilmenite) have been recorded at high pressure (up to 27 GPa) and at high temperature (up to 1820 K). No phase transitions could be evidenced in both cases. In particular, no cation disordering can be evidenced from the high temperature spectra. The observed Raman wavenumber shifts with pressure and with temperature are used to calculate the intrinsic mode anharmonic parameters. The low absolute values of these parameters indicate that geikielite has a nearly quasi-harmonic behaviour, at least to moderate temperatures. However, systematics and the temperature evolution of Raman linewidths suggest that the absolute values of the anharmonic parameters increase at high temperatures. Anharmonic corrections are applied to Kieffer modelling of the constant volume heat capacity of geikielite. They amount to +4 J · mol-1 · K-1 at 1800 K, i.e. are much lower than those inferred for, for instance, olivine and garnet structures. These results are used to discuss some implications on the phase relations of the high-pressure MgSiO3-ilmenite, and the factors controlling the occurence of order-disorder transitions in ilmenite structures.  相似文献   

17.
An empirical model for investigating the behaviour of CaCO3 polymorphs incorporating a shell model for oxygen has been created. The model was constructed by fitting to: the structure of aragonite and calcite; their elastic, static and high-frequency dielectric constants; phonon frequencies at the wave vectors [&frac; 0 2] and [0 0 0] of calcite; and vibrational frequencies of the carbonate deformation modes of calcite. The high-pressure phase transition between calcite I and II is observed. The potentials for the CO3 group were transferred to other carbonates, by refitting the interaction between CO3 and the cation to both the experimental structures and their bulk modulus, creating a set of potentials for calculating the properties of a wide range of carbonate materials. Defect energies of substitutional cation defects were analyzed for calcite and aragonite phases. The results were rationalized by studying the structure of calcite and aragonite in greater detail.  相似文献   

18.
Calcite and aragonite have been modeled using rigid-ion, two-body Born-type potentials, supplemented by O-C-O angular terms inside the CO3 groups. A shell model has also been developed for calcite. Atomic charges, repulsive parameters and force constants have been optimized to reproduce the equilibrium crystal structures, the elastic constants and the Raman and infrared vibrational frequencies. The rigid-ion potential RIM (atomic charges:z O= -0.995e,z C = 0.985e,z Ca = 2.0e) fitted to calcite properties is able to account for those of aragonite as well. Experimental unit-cell edges, elastic constants, internal and lattice frequencies are reproduced with average relative errors of 2.1, 5.5, 2.4, 15.1% for calcite and of 0.2, 19.4, 2.5, 11.8% for aragonite, respectively. The RIM potential is suitable for thermodynamic and phase diagram simulations in the CaCO3 system, and is discussed and compared to other potentials.  相似文献   

19.
Prolonged grinding increases the energy of solids by the production of stored energy in the form of new surfaces and internal defects. Moreover, grinding also generates quasi-hydrostatic pressures which can result in polymorphic transformations and mineral decomposition. Here we demonstrate the solid-state transformation of metastable to stable polymorphs (aragonite → calcite, anatase → rutile); the transformation of low-pressure to high-pressure phases (calcite → aragonite); and the lowering of the dehydration and decarbonation temperatures of minerals (siderite → magnetite or hematite, diaspore → corundum).In the presence of a fluid phase, stored energy from grinding can be released, resulting in accelerated reaction rates and, more importantly, phase transformations. In this paper we demonstrate the following transformations: ground calcite → magnesian calcite (at low Mg2+ concentration in solution), ground calcite → aragonite (at high Mg2+ concentration), ground magnesite → hydromagnesite, and ground dolomite → aragonite + Mg2+.Assuming an analogy between laboratory and natural grinding, tectonic activity may have important consequences on the release of hydrothermal fluids, the solubilization of minerals and on solid-state transformations. As examples the possible role of deformation on the formation of metamorphic aragonite and diaspore-bauxites is discussed.  相似文献   

20.
Because of major differences in both bulk chemical composition and silicate mineralogy between metabasalts and metaperidotites, valid comparison of the degree or intensity of carbonate alteration cannot be made in terms of weight per cent CO2. Molar CO2/CaO is preferred as an index of the intensity of carbonate alteration in metabasalts; molar CO2/CaO in carbonatized metabasalts is independent of CaO/MgO and only mildly sensitive to bulk composition and to the proportions of tremolite and clinozoisite. Molar CO2/CaO reflect the proportions of calcite and dolomite in metabasalts and the proportions of dolomite and magnesite in metaperidotites. However, neither molar CO2/CaO nor the proportions of dolomite and magnesite are reliable measures of carbonate alteration in metaperidotites of variable composition because both are strongly dependent on MgO/CaO in the whole rock. The preferred alteration index in metaperidotites is m CO2/m (CaO + MgO + FeO), which represents the proportion of total relevant cations that exist in carbonate form. An empirical equation relating molar CO2/CaO in metabasalts (x) and MCO2/m(CaO+MgO+FeO) in metaperidotites (y) is: y=0.16+0.30 x.  相似文献   

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