室温条件下青海湖水中镁离子浓度对沉淀碳酸钙同质多像类型的调控

青海湖是我国唯一报道过的现代湖底沉积物中白云石、方解石和文石等多种碳酸盐矿物共存的高原内陆咸水湖泊.以青海湖水和除菌青海湖水作为载体,以CaCl2和MgCl2·6 H2O作为反应原料,在实验室常温条件下采取控制变量法制备出不同浓度Mg2+参与下的钙质沉淀物,探讨Mg2+浓度对沉淀物类型的影响.仅添加CaCl2时,青海湖...     

TEMPERATURE EFFECT ON PRECIPITATION OF CALCIUM CARBONATE FROM CALCIUM BICARBONATE SOLUTIONS AND ITS APPLICATION TO CAVERN ENVIRONMENTS

Solutions of calcium bicarbonate were allowed to lose carbon dioxide and evaporate to dryness under controlled temperature conditions. With filtered solutions prepared from spar calcite, precipitates were 100% calcite in the 2° to 100°C temperature range. When, in analogous experiments, coralline aragonite was the starting material, the precipitates were 100% calcite. Essentially the same was true when carbonate rocks from karst areas were used to prepare the experimental solutions. An artificially prepared mixture (maximum crystal size of about 7 u) of 70% aragonite and 30% calcite was also used in the study. The precipitates from this starting material were apparently affected by seed nuclei which passed through the filter. The stability of calcium carbonate seed nuclei appears to vary with temperature. Natural calcium bicarbonate solutions from caves yielded only calcite at 25°C. Calcite should be the dominant or only polymorph of CaCO₃ formed by the loss of carbon dioxide and evaporation of natural calcium bicarbonate solutions if temperature is the controlling factor. Since appreciable amounts of aragonite are found in many cave deposits, factors other than temperature must influence the polymorphs formed. POBEGUIN (1955) proposed that rapid evaporation and slow diffusion of solutions favor aragonite. If so, layers of aragonite and calcite in speleothems may reprsent alternate wet and dry paleoclimates. During these periods, rate of introduction of solution and rate of evaporation would change markedly.     

The effect of cobalt ion on nucleation of calcium-carbonate polymorphs

Cobalt, like Mg, may cause the precipitation of aragonite rather than calcite in aqueous solutions due to the adsorption and crystal poisoning of calcite by a hydrated ion. Solutions containing NaCl and CaCl₂, having the ionic strength and Ca content of seawater (35‰ salinity), were spiked with known amounts of CoCl₂. Calcium carbonate was precipitated by the addition of 0.7 ml of 1 M Na₂CO₃. All experimental runs were made at 25°C, and all products were examined by X-ray diffraction. At low concentrations of Co (< 5·^?4M) calcite and vaterite formed. At concentrations from 5·10^?4 M to 2·10^?3M, the products consisted of combinations of calcite and vaterite; aragonite and calcite; aragonite and vaterite; calcite, vaterite and aragonite. In solutions of 3·10^?3M CoCl₂, most precipitates were aragonite with only one sample containing a small amount of calcite. All precipitates from 5·10^?3M CoCl₂ solutions either contained aragonite or were amorphous. Solutions with concentrations of 1 · 10^?2M CoCl₂ produced only amorphous precipitates. All precipitates contained an amorphous violet phase, assumed to be basic cobaltous carbonate (2CoCO₃·Co(OH)₂·H₂O).     

碳酸钙矿物低温化学合成及其同质多象转变矿物学机理研究

通过缓慢分解Ca²⁺-Mg²⁺-HCO₃^--Cl^--H₂O溶液和以菱锶矿(或碳钡矿、白铅矿)为晶种的附晶生长法,在0-90℃温度范围内定向合成了碳酸钙同质多象变体.矿物合成实验结果表明,随着温度升高,有利于亚稳态文石和不稳定六方方解石的生成;随着溶液中Mg²⁺离子浓度增大和Ca(HCO₃)₃溶液浓度减小,均有利于亚稳态文石的形成.以XRD和SEM技术为实验手段,详细研究了碳酸钙同质多象转变过程.结果显示:在流体参与的情况下,文石→方解石和六方方解石→方解石的同质多象转变速率很快,并且其转变的矿物学机理为溶解/再沉淀.     

The dolomitization of CaCO3: an experimental study at 252–295°C

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.     

The solubility of calcite in seawater solutions of various magnesium concentration, It = 0.697 m at 25 °C and one atmosphere total pressure

Stoichiometric solubility constants of calcite in initially supersaturated solutions of various magnesium to calcium concentration ratios but identical ionic strength were determined at 25°C and one atmosphere total pressure.The thermodynamic solubility constant of calcite is used with ion pairing equations to interpret the data reported in this study. Results indicate that even though magnesian calcites, rather than pure calcite, precipitate from seawater solutions containing magnesium ions, the incorporation of MgCO₃ in the calcite crystal lattice does not extensively alter the equilibrium calcium carbonate activity product.The equilibrium activity of the ionic species in solution and the composition of magnesian calcite overgrowths precipitated from solutions of similar composition are used to calculate the solubility of magnesian calcites. The values for magnesian calcite solubilities obtained by this approach are lower than those obtained from the dissolution kinetics of biogenic carbonates.     

Calcite and aragonite saturation States of Kamaran strait surface seawater, Yemen: summer time

Surface seawater samples from Kamaran Strait of Yemen were collected for physical and chemical parameter determinations. This work reports the results of air and surface seawater temperature, salinity, pH, and total alkalinity measurements. The air temperature ranged from 29.9°C to 36.5°C with an average value of 31.5?±?1.5°C, whereas the seawater surface temperature ranged from 34.0°C to 36.0°C with a mean value of 34.5?±?0.5°C. The salinity was observed to be high, ranging from 38.03 to 38.81 with an average value of 38.45?±?0.22. The pH ranged from 7.74 to 8.27 with a mean value of 8.11?±?0.10. The total alkalinity was found to range from 2.3860 to 2.5000 meq L^?1 with an average value of 2.4288?±?0.0351 meq L^?1. The result of the study showed that there was a negative correlation between the pH and surface seawater temperature and salinity. The surface seawater of the Kamaran Strait was found to be several fold supersaturated with respect to calcium carbonate. The measured percent degree of saturation ranged from 454% to 668% with respect to calcite and from 246% to 361% with respect to aragonite. The lowest value of supersaturation with respect to both calcite and aragonite were found in front of as-Salif port, where human and developmental activities are intensively increased. The visual inspection of coral reefs distribution and their intensity were obviously observed in areas of high value of supersaturation with respect to both minerals, high transparency of seawater column, and low human activities. Further studies are needed to investigate the occurrence, distribution, and mineralogy of corals and the effects of physical and chemical parameters upon their growth in the region.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.     

淡水珍珠中球文石的XRD谱

球文石是CaCO3的同质多象变体，在自然界中很少出现。对不同质量淡水珍珠进行XRD物相分析，结果表明不同颜色的优质淡水珍珠中几乎全部由文石组成，方解石不发育；劣质淡水珍珠中主要含有文石、球文石；在劣质的淡水无光珠发现有球文石，可能与这些珍珠混有较多的有机物有关，文中例举了含球文石与不含球文石的淡水珍珠XRD谱。     

The role of sulfate groups in controlling CaCO3 polymorphism

The nucleation and growth of CaCO₃ phases from aqueous solutions with SO₄²⁻:CO₃²⁻ ratios from 0 to 1.62 and a pH of ∼10.9 were studied experimentally in batch reactors at 25 °C. The mineralogy, morphology and composition of the precipitates were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and microanalyses. The solids recovered after short reaction times (5 min to 1 h) consisted of a mixture of calcite and vaterite, with a S content that linearly correlates with the SO₄²⁻:CO₃²⁻ ratio in the aqueous solution. The solvent-mediated transformation of vaterite to calcite subsequently occurred. After 24 h of equilibration, calcite was the only phase present in the precipitate for aqueous solutions with SO₄²⁻:CO₃²⁻ ? 1. For SO₄²⁻:CO₃²⁻ > 1, vaterite persisted as a major phase for a longer time (>250 h for SO₄²⁻:CO₃²⁻ = 1.62). To study the role of sulfate in stabilizing vaterite, we performed a molecular simulation of the substitution of sulfate for carbonate groups into the crystal structure of vaterite, aragonite and calcite. The results obtained show that the incorporation of small amounts (<3 mole%) of sulfate is energetically favorable in the vaterite structure, unfavorable in calcite and very unfavorable in aragonite. The computer modeling provided thermodynamic information, which, combined with kinetic arguments, allowed us to put forward a plausible explanation for the observed crystallization behavior.     

Rates of aragonite conversion to calcite in dilute aqueous fluids at 50 to 100°C: experimental calibration using Ca-isotope attenuation

Aragonite was converted to calcite in dilute CaCl₂ fluid at temperatures ranging from 50 to 100°C. Surface areas of aragonite and calcite seed crystals were varied by over an order of magnitude to permit independent assessment of calcite nucleation and growth processes. Aragonite conversion rates were measured using isotopic attenuation of dissolved ⁴⁴Ca, which was added to the fluid at the beginning of each experiment. Measured conversion rates were found to be constant with respect to time and proportional to the initial surface area of aragonite. Rates were independent of the surface area of calcite seed crystals owing to heterogeneous nucleation of calcite on aragonite during experiments. The data imply that calcite nucleates on aragonite surfaces until the level of saturation with respect to calcite reaches a critical threshold value where further nucleation is precluded. Thereafter, conversion to calcite occurs at a steady state rate consistent with aragonite dissolution at a fixed level of saturation. Aragonite converts to calcite under these conditions and in dilute fluids at rates of approximately 10 and 100 microns/yr at 25 and 100°C, respectively.     

Ca-Mg inter-diffusion in synthetic polycrystalline dolomite-calcite aggregate at elevated temperatures and pressure

This study measures the reaction rate of dolomite and aragonite (calcite) into Mg-calcite at 800, 850, and 900°C and 1.6 GPa. The dry synthetic dolomite-aragonite aggregate transformed very rapidly into dolomite-calcite polycrystalline aggregate while Mg-calcites formed at a relatively slow rate, becoming progressively richer in Mg with run time. We modeled the reaction progress semi-empirically by the first-order rate law. The temperature dependence of the overall transport rate of MgCO₃ into calcite can be described by the kinetic parameters (E?=?231.7 kJ/mol and A _o ?=?22.69 h^?1). Extrapolation using the Arrhenius equation to the conditions during exhumation of UHPM rocks indicates that the reaction of dolomite with aragonite into Mg-saturated calcite can be completed as the P-T path enters the Mg-calcite stability field in a geologically short time period (<1 Ky). On the other hand, the extrapolation of the rate to prograde metamorphic conditions reveals that the Mg-calcite formed from dolomitic marble in the absence of metamorphic fluid may not reach Mg-saturation until temperatures corresponding to high-grade metamorphism (e.g., >340°C and >10 My). SEM-EDS analysis of individual calcite grains shows compositional gradients of Mg in the calcite grains. The Mg-Ca inter-diffusion coefficient at 850°C is around 1.68?×?10^?14 m²/sec if diffusion is the major control of the reaction. The calculated closure temperatures for Ca-Mg inter-diffusion as a function of cooling rate and grain size reveal that Ca/Mg resetting in calcite in a dry polycrystalline carbonate aggregate (with grain size around 1 mm) may not occur at temperatures below 480°C at a geological cooling rate around 10°C/My, unless other processes, such as short-circuit interdiffusion along grain boundaries and dislocations, are involved.     

Calcium isotope fractionation in calcite and aragonite

Calcium isotope fractionation was measured on skeletal aragonite and calcite from different marine biota and on inorganic calcite. Precipitation temperatures ranged from 0 to 28°C. Calcium isotope fractionation shows a temperature dependence in accordance with previous observations: 1000 · ln(α_cc) = −1.4 + 0.021 · T (°C) for calcite and 1000 · ln(α_ar) = −1.9 + 0.017 · T (°C) for aragonite. Within uncertainty the temperature slopes are identical for the two polymorphs. However, at all temperatures calcium isotopes are more fractionated in aragonite than in calcite. The offset in δ^44/40Ca is about 0.6‰. The underlying mechanism for this offset may be related to the different coordination numbers and bond strengths of the calcium ions in calcite and aragonite crystals, or to different Ca reaction behavior at the solid-liquid interface. Recently, the observed temperature dependence of the Ca isotope fractionation was explained quantitatively by the temperature control on precipitation rates of calcium carbonates in an experimental setting (Lemarchand et al., 2004). We show that this mechanism can in principle also be applied to CaCO₃ precipitation in natural environments in normal marine settings. Following this model, Ca isotope fractionation in marine Ca carbonates is primarily controlled by precipitation rates. On the other hand the larger Ca isotope fractionation of aragonite compared to calcite can not be explained by different precipitation rates. The rate control model of Ca isotope fractionation predicts a strong dependence of the Ca isotopic composition of carbonates on ambient CO₃²⁻ concentration. While this model is in general accordance with our observations in marine carbonates, cultured specimens of the planktic foraminifer Orbulina universa show no dependence of Ca-isotope fractionation on the ambient CO₃²⁻ concentration. The latter observation implies that the carbonate chemistry in the calcifying vesicles of the foraminifer is independent from the ambient carbonate ion concentration of the surrounding water.     

Effect of pH on boron coprecipitation by calcite: further evidence for nonequilibrium partitioning of trace elements

The influence of pH and concentration on boron coprecipitation by calcite were evaluated under near-equilibrium conditions at 25°C. Calcite was precipitated by adding a metastable polymorph (vaterite or aragonite) to a solution of known boron concentration. This method maintains a nearly constant solution composition during the slow conversion of the metastable polymorph to calcite.Boron uptake in calcite was found to be strongly pH-dependent, increasing two orders of magnitude from pH 8.5 to pH 10.5. Boron incorporation into calcites precipitated from vaterite-saturated solutions was five times greater than in calcites precipitated from aragonite-saturated solutions. Ostensibly, these results suggest that the calcite precipitation rates were not low enough to attain equilibrium partitioning of boron into calcite. However, scanning electron micrograph analyses showed that the prevalent crystal forms of calcite generated from aragonite and those generated from vaterite were distinctly different. The different quantities of boron incorporated into these calcites may reflect different crystal growth mechanisms, consistent with face-dependent, nonequilibrium partitioning of trace elements in calcite.At a constant pH of 9.0, boron uptake increased from less than 15 to over 290 mg/kg CaCO₃ as the solution boron concentration was increased from 5 to 100 mg/kg. Our results agree with those of other investigators, despite differences in solution composition, and calcite precipitation techniques used. The agreement between the studies may be because the crystal growth morphology of the calcite was rhombohedral in both cases.     

Identification and composition of secondary meniscus calcite in fossil coral and the effect on predicted sea surface temperature

This study uses electron backscatter diffraction (EBSD) and atomic force microscopy (AFM) to identify secondary calcite in coral skeletons. Secondary calcite appears to have nucleated on the original aragonite dissepiments, producing horizontal structures that mimic the morphology of the original coral aragonite, forming dissepiment-like meniscus structures. The Sr/Ca and δ¹⁸O of the pristine aragonite and secondary calcite were analysed by secondary ion mass spectrometry (SIMS). The effect of calcite inclusion on the mean geochemistry of the coral carbonate and subsequent sea surface temperature (SST) calculations were determined for both Sr/Ca and δ¹⁸O. Inclusion of as little as 1% secondary calcite within the primary coral aragonite elevates the Sr/Ca-derived SST by 1.2 °C and could markedly offset estimates of past tropical climate. Conversely, inclusion of 10% secondary calcite has little effect on the SST estimated from δ¹⁸O (+ 0.6 °C) indicating that this proxy is relatively robust to even large amounts of calcite. The different extents to which the two proxies would be influenced by inadvertent inclusion of such meniscus calcite demonstrate the importance of a multi-proxy approach.     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^?1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^?1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^–1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^–1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

A thermochemical study of vaterite

Vaterite is shown to be unstable with respect to calcite at 25°C by measurements of the enthalpies of solution in 0·1 N HCl under 0·97 atm CO₂ and the solubilities in water under 0·97 atm CO₂ of the two polymorphs. For a pure, synthetic vaterite ΔH (tr) = ?1036 ±16 cal mol^?1 and ΔG(tr) = ?790 ± 25 cal mol^?1 for the transition to calcite. For other vaterites aged longer during preparation ΔH(tr) is smaller and shows a linear relationship with the X-ray line broadening which extrapolates to ΔH(tr) = ?545 ± 30 cal mo^?1 for zero broadening. The use of X-ray line broadening as a measure of crystal imperfection and stability is discussed for various synthetic and natural vaterites.     

Experimental study of the aragonite to calcite transition in aqueous solution

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.     

'Forbidden zone' subduction of sediments to 150 km depth— the reaction of dolomite to magnesite + aragonite in the UHPM metapelites from western Tianshan, China

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.