'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.     

Fate of carbonates within oceanic plates subducted to the lower mantle, and a possible mechanism of diamond formation

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.     

Origin of ultramafic-hosted magnesite on Margarita Island,Venezuela

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.     

Ternary Ca–Fe–Mg carbonates: subsolidus phase relations at 3.5 GPa and a thermodynamic solid solution model including order/disorder

Subduction carries atmospheric and crustal carbon hosted in the altered oceanic crystalline basement and in pelagic sediments back into the mantle. Reactions involving complex carbonate solid solutions(s) lead to the transfer of carbon into the mantle, where it may be stored as graphite/diamond, in fluids or melts, or in carbonates. To constrain the thermodynamics and thus reactions of the ternary Ca–Mg–Fe carbonate solid solution, piston cylinder experiments have been performed in the system CaCO₃–MgCO₃–FeCO₃ at a pressure of 3.5 GPa and temperatures of 900–1,100°C. At 900°C, the system has two miscibility gaps: the solvus dolomite–calcite, which closes at X _MgCO3 ~0.7, and the solvus dolomite–magnesite, which ranges from the Mg to the Fe side of the ternary. With increasing temperature, the two miscibility gaps become narrower until complete solid solutions between CaCO₃–Ca_0.5Mg_0.5CO₃ is reached at 1,100°C and between CaCO₃–FeCO₃ at 1,000°C. The solvi are characterized by strong compositional asymmetry and by an order–disorder mechanism. To deal with these features, a solid solution model based on the van Laar macroscopic formalism has been calculated for ternary carbonates. This thermodynamic solid solution model is able to reproduce the experimentally constrained phase relations in the system CaCO₃–MgCO₃–FeCO₃ in a broad P–T range. To test our model, calculated phase equilibria were compared with experiments performed in carbonated mafic protolithes, demonstrating the reliability of our solid solution model at pressures up to 6 GPa in complex systems.     

Reaction kinetics of dolomite rim growth

Reaction rims of dolomite (CaMg[CO₃]₂) were produced by solid-state reactions at the contacts of oriented calcite (CaCO₃) and magnesite (MgCO₃) single crystals at 400 MPa pressure, 750–850 °C temperature, and 3–146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO₃ interface with length ranging from about 6 to 41 µm. At the same time, a 5–71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO₃. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12–80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the $[11\bar{2}0]$ equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E _a (CaO) = 192 ± 54 kJ/mol and E _a (MgO) = 198 ± 44 kJ/mol, respectively.     

Double carbonate breakdown reactions at high pressures: an experimental study in the system CaO–MgO–FeO–MnO–CO2

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.     

Calciocarbonatite and magnesiocarbonatite rocks and magmas represented in the system CaO-MgO-CO2-H2O at 0.2 GPa

Summary ?The low-pressure eutectic for the coprecipitation of calcite, portlandite, and periclase/brucite (with H₂O-rich vapor) has served as a model for the existence and crystallization of carbonatite magmas. Attempts to determine conditions for the appearance of dolomite at this eutectic have been unsuccessful. We have discovered a second low-temperature eutectic for more magnesian liquids which excludes portlandite and includes dolomite (all results are vapor-saturated). Addition of Ca(OH)₂-Mg(OH)₂ to CaCO₃-MgCO₃ at 0.2 GPa depresses the liquidus to temperatures below the crest of the calcite-dolomite solvus; the vapor-saturated liquidus surface falls steeply, and the field boundary for liquids coexisting with calcite and periclase reaches a peritectic at 880 °C, where a narrow field for liquidus dolomite begins, extending down to the eutectic at 659 °C for the coprecipitation of calcite, dolomite and periclase (brucite should replace periclase at slightly higher pressures). The calcite liquidus is very large. The field boundary for coexistence of calcite and dolomite extends approximately in the direction from CaMg(CO₃)₂ towards Mg(OH)₂. The results illustrate conditions for the formation of mineral-specific cumulates from variable magma compositions. Hydrous (or sodic) carbonate-rich liquids with compositions from CaCO₃ to CaMg(CO₃)₂ will precipitate calcite-carbonatites first, followed by calcite-dolomite-carbonatites, with the prospect of precipitating dolomite-carbonatite alone through a limited temperature interval, and with periclase joining the assemblage in the closing stages. Periclase in the Fe-free system may represent the ubiquitous occurrence of magnetite in natural carbonatites. The restricted range for the precipitation of dolomite-carbonatites adds credibility to the evidence for primary magnesiocarbonatite (near-dolomite composition) magmas. Magnesiocarbonatite magmas can precipitate much calcite-carbonatite rock.

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Zusammenfassung ?Calciokarbonatitische und magnesiokarbonatitische Gesteine und Magmen im System CaO-MgO-CO ₂ -H ₂ O bei 0.2 GPa Das Niedrigdruck-Eutektikum der gemeinsamen Ausscheidung von Calcit, Portlandit und Periklas/Brucit (mit H₂O-reicher Fluidphase) diente als Modell um die Existenz und Kristallisation karbonatitischer Magmen zu erkl?ren. Versuche die Bedingungen des Auftretens von Dolomit an diesem Eutektikum zu bestimmen blieben bisher ergebnislos. Wir entdeckten ein zweites Niedrigtemperatur-Eutektikum für magnesiumreichere Schmelzen, das Portlandit ausschlie?t, aber Dolomit inkludiert (alle Ergebnisse bei Fluids?ttigung). Die Zugabe von Ca(OH)₂-Mg(OH)₂ zu CaCO₃-MgCO₃ bei 0.2 GPa senkt den Liquidus auf Temperaturen unter die Solvus-Schwelle von Calcit-Dolomit. Die fluidges?ttigte Liquidusfl?che verl?uft steil und die Grenzfl?che von Schmelze, die mit Calcit und Periklas koexistiert erreicht ein Peritektikum bei 880 °C. Dort ?ffnet sich ein schmales Feld für Liquidus-Dolomit, das bis zum Eutektikum bei 659 °C reicht, an dem Calcit, Dolomit und Periklas (Brucit sollte Periklas bei geringfügig h?heren Drucken ersetzen) gemeinsam ausgeschieden werden. Der Calcit- Liquidus ist sehr gro?. Die Linie an der Calcit und Dolomit koexistieren erstreckt sich ungef?hr von CaMg(CO₃)₂ zu Mg(OH)₂. Die Ergebnisse zeigen die Bildungsbedingungen für die Bildung mineralspezifischer Kumulate aus unterschiedlichen Magmenzusammensetzungen. Aus w?ssrigen (oder Na-reichen) karbonatreichen Schmelzen mit Zusammensetzungen zwischen CaCO₃ und CaMg(CO₃)₂ werden sich zuerst Calcitkarbonatite und dann Calcit-Dolomitkarbonatite ausscheiden, mit der M?glichkeit Dolomitkarbonatite über ein sehr eingeschr?nktes Temperaturintervall zu bilden und mit Periklas, der zu dieser Vergesellschaftung im Endstadium hinzukommt. Periklas im Fe-freien System k?nnte das weitverbreitete Analog zu Magnetit in natürlichen Karbonatiten sein. Der enge Bereich für die Ausscheidung von Dolomitkarbonatiten untermauert die Existenz prim?rer magnesiokarbonatitischer Magmen (nahe der Zusammensetzung von Dolomit). Magnesiokarbonatitische Magmen k?nnen daher entsprechende Mengen an calcitkarbonatitischen Gesteinen ausscheiden.

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Received July 20, 1998;/revised version accepted August 18, 1999     

Production of mud‐grade carbonates by marine fish: Crystalline products and their sedimentary significance

Recent work has established that marine teleost (bony) fish represent a prolific source of mud grade, mainly high‐Mg calcite, carbonate sediment by means of primary precipitation within the intestine. Previously documented crystalline products display a diverse array of morphologies, many unique in shallow tropical marine settings, and have a wide range of magnesium contents (from 18 to 39 mol% MgCO₃). This study utilizes scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction and liquid ion chromatography to provide a more extensive and expansive morphological, mineralogical and chemical characterization of the crystalline forms produced by a wider range of piscine functional groups (covering 21 different fish species common in The Bahamas). Several crystal morphologies not previously described in fish‐derived carbonates are documented, and chemical composition is found to be more variable than previously reported: in addition to high‐Mg calcites with >18 mol% MgCO₃, high‐Mg calcites with lower MgCO₃ contents and low‐Mg calcites are identified. From the expanded species range, MgCO₃ content in fish‐derived carbonates ranges from ca 0˙5 to > 40 mol%, and particle length is in the range 0˙1 to >50 μm (typically <2 μm for individual crystals). Amorphous Mg‐carbonates (with detectable CaCO₃ of <2 mol%) are also found to varying extent in the precipitates of many species. Dominant mineralogy and MgCO₃ content varies with producing species and crystal morphology (itself a species‐dependent variable). Given the very small grain size and often high MgCO₃ contents of these carbonates, interesting questions arise about their preservation potential. Thus, the extent to which carbonates produced by different species may follow different post‐excretion preservation pathways is considered.     

Subsolidus and melting relations for the join CaCO3-MgCO3 at 10 kbar

Mixtures of pure dry CaCO₃ and MgCO₃ were reacted at 10 kbar in a piston-cylinder apparatus. Solidus and liquidus boundaries were delineated by interpretation of quenched textures. X-ray determined compositions of quenched carbonates are not a reliable guide to the phase relations. The binary melting loop for CaCO₃-MgCO₃ extends from CaCO₃ at 1460°C through a liquidus minimum near 30 wt% MgCO₃ and 1075°C, and it is terminated at the incongruent melting reaction for dolomite solid solution at 1125° C (liquid with 32 wt% MgCO₃) Magnesite solid solution dissociates at 1090°C to produce dolomite + periclase + CO₂, truncating the dolomite-magnesite solvus. The 10 kb liquidus minimum at 1075°C and 30 wt% MgCO₃ occurs at lower temperature and higher $\text{Ca}\text{Mg}$ ratio than the 27 kbar liquidus minimum at 1290°C and 38 wt% MgCO₃. This relationship suggests that the first liquid produced by melting of a carbonate-bearing peridotite has increasing $\text{Mg}\text{Ca}$ ratio with increasing pressure. These phase relations provide part of the framework required to trace paths of crystallization of kimberlite and carbonatite magmas.     

Thermochemistry of carbonate-pyroxene equilibria

The enthalpies of drop solution of calcite, magnesite, dolomite, wollastonite and diopside have been measured in a lead borate solvent at 977 K in a Calvettype microcalorimeter. The carbonate calorimetry was done under flowing gas atmosphere. Both natural and synthetic samples were used. From these calorimetric data, the enthalpies of several reactions of carbonate with quartz were calculated. The enthalpies of these reactions (kJ/mol) at 298 K are: calcite+quartzwollastonite+CO₂, 92.3±1.0; magnesite+quartzenstatite+CO₂, 82.9±2.8; dolomite+quartzdiopside+CO₂, 163.0±1.9. These values generally are in agreement with those calculated from Robie et al., Helgeson et al., Berman and Holland and Powell. The enthalpy of dolomite-quartz reaction overlaps marginally with those from Berman and Holland and Powell. The enthalpy of formation of dolomite from magnesite and calcite (-11.1±2.5 kJ/mol) was also derived from the measured enthalpies, and this value is consistent with that from acid solution calorimetric measurements as shown by Navrotsky and Capobianco, but different from values in the earlier literature. These results support the premise that drop-solution of carbonates into molten lead borate results in a well-defined final state consisting of dissolved oxide and evolved CO₂. This was also confirmed by weight change experiments. Thus, oxide melt calorimetry is applicable to carbonates.     

The system CaO-MgO-SiO2-CO2 at 1 GPa, metasomatic wehrlites, and primary carbonatite magmas

New experimental data in CaO-MgO-SiO₂-CO₂ at 1 GPa define the vapor-saturated silicate-carbonate liquidus field boundary involving primary minerals calcite, forsterite and diopside. The eutectic reaction for melting of model calcite (1% MC)-wehrlite at 1 GPa is at 1100 °C, with liquid composition (by weight) 72% CaCO₃ (CC), 9% MgCO₃ (MC), and 18% CaMgSi₂O₆ (Di). These data combined with previous results permit construction of the isotherm-contoured vapor-saturated liquidus surface for the calcite/dolomite field, and part of the adjacent forsterite and diopside fields. Nearly pure calcite crystals in mantle xenoliths cannot represent equilibrium liquids. We recently determined the complete vapor-saturated liquidus surface between carbonates and model peridotites at 2.7 GPa; the peritectic reaction for dolomite (25% MC)-wehrlite at 2.7 GPa occurs at 1300 °C, with liquid composition 60% CC, 29% MC, and 11% Di. The liquidus field boundaries on these two surfaces provide the road-map for interpretation of magmatic processes in various peridotite-CO₂ systems at depths between the Moho and about 100 km. Relationships among kimberlites, melilitites, carbonatites and the liquidus phase boundaries are discussed. Experimental data for carbonatite liquid protected by metasomatic wehrlite have been reported. The liquid trends directly from dolomitic towards CaCO₃ with decreasing pressure. The 1.5 GPa liquid contains 87% CC and 4% Di, much lower in silicate components than our phase boundary. However, the liquids contain approximately the same CaCO₃ (90 ± 1 wt%) in terms of only carbonate components. For CO₂-bearing mantle, all magmas at depth must pass through initial dolomitic compositions. Rising dolomitic carbonatite melt will vesiculate and may erupt as primary magmas through cracks from about ˜70 km. If it percolates through metasomatic wehrlite from 70 km toward the Moho at 35–40 km, primary calcic siliceous carbonatite magma can be generated with silicate content at least 11–18% (70–40 km) on the silicate-carbonate boundary. Received: 22 June 1998 / Accepted: 7 July 1999     

First-principles-based calculations of the CaCO<Subscript>3</Subscript>–MgCO<Subscript>3</Subscript> and CdCO<Subscript>3</Subscript>–MgCO<Subscript>3</Subscript> subsolidus phase diagrams

 Planewave pseudopotential calculations of supercell total energies were used as bases for first-principles calculations of the CaCO₃–MgCO₃ and CdCO₃–MgCO₃ phase diagrams. Calculated phase diagrams are in qualitative to semiquantitative agreement with experiment. Two unobserved phases, Cd₃Mg (CO₃)₄ and CdMg₃(CO₃)₄, are predicted. No new phases are predicted in the CaCO₃–MgCO₃ system, but a low-lying metastable Ca₃Mg(CO₃)₄ state, analogous to the Cd₃Mg(CO₃)₄ phase is predicted. All of the predicted lowest-lying metastable states, except for huntite CaMg₃(CO₃)₄, have dolomite-related structures, i.e. they are layer structures in which A _m B _n cation layers lie perpendicular to the rhombohedral [111] vector. Received: 6 May 2002 / Accepted: 23 October 2002 Acknowledgements This work was partially supported by NSF contract DMR-0080766 and NIST.     

The partitioning of Fe and Mg between olivine and carbonate and the stability of carbonate under mantle conditions

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.     

Decarbonation reaction of magnesite in subducting slabs at the lower mantle

High-pressure and temperature experiments (28–62 GPa, and 1,490–2,000 K, corresponding to approximately 770–1,500 km depth in the mantle) have been conducted on a MgCO₃ + SiO₂ mixture using a laser-heated diamond anvil cell combined with analytical transmission electron microscope observation of the product phases to constrain the fate of carbonates carried on the subducting basalt into the lower mantle. At these conditions, the decarbonation reaction MgCO₃ (magnesite) + SiO₂ (stishovite) → MgSiO₃ (perovskite) + CO₂ (solid) has been recognized. This indicates that above reaction takes place as a candidate for decarbonation of the carbonated subducting mid ocean ridge basalts in the Earth’s lower mantle.     

Origin of the Rubian carbonate-hosted magnesite deposit, Galicia, NW Spain: mineralogical, REE, fluid inclusion and isotope evidence

The Rubian magnesite deposit (West Asturian—Leonese Zone, Iberian Variscan belt) is hosted by a 100-m-thick folded and metamorphosed Lower Cambrian carbonate/siliciclastic metasedimentary sequence—the Cándana Limestone Formation. It comprises upper (20-m thickness) and lower (17-m thickness) lens-shaped ore bodies separated by 55 m of slates and micaceous schists. The main (lower) magnesite ore body comprises a package of magnesite beds with dolomite-rich intercalations, sandwiched between slates and micaceous schists. In the upper ore body, the magnesite beds are thinner (centimetre scale mainly) and occur between slate beds. Mafic dolerite dykes intrude the mineralisation. The mineralisation passes eastwards into sequence of bedded dolostone (Buxan) and laminated to banded calcitic marble (Mao). These show significant Variscan extensional shearing or fold-related deformation, whereas neither Rubian dolomite nor magnesite show evidence of tectonic disturbance. This suggests that the dolomitisation and magnesite formation postdate the main Variscan deformation. In addition, the morphology of magnesite crystals and primary fluid inclusions indicate that magnesite is a neoformed hydrothermal mineral. Magnesite contains irregularly distributed dolomite inclusions (<50 μm) and these are interpreted as relics of a metasomatically replaced dolostone precursor. The total rare earth element (REE) contents of magnesite are very similar to those of Buxan dolostone but are depleted in light rare earth elements (LREE); heavy rare earth element concentrations are comparable. However, magnesite REE chondrite normalised profiles lack any characteristic anomaly indicative of marine environment. Compared with Mao calcite, magnesite is distinct in terms of both REE concentrations and patterns. Fluid inclusion studies show that the mineralising fluids were MgCl₂–NaCl–CaCl₂–H₂O aqueous brines exhibiting highly variable salinities (3.3 to 29.5 wt.% salts). This may be the result of a combination of fluid mixing, migration of pulses of variable-salinity brines and/or local dissolution and replacement processes of the host dolostone. Fluid inclusion data and comparison with other N Iberian dolostone-hosted metasomatic deposits suggest that Rubian magnesite probably formed at temperatures between 160 and 200°C. This corresponds, at hydrostatic pressure (500 bar), to a depth of formation of ~~5 km. Mineralisation-related Rubian dolomite yields δ ¹⁸O values (δ ¹⁸O: 12.0–15.4‰, mean: 14.4±1.1‰) depleted by around 5‰ compared with barren Buxan dolomite (δ ¹⁸O: 17.1–20.2‰, mean: 19.4±1.0‰). This was interpreted to reflect an influx of ¹⁸O-depleted waters accompanied by a temperature increase in a fluid-dominated system. Overlapping calculated δ ¹⁸O_fluid values (~+5‰ at 200°C) for fluids in equilibrium with Rubian dolomite and magnesite show that they were formed by the same hydrothermal system at different temperatures. In terms of δ ¹³C values, Rubian dolomite (δ ¹³C: −1.4 to 1.9‰, mean: 0.4±1.3‰) and magnesite (δ ¹³C: −2.3 to 2.4‰, mean: 0.60±1.0‰) generally exhibit more negative δ ¹³C values compared with Buxan dolomite (δ ¹³C: −0.2 to 1.9‰, mean: 0.8±0.6‰) and Mao calcite (δ ¹³C: −0.3 to 1.5‰, mean: 0.6±0.6‰), indicating progressive modification to lower δ ¹³C values through interaction with hydrothermal fluids. ⁸⁷Sr/⁸⁶Sr ratios, calculated at 290 Ma, vary from 0.70849 to 0.70976 for the Mao calcite and from 0.70538 to 0.70880 for the Buxan dolostone. The ⁸⁷Sr/⁸⁶Sr ratios in Rubian magnesite are more radiogenic and range from 0.71123 to 0.71494. The combined δ ¹⁸O–δ ¹³C and ⁸⁷Sr/⁸⁶Sr data indicate that the magnesite-related fluids were modified basinal brines that have reacted and equilibrated with intercalated siliciclastic rocks. Magnesite formation is genetically linked to regional hydrothermal dolomitisation associated with lithospheric delamination, late-Variscan high heat flow and extensional tectonics in the NW Iberian Belt. A comparison with genetic models for the Puebla de Lillo talc deposits suggests that the formation of hydrothermal replacive magnesite at Rubian resulted from a metasomatic column with magnesite forming at higher fluid/rock ratios than dolomite. In this study, magnesite generation took place via the local reaction of hydrothermal dolostone with the same hydrothermal fluids in very high permeability zones at high fluid/rock ratios (e.g. faults). It was also possibly aided by additional heat from intrusive dykes or sub-cropping igneous bodies. This would locally raise isotherms enabling a transition from the dolomite stability field to that of magnesite.Editorial handling: F. Tornos     

Melting relationships in the systems CaOCO2 and MgOCO2 to 33 kilobars

The melting temperatures of calcite and magnesite in the presence of excess CO₂ have been measured using Ag₂C₂O₄ in sealed capsules m a piston-cylinder apparatus. At 27 kbar, 11.5 wt % CO₂ dissolves in molten CaCO₂, depressing the freezing temperature from 1610 to 1505°C; and 6.5 wt % CO₂ dissolves in molten MgCO₃, depressing the freezing temperature from 1590 to 1510°C. The eutectic between calcite and lime was located at 1385°C at 27 kbar. These and other new results, combined with previously published data, permit completion of PT diagrams for the systems CaO-CO₂ and MgO-CO₂ from 1 bar to 35 kbar. The dissociation curve for each carbonate terminates at an invariant point where melting begins, at 40 bars and 1230°C for CaO-CO₂ and 23 kbar and 1550°C for MgO-CO₂ The differences between the two systems are explained by the different solubilities of CO₂ in the invariant liquids consequent upon the large pressure difference between the locations of these two invariant points. The results show that the temperatures for the beginning of melting of carbonates in the asthenosphere are lowered by about 100°C in the presence of CO₂.     

Change in carbonate budget and composition during subduction below metal saturation boundary

It is generally accepted that carbonates can be subducted to the mantle depths, where they are reduced with iron metal to produce a diamond. In this work, we found that this is not always the case. The mantle carbonates from inclusions in diamonds show a wide range of cation compositions (Mg, Fe, Ca, Na, and K). Here we studied the reaction kinetics of these carbonates with iron metal at 6–6.5 GPa and 1000–1500 °C. We found that the reduction of carbonate with Fe produces C-bearing species (Fe, Fe-C melt, Fe₃C, Fe₇C₃, C) and wüstite containing Na₂O, CaO, and MgO. The reaction rate constants (k = Δx²/2t) are log-linear relative to 1/T and their temperature dependences are determined to bek_MgCO3 (m²/s) = 4.37 × 10^?3 exp [?251 (kJ/mol)/RT]k_CaMg(CO3)2 (m²/s) = 1.48 × 10^?3 exp [?264 (kJ/mol)/RT]k_CaCO3 (m²/s) = 3.06 × 10^?5 exp [?245 (kJ/mol)/RT] andk_Na2CO3 (m²/s) = 1.88 × 10^?10 exp [?155 (kJ/mol)/RT].According to obtained results at least, 45–70 vol% of carbonates preserve during subduction down to the 660-km discontinuity if no melting occurs. The slab stagnation and warming, subsequent carbonate melting, and infiltration into the mantle saturated with iron metal are accompanied by a reduction of carbonate melt with Fe. The established sequence of reactivity of carbonates: FeCO₃ ≥ MgCO₃ > CaMg(CO₃)₂ > CaCO₃ ? Na₂CO₃, where K₂CO₃ does not react at all with iron metal, implies that during reduction carbonate melt with Fe evolves toward alkali-rich. The above conclusions are consistent with the findings of carbonates in inclusions in diamonds from the lower mantle and high concentrations of alkalis, particularly K, in mantle carbonatite melts entrapped by diamonds from kimberlites and placers worldwide.     

Experimental investigation of the metamorphism of siliceous dolomites III. Equilibrium data for the reaction: 1 Tremolite + 11 dolomite ⇌ 8 forsterite + 13 calcite + 9 CO2 +1H2O for the total pressures of 3,000 and 5,000 bars

The temperature-X _{CO 2}-equilibrium data for the reaction 1 tremolite + 11 dolomite 8 forsterite + 13 calcite + 9 CO₂ +1H₂O have been determined at total pressures (P _{CO 2} + P _H2_O) of 3,000 and 5,000 bars. The results are shown in Figure 2 along with the data for the total pressure of 1,000 bars (Metz, 1967).The MgCO₃ contents of the magnesian-calcites formed during the experiments agree very well with the calcite-dolomite-solvus which can be recalculated from Equation (1) and the activity coefficients for MgCO₃ in magnesiancalcite as given by Gordon and Greenwood (1970).If the T-X _{CO 2}-equilibrium data are calculated from the equilibrium constant as given by Skippen (1974), assuming ideal mixing of CO₂ and H₂O, good agreement is achieved for the total pressure of 1,000 bars (see Figs. 4 and 5). At a total pressure of 3,000 bars, however, the calculated equilibrium temperatures are about 40 ° C below the experimentally determined values (see Fig. 6). This difference increases up to 70 ° C for a total pressure of 5,000 bars (see Fig. 7).From the experimentally determined equilibrium conditions of the assemblage: tremolite + dolomite + forsterite + magnesian calcite (see Fig. 8) the pressure of metamorphism can be estimated if the temperature is determined by the MgCO₃-content of the magnesian-calcite from the calcite-dolomite solvus. However, when using the data of Figure 8, attention has to be drawn to the limiting condition of X _{CO 2}0.2.Simplified reaction equation not considering solid solution in the carbonates     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part I: δ18O Matrix Effects

We document the development of a suite of carbonate mineral reference materials for calibrating SIMS determinations of δ¹⁸O in samples with compositions along the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂]. Under routine operating conditions for the analysis of carbonates for δ¹⁸O with a CAMECA IMS 1280 instrument (at WiscSIMS, University of Wisconsin‐Madison), the magnitude of instrumental bias along the dolomite–ankerite series decreased exponentially by ~ 10‰ with increasing Fe content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mol% Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the sample matrix effect) was calibrated using the Hill equation, which relates bias to the Fe# of dolomite–ankerite [i.e., molar Fe/(Mg+Fe)] for thirteen reference materials (Fe# = 0.004–0.789); for calibrations employing either 10 or 3 μm diameter spot size measurements, this yielded residual values ≤ 0.3–0.4‰ relative to CRM NBS 19 for most reference materials in the suite. Analytical precision was ± 0.3‰ (2s, standard deviations) for 10‐μm spots and ± 0.7‰ (2s) for 3‐μm spots, based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses. Analytical uncertainty for individual sample analyses was approximated by a combination of precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 0.5‰ (2s) for 10‐μm spots and ± 1‰ (2s) for 3‐μm spots.