Igor S. Sharygin

The system K2CO3-MgCO3 at 6 GPa and 900–1450 °C

Abstract Phase relations in the K2CO3-MgCO3 system have been studied in high-pressure high-temperature (HPHT) multi-anvil experiments using graphite capsules at 6.0 ± 0.5 GPa pressures and 900-1450 °C temperatures. Subsolidus assemblies comprise the fields K2CO3+K2Mg(CO3)2 and K2Mg(CO3)2+MgCO3 with the transition boundary near 50 mol% MgCO3 in the system. The K2CO3-K2Mg(CO3)2 eutectic is established at 1200 °C and 25 mol% MgCO3. Melting of K2CO3 occurs between 1400 and 1450 °C. We propose that K2Mg(CO3)2 disappears between 1200 and 1300 °C via congruent melting. Magnesite is observed as a subliquidus phase to temperatures in excess of 1300 °C. At 6 GPa, melting of the K2Mg(CO3)2+MgCO3 assemblage can be initiated either by heating to 1300 °C under “dry” conditions or by adding a certain amount of water at 900-1000 °C. Thus, the K2Mg(CO3)2 could control the solidus temperature of the carbonated mantle under “dry” conditions and cause formation of the K- and Mg-rich carbonatite melts similar to those found as microinclusions in “fibrous” diamonds. The K2Mg(CO3)2 compound was studied using in situ X‑ray coupled with a DIA-type multi-anvil apparatus. At 6.5 GPa and 1000 °C, the structure of K2Mg(CO3)2 was found to be orthorhombic with lattice parameters a = 8.8898(7), b = 7.8673(7), and c = 5.0528(5), V = 353.39(4). No structure change was observed during pressure decrease down to 1 GPa. However, recovered K2Mg(CO3)2 exhibited a trigonal R3̅m structure previously established at ambient conditions.

Melting and subsolidus phase relations in the system Na2CO3-MgCO3±H2O at 6 GPa and the stability of Na2Mg(CO3)2 in the upper mantle

Abstract Phase relations in the Na2CO3-MgCO3 system have been studied in high-pressure high-temperature (HPHT) multi-anvil experiments using graphite capsules at 6.0 ± 0.5 GPa pressures and 900-1400 °C temperatures. Sub-solidus assemblages are represented by Na2CO3+Na2Mg(CO3)2 and Na2Mg(CO3)2+MgCO3, with the transition boundary near 50 mol% MgCO3 in the system. The Na2CO3-Na2Mg(CO3)2 eutectic is established at 1200 °C and 29 mol% MgCO3. Melting of Na2CO3 occurs between 1350 and 1400 °C. We propose that Na2Mg(CO3)2 disappears between 1200 and 1250 °C via congruent melting. Magnesite remains as a liquidus phase above 1300 °C. Measurable amounts of Mg in Na2CO3 suggest an existence of MgCO3 solid-solutions in Na2CO3 at given experimental conditions. The maximum MgCO3solubility in Na-carbonate of about 9 mol% was established at 1100 and 1200 °C. The Na2CO3 and Na2Mg(CO3)2 compounds have been studied using in situ X‑ray coupled with a DIA-type multi-anvil apparatus. The studies showed that eitelite is a stable polymorph of Na2Mg(CO3)2 at least up to 6.6 GPa and 1000 °C. In contrast, natrite, γ-Na2CO3, is not stable at high pressure and is replaced by β-Na2CO3. The latter was found to be stable at pressures up to 11.7 GPa at 27 °C and up to 15.2 GPa at 1200 °C and temperatures at least up to 800 °C at 2.5 GPa and up to 1000 °C at 6.4 GPa. The X‑ray and Raman study of recovered samples showed that, under ambient conditions, β-Na2CO3 transforms back to γ-Na2CO3. Eitelite [Na2Mg(CO3)2] would be an important mineral controlling insipient melting in subducting slab and upwelling mantle. At 6 GPa, melting of the Na2Mg(CO3)2+MgCO3 assemblage can be initiated, either by heating to 1300 °C under “dry” conditions or at 900-1100 °C under hydrous conditions. Thus, the Na2Mg(CO3)2 could control the solidus temperature of the carbonated mantle under “dry” conditions and cause formation of the Na- and Mg-rich carbonatite melts similar to those found as inclusions in olivines from kimberlites and the deepest known mantle rock samples-sheared peridotite xenoliths (190-230 km depth).

Thermal equation of state and thermodynamic properties of molybdenum at high pressures

A comprehensive P-V-T dataset for bcc-Mo was obtained at pressures up to 31 GPa and temperatures from 300 to 1673 K using MgO and Au pressure calibrants. The thermodynamic analysis of these data was performed using high-temperature Birch-Murnaghan (HTBM) equations of state (EOS), Mie-Gruneisen-Debye (MGD) relation combined with the room-temperature Vinet EOS, and newly proposed Kunc-Einstein (KE) approach. The analysis of room-temperature compression data with the Vinet EOS yields V0 = 31.14 ± 0.02 A3, KT = 260 ± 1 GPa, and KT′ = 4.21 ± 0.05. The derived thermoelastic parameters for the HTBM include (∂KT/∂T)P = −0.019 ± 0.001 GPa/K and thermal expansion α = a0 + a1T with a0 = 1.55 ( ± 0.05) × 10−5 K−1 and a1 = 0.68 ( ± 0.07) × 10−8 K−2. Fitting to the MGD relation yields γ0 = 2.03 ± 0.02 and q = 0.24 ± 0.02 with the Debye temperature (θ0) fixed at 455-470 K. Two models are proposed for the KE EOS. The model 1 (Mo-1) is the best fit to our P-V-T data, whereas the second model (Mo-2) is derived by including the shock compression and other experimental measurements. Nevertheless, both models provide similar thermoelastic parameters. Parameters used on Mo-1 include two Einstein temperatures ΘE10 = 366 K and ΘE20 = 208 K; Gruneisen parameter at ambient condition γ0 = 1.64 and infinite compression γ∞ = 0.358 with β  = 0.323; and additional fitting parameters m = 0.195, e0 = 0.9 × 10−6 K−1, and g = 5.6. Fixed parameters include k = 2 in Kunc EOS, mE1 = mE2 = 1.5 in expression for Einstein temperature, and a0 = 0 (an intrinsic anharmonicity parameter). These parameters are the best representation of the experimental data for Mo and can be used for variety of thermodynamic calculations for Mo and Mo-containing systems including phase diagrams, chemical reactions, and electronic structure.A comprehensive P-V-T dataset for bcc-Mo was obtained at pressures up to 31 GPa and temperatures from 300 to 1673 K using MgO and Au pressure calibrants. The thermodynamic analysis of these data was performed using high-temperature Birch-Murnaghan (HTBM) equations of state (EOS), Mie-Gruneisen-Debye (MGD) relation combined with the room-temperature Vinet EOS, and newly proposed Kunc-Einstein (KE) approach. The analysis of room-temperature compression data with the Vinet EOS yields V0 = 31.14 ± 0.02 A3, KT = 260 ± 1 GPa, and KT′ = 4.21 ± 0.05. The derived thermoelastic parameters for the HTBM include (∂KT/∂T)P = −0.019 ± 0.001 GPa/K and thermal expansion α = a0 + a1T with a0 = 1.55 ( ± 0.05) × 10−5 K−1 and a1 = 0.68 ( ± 0.07) × 10−8 K−2. Fitting to the MGD relation yields γ0 = 2.03 ± 0.02 and q = 0.24 ± 0.02 with the Debye temperature (θ0) fixed at 455-470 K. Two models are proposed for the KE EOS. The model 1 (Mo-1) is the best fit to our P-V-T data, whereas the second model (Mo-2) is derived by including...

Melting of kimberlite of the Udachnaya-East pipe: Experimental study at 3–6.5 GPa and 900–1500°C

200 Kimberlites are the products of crystallization of the deepest magmas generated in the Earth’s mantle (below 150 km) and are the main sources of natural diamonds. In spite of significant progress in under� standing kimberlite petrogenesis, many problems, such as reconstruction of the compositions of primary kimberlite melts and their evolution during intrusion, are still debatable. The main problem is that the com� position of kimberlites does not correspond to the composition of parental melts. First, kimberlites are contaminated by a significant portion of xenogenic material represented by xenoliths and their fragments (xenocrysts). Second, most kimberlites worldwide underwent postmagmatic alterations to various

First finding of burkeite in melt inclusions in olivine from sheared lherzolite xenoliths.

For the first time burkeite was observed as a daughter phase in the melt inclusions in olivine by Raman spectroscopy. The olivine comes from sheared lherzolite xenoliths from the Udachnaya-East kimberlite pipe (Yakutia, Russia). This anhydrous sulfate-carbonate mineral (Na(6)(CO(3))(SO(4))(2)) is generally considered to be a characteristic mineral in saline soils or in continental lacustrine evaporite deposits. Recently, however, this mineral was identified in hydrothermal fluids. Our observations indicate that burkeite can also be formed from a mantle-derived melt.

Eitelite in sheared peridotite xenoliths from Udachnaya-East kimberlite pipe (Russia) – a new locality and host rock type

For the first time eitelite Na 2 Mg(CO 3 ) 2 was observed as a daughter phase in the melt inclusions in olivine from one of the deepest known mantle rocks sampled by kimberlite magma – sheared peridotite xenoliths (190 – 230 km), taken from the Devonian (~370 Ma) Udachnaya-East kimberlite pipe (Siberian craton, Russia). Eitelite was identified by confocal Raman spectroscopy and confirmed by energy-dispersive X-ray spectroscopy. Raman spectra of eitelite in the melt inclusions are characterized by a very strong band at 1105 cm −1 attributed to CO 3 2− symmetric stretching, and weaker bands at 207–208 and 260–263 cm −1 due to lattice vibration. Our findings of eitelite in the melt inclusions entrapped by olivine of mantle xenoliths indicate that this rare carbonate can crystallise from primitive mantle-derived alkaline carbonatite melt.

Experimental constraints on the role of chloride in the origin and evolution of kimberlitic magma

graphite tube isolated from a capsule with the sample by the MgO insulator was applied as a heater. The sample powder was loaded in a Au-Pd or Pt capsule and after accurate drying welded by arc welding. The inner walls of Ptcapsules were shielded by Re foil for minimization of iron loss. Each cell contained two capsules: one with the composition of model kimberlite (this study) and another with the composition of natural kimberlite. The results of experiments with the natural composi� tion will be presented in the next paper. The tempera� ture in each run was controlled by a W97Re3-W75Re25 thermocouple located in the center of the heater and isolated by the Al2O3 insulator from it. The tempera� ture gradient in the sample measured using a two� pyroxene thermometer did not exceed 50°С at 1500°С and 5 GPa. The pressure in the sample was maintained by the calibration performed at room tem� perature by change in the electric resistance for the transitions Bi I-II (2.55 GPa), Ba I-II (5.5 GPa), and Bi III-IV (7.7 GPa) and corrected for high tempera� tures by phase transitions graphite-diamond, quartz- coesite, and garnet-perovskite in the CaGeO 3 system. The error in pressure measurement was estimated on the level of 0.2 GPa. The composition of phases was determined on a JEOL Superprobe JXA�8800 micro� probe analyzer at Tohoku University.

Phase relationships in the system K2CO3-CaCO3 at 6 GPa and 900-1450 °C

Abstract Phase relations in the system K2CO3-CaCO3 have been studied in the compositional range, X(K2CO3), from 100 to 10 mol%, at 6.0 GPa and 900-1450 °C. At 900-950 °C, the system has three intermediate compounds: K6Ca2(CO3)5, K2Ca(CO3)2, and K2Ca3(CO3)4. The K2Ca(CO3)2 compound decomposes to the K6Ca2(CO3)5 + K2Ca3(CO3)4 assembly above 950 °C. The K6Ca2(CO3)5 and K2Ca3(CO3)4 compounds melt congruently slightly above 1200 and 1300 °C, respectively. The eutectics were established at 64 and 44 mol% near 1200 °C and at 23 mol% near 1300 °C. K2CO3 remains as a liquidus phase at 1300 °C and 75 mol% and melts at 1425 ± 20 °C. Aragonite remains as a liquidus phase at 1300 °C and 20 mol% and at 1400 °C and 10 mol%. CaCO3 solubility in K2CO3 and K2CO3 solubility in aragonite are below the detection limit (<0.5 mol%). Infiltration of subduction-derived K-rich Ca-Mg-Fe-carbonatite into the Fe0-saturated mantle causes the extraction of (Mg,Fe)CO3 components from the melt, which shifts its composition toward K-Ca-carbonatite. According to our data this melt can be stable at the P-T conditions of subcratonic lithosphere with geothermal gradient of 40 mW/m2 corresponding to temperature of 1200 °C at 6 GPa.

The system Na2CO3–CaCO3–MgCO3 at 6 GPa and 900–1250°C and its relation to the partial melting of carbonated mantle

ABSTRACT In order to constrain the Na2CO3–CaCO3–MgCO3 T–X diagram at 6 GPa in addition to the binary and pseudo-binary systems we conducted experiments along the Na2CO3–Ca0.5Mg0.5CO3 join. At 900–1000°C, melting does not occur and isothermal sections are presented by one-, two- and three-phase regions containing Ca-bearing magnesite, aragonite, Na2CO3 (Na2) and Na2(Ca1–0.9Mg0-0.1)3-4(CO3)4-5 (Na2Ca3-4), Na4(Ca1–0.6Mg0–0.4)(CO3)3 (Na4Ca), Na2(Ca0-0.08Mg1–0.92)(CO3)2 (Na2Mg) phases with intermediate compositions. The minimum melting point locates between 1000°C and 1100°C. This point would resemble that of three eutectics: Mgs–Na2Ca3–Na2Mg, Na2Mg–Na2Ca3–Na4Ca or Na2Mg–Na4Ca–Na2, in the compositional interval of [45Na2CO3·55(Ca0.6Mg0.4)CO3]–[60Na2CO3·40Ca0.6Mg0.4CO3]. The liquidus projection has seven primary solidification phase regions for Mgs, Dol, Arg, Na2Ca3, Na4Ca, Na2 and Na2Mg. The results suggest that extraction of Na and Ca from silicate to carbonate components has to decrease minimum melting temperature of carbonated mantle rocks to 1000–1100°C at 6 GPa and yields Na-rich dolomitic melt with a Na# (Na2O/(Na2O + CaO + MgO)) ≥ 28 mol%.

Inclusions of Cr- and Cr–Nb-Rutile in pyropes from the Internatsionalnaya kimberlite pipe, Yakutia

The results of study of rutile inclusions in pyrope from the Internatsionalnaya kimberlite pipe are presented. Rutile is characterized by unusually high contents of impurities (up to 25 wt %). The presence of Cr2O3 (up to 9.75 wt %) and Nb2O5 (up to 15.57 wt %) are most typical. Rutile inclusions often occur in assemblage with Ti-rich oxides: picroilmenite and crichtonite group minerals. The Cr-pyropes with inclusions of rutile, picroilmenite, and crichtonite group minerals were formed in the lithospheric mantle beneath the Mirnyi field during their joint crystallization from melts enriched in Fe, Ti, and other incompatible elements as a result of metasomatic enrichment of the depleted lithospheric mantle.