A. V. Spivak

Diamond formation in carbonate-silicate-sulfide-carbon melts : Raman-and IR-microspectroscopy

An experimental study on diamond nucleation and growth in a carbon solution in multicomponent carbonate, carbonate-silicate, silicate and sulfide melts was performed using a high-pressure toroidal anvil-with-hole cell with graphite resistive furnace. The boundary conditions of diamond spontaneous crystallization and seeded growth are determined for all the diamond growth media with the use of the PT diagram of diamond crystal growth. A density of diamond nucleation in the studied carbonate, carbonate-silicate, silicate, and sulfide melts with dissolved carbon exceeds (3.0–5.0) × 10 2 nuclei/mm 3 with a maximum around 1.0 × 10 5 nuclei/mm 3 at formation of polycrystalline “diamondite”. Raman spectra of quenched carbonate-carbon, carbonate-silicate-carbon, silicate-carbon and sulfide-carbon melts contain bands relating to the region of C-C stretching modes in diamond and graphite microphases. FTIR spectra show that nitrogen defects in the carbonate-synthetic diamond are characterized with the mixed Ib-IaA type and reveal a high nitrogen concentration (up to 850 ppm).

Melting and decomposition of MgCO3 at pressures up to 84 GPa

AbstractnMagnesium carbonate MgCO3 (magnesite) was experimentally studied at pressures of 12–84xa0GPa and temperatures between 1,600 and 3,300xa0K. We applied the high-pressure technique using a multianvil press and a diamond anvil cell with laser heating. The phase relations and melting of magnesite were investigated by means of Raman and time-resolved multi-wavelength spectroscopy. Magnesite is found to melt congruently within the entire studied pressure range at temperatures of 2,100–2,650xa0K. At temperatures above 2,700xa0K, we observed decomposition of magnesite with formation of MgO and a carbon phase (diamond). Our results demonstrate that at high pressures, the magnesium carbonate melt can exist at a wide range of thermodynamic conditions.n

Fundamentals of the mantle carbonatite concept of diamond genesis

In the mantle carbonatite concept of diamond genesis, the data of a physicochemical experiment and analytical mineralogy of inclusions in diamond conform well and solutions to the following genetic problems are generalized: (1) we substantiate that upper mantle diamond-forming melts have peridotite/eclogite–carbonatite–carbon compositions, melts of the transition zone have (wadsleyite ↔ ringwoodite)–majorite–stishovite–carbonatite–carbon compositions, and lower mantle melts have periclase/wüstite–bridgmanite–Ca-perovskite–stishovite–carbonatite–carbon compositions; (2) we plot generalized diagrams of diamondforming media illustrating the variable compositions of growth melts of diamonds and paragenetic phases, their genetic relationships with mantle matter, and classification relationships between primary inclusions; (3) we study experimentally equilibrium diagrams of syngenesis of diamonds and primary inclusions characterizing the diamond nucleation and growth conditions and capture of paragenetic and xenogenic minerals; (4) we determine the fractional phase diagrams of syngenesis of diamonds and inclusions illustrating regularities in the ultrabasic–basic evolution and paragenetic transitions in diamond-forming systems of the upper and lower mantle. We obtain evidence for physicochemically similar melt–solution ways of diamond genesis at mantle depths with different mineral compositions.

Raman study of MgCO 3 –FeCO 3 carbonate solid solution at high pressures up to 55 GPa

AbstractnMagnesite, siderite and ferromagnesites Mg1−xFexCO3 (xxa0=xa00.05, 0.09, 0.2, 0.4) were characterized using in situ Raman spectroscopy at high pressures up to 55xa0GPa. For the Mg–Fe-carbonates, the Raman peak positions of six modes (T, L, ν4, ν1, ν3 and 2ν2) in the dependence of iron content in the carbonates at ambient conditions are presented. High-pressure Raman spectroscopy shows that siderite undergoes a spin transition at ~40xa0GPa. The examination of the solid solutions with compositions Mg0.6Fe0.4CO3, Mg0.8Fe0.2CO3, Mg0.91Fe0.09CO3 and Mg0.95Fe0.05CO3 indicates that with increase in the amount of the Fe spin transition pressure increases up to ~45xa0GPa.

Congruent melting of calcium carbonate in a static experiment at 3500 K and 10–22 GPa: Its role in the genesis of ultradeep diamonds

Resulting from static experiments performed to study the phase state of CaCO3, it was found that its melting is congruent at 20–22 GPa and 3500 K. The obtained experiment data show that the field of congruent melting of calcium carbonate is rather broad (form 2300 to 3500–3800 K at 20–22 GPa). However, the potential presence of a high-temperature phase boundary at which CaCO3 is decomposed into CaO and CO2 is not ruled out. The existence of a wide area of congruent melting of calcium carbonate (a common primary inclusion in diamonds of the transition zone and lower mantle of the Earth) allow one to consider deep-seated melts as potential parental media for ultradeep diamonds.

Magmatic evolution of the material of the Earth’s lower mantle: Stishovite paradox and origin of superdeep diamonds (Experiments at 24–26 GPa)

The ultrabasic–basic magmatic evolution of the lower mantle material includes important physicochemical phenomena, such as the stishovite paradox and the genesis of superdeep diamonds. Stishovite SiO2 and periclase–wüstite solid solutions, (MgO · FeO)ss, associate paradoxically in primary inclusions of superdeep lower mantle diamonds. Under the conditions of the Earth’s crust and upper mantle, such oxide assemblages are chemically impossible (forbidden), because the oxides MgO and FeO and SiO2 react to produce intermediate silicate compounds, enstatite and ferrosilite. Experimental and physicochemical investigations of melting phase relations in the MgO–FeO–SiO2–CaSiO3 system at 24 GPa revealed a peritectic mechanism of the stishovite paradox, (Mg, Fe)SiO3 (bridgmanite) + L = SiO2 + (Mg, Fe)O during the ultrabasic–basic magmatic evolution of the primitive oxide–silicate lower mantle material. Experiments at 26 GPa with oxide–silicate–carbonate–carbon melts, parental for diamonds and primary inclusions in them, demonstrated the equilibrium formation of superdeep diamonds in association with ultrabasic, (Mg, Fe)SiO3 (bridgmanite) + (MgO · FeO)ss (ferropericlase), and basic minerals, (FeO · MgO)ss (magnesiowüstite) + SiO2 (stishovite). This leads to the conclusion that a peritectic mechanism, similar to that responsible for the stishovite paradox in the pristine lower mantle material, operates also in the parental media of superdeep diamonds. Thus, this mechanism promotes both the ultrabasic–basic evolution of primitive oxide–silicate magmas in the lower mantle and oxide–silicate–carbonate melts parental for superdeep diamonds and their paradoxical primary inclusions.

Melting relations of multicomponent carbonate MgCO3–FeCO3–CaCO3–Na2CO3 system at 12–26 GPa: application to deeper mantle diamond formation

AbstractnCarbonatic components of parental melts of the deeper mantle diamonds are inferred from their primary inclusions of (Mg, Fe, Ca, Na)-carbonate minerals trapped at PT conditions of the Earth’s transition zone and lower mantle. PT phase diagrams of MgCO3–FeCO3–CaCO3–Na2CO3 system and its ternary MgCO3–FeCO3–Na2CO3 boundary join were studied at pressures between 12 and 24xa0GPa and high temperatures. Experimental data point to eutectic solidus phase relations and indicate liquidus boundaries for completely miscible (Mg, Fe, Ca, Na)- and (Mg, Fe, Ca)-carbonate melts. PT fields for partial carbonate melts associated with (Mg, Fe)-, (Ca, Fe, Na)-, and (Na2Ca, Na2Fe)-carbonate solid solution phases are determined. Effective nucleation and mass crystallization of deeper mantle diamonds are realized in multicomponent (Mg, Fe, Ca, Na)-carbonatite–carbon melts at 18 and 26xa0GPa. The multicomponent carbonate systems were melted at temperatures that are lower than the geothermal ones. This gives an evidence for generation of diamond-parental carbonatite melts and formation of diamonds at the PT conditions of transition zone and lower mantle.n

The system MgCO3–FeCO3–CaCO3–Na2CO3 at 12–23 GPa: Phase relations and significance for the genesis of ultradeep diamonds

Physical–chemical experimental studies at 12–23 GPa of phase relationships within four-members carbonate system MgCO3–FeCO3–CaCO3–Na2CO3 and its marginal system MgCO3–FeCO3–Na2CO3 were carried out. The systems are quite representative for a set of carbonate phases from inclusions in diamonds within transitional zone and lower mantle. PT-phase diagrams of multicomponent carbonate systems are suggested. PT parameters of boundaries of their eutectic melting (solidus), complete melting (liquids) are established. These boundaries define area of partial melting. Carbonate melts are stable, completely mixable, and effective solvents of elemental carbon thus defining the possibility of ultra-deep diamonds generation.

On origin and evolution of diamond-forming lower-mantle systems: physicochemical studies in experiments at 24 and 26 GPa

The MgO – FeO – SiO2 – CaO system is representative for the dominant lower-mantle ultramafic assemblage ferropericlase (MgOFeO)ss + bridgmanite (Mg,Fe)SiO3 + Ca-perovskite CaSiO3. Melting relations of the system were studied over its polythermal section (MgO)70(FeO)30 – (SiO2)70(FeO)30 at 24 GPa. A peritectic reaction of bridgmanite with melt was revealed to form the mafic assemblage stishovite SiO2 + periclase-wustite solid solution phases (MgOFeO)ss (effect of stishovite paradox). Experimental phase relations demonstrate the possibility of ultramafic-mafic fractional evolution of the lower-mantle magma and in situ formation of stishovite. Moreover, origin of ultradeep diamonds and associated phases in melts of the MgO – FeO – SiO2 – CaO – (Mg-Fe-Na-K-carbonate) – carbon system have been examined at 26 GPa. A key role of the peritectic reaction of bridgmanite in genesis of mafic inclusions in lower-mantle diamonds is verified.

The stishovite paradox in the evolution of lower mantle magmas and diamond-forming melts (experiment at 24 and 26 GPa)

Experimental studies of phase relations in the oxide–silicate system MgO–FeO–SiO2 at 24 GPa show that the peritectic reaction of bridgmanite controls the formation of stishovite as a primary in situ mineral of the lower mantle and as an effect of the stishovite paradox. The stishovite paradox is registered in the diamond-forming system MgO–FeO–SiO2–(Mg–Fe–Ca–Na carbonate)–carbon in experiments at 26 GPa as well. The physicochemical mechanisms of the ultrabasic–basic evolution of deep magmas and diamondforming media, as well as their role in the origin of the lower mantle minerals and genesis of ultradeep diamonds, are studied.