Yu. A. Litvin

Experimental characterization of diamond crystallization in melts of mantle silicate-carbonate-carbon systems at 7.0–8.5 GPa

Diamond crystallization from carbon solutions in compositionally variable melts of model eclogite with dolomite [CaMg(CO3)2], potassium carbonate (K2CO3), and multicomponent K-Na-Ca-Mg-Fe carbonates was studied at 7.0–8.5 GPa. Concentration barriers for the nucleation of the diamond were determined at a standard pressure of 8.5 GPa for variable proportions of silicate and carbonate components in the growth solutions. They correspond to 35, 65, and 40 wt % of silicate components for systems with dolomite, K2CO3, and carbonatites, respectively. At higher contents of silicates in silicate-carbonate melts, the nucleation of diamond phase ceases, but diamond crystallization on seed crystals continues and is accompanied by the spontaneous crystallization of thermodynamically unstable graphite. In melts of the albite (NaAlSi3O8)-K2CO3-C compositions, the concentration barrier of diamond nucleation at 8.5 GPa is up to 90–92 wt % of the albite component, and diamond growth on seeds was observed in albite-carbon melts. Using mineralogical and experimental data, we developed a model of mantle carbonate-silicate (carbonatite) melts as the main parental media for natural diamonds; it was shown that the composition of the silicate constituent of such parental melts is variable and corresponds to the mantle ultrabasic-basic series. With respect to concentration contributions and dominant role in the genesis of diamond in the Earth’s mantle, major (carbonate and silicate) and minor or admixture components were distinguished. The latter include both soluble in carbonate-silicate melts (oxides, phosphates, chlorides, carbon dioxide, and water) and insoluble components (sulfides, metals, and carbides). Both major and minor components may affect the position of the concentration barriers of diamond nucleation in natural parent media.

Parental media of natural diamonds and primary mineral inclusions in them: Evidence from physicochemical experiment

A generalized diagram was constructed for the compositions of multicomponent heterogeneous parental media for diamonds of kimberlite deposits on the basis of the mantle carbonatite concept of diamond genesis. The boundary compositions on the diagram of the parental medium are defined by the components of minerals of the peridotite and eclogite parageneses, mantle carbonatites, carbon, and the components of volatile compounds of the C-O-H system and accessory phases, both soluble (chlorides, phosphates, and others) and insoluble (sulfides and others) in carbonate-silicate melts. This corresponds to the compositions of minerals, melts, and volatile components from primary inclusions in natural diamonds, as well as experimental estimations of their phase relations. Growth media for most natural diamonds are dominated by completely miscible carbonate-silicate melts with dissolved elemental carbon. The boundary compositions for diamond formation (concentration barriers of diamond nucleation) in the cases of peridotite-carbonate and eclogite-carbonate melts correspond to 30 wt % peridotite and 35 wt % eclogite; i.e., they lie in the carbonatite concentration range. Phase relations were experimentally investigated at 7 GPa for the melting of the multicomponent heterogeneous system eclogite-carbonatite-sulfide-diamond with a composition close to the parental medium under the conditions of the eclogite paragenesis. As a result, “the diagram of syngenesis” was constructed for diamond, as well as paragenetic and xenogenic mineral phases. Curves of diamond solubility in completely miscible carbonate-silicate and sulfide melts and their relationships with the boundaries of the fields of carbonate-silicate and sulfide phases were determined. This allowed us to establish the physicochemical mechanism of natural diamond formation and the P-T conditions of formation of paragenetic silicate and carbonate minerals and coexistence of xenogenic sulfide minerals and melts. Physicochemical conditions of the capture of paragenetic and xenogenic phases by growing diamonds were revealed. Based on the mantle carbonatite concept of diamond genesis and experimental data, a genetic classification of primary inclusions in natural diamond was proposed. The phase diagrams of syngenesis of diamond, paragenetic, and xenogenic phases provide a basis for the analysis of the physicochemical history of diamond formation in carbonatite magma chambers and allow us to approach the formation of such chambers in the mantle material of the Earth.

Solubility of hydrogen and carbon in reduced magmas of the early Earth’s mantle

The solubility of volatile compounds in magmas and the redox state of their mantle source are the main factors that control the transfer of volatile components from the planet’s interior to its surface. In theories of the formation of the Earth, the composition of gases extracted by primary planetary magmas is accounted for by the large-scale melting of the early mantle in the presence of the metallic Fe phase [1, 2]. The fused metallic Fe phase and the melted silicate material experienced gravitational migration that exerted influence upon the formation of the metallic core of the planet. The large-scale melting of the early Earth should have been accompanied by the formation of volatile compounds, whose composition was controlled by the interaction of H and C with silicate and metallic melts, a process that remains largely unknown as of yet.

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.

Physicochemical formation conditions of natural diamond deduced from experimental study of the eclogite-carbonatite-sulfide-diamond system

A diagram of the syngenesis of diamond, silicate, carbonate, and sulfide minerals and melts is compiled based on experimental data on phase relations in the heterogeneous eclogite-carbonate-sulfidediamond system at P = 7 GPa. Evidence is provided that silicate and carbonate minerals are paragenetic, whereas sulfides are xenogenic with respect to diamond. Diamond and paragenetic phases are formed in completely miscible carbonate-silicate growth melts with dissolved elemental carbon. Coherent data of physicochemical experiment and mineralogy of primary inclusions in natural diamonds allows us to prove the mantle-carbonatite theory of diamond origin. The genetic classification of primary inclusions in natural diamonds is based on this theory. The phase diagrams of syngenesis are applicable to interpretation of diamond and syngenetic minerals formation in natural magma sources. They ascertain physicochemical mechanism of natural diamond formation and conditions of entrapment of paragenetic and xenogenic mineral phases by growing diamonds.

Conditions of magmatic crystallization of Na-bearing majoritic garnets in the earth mantle: Evidence from experimental and natural data

Results of experimental study at 7.0–8.5 GPa and 1300–1900°C of the systems pyrope Mg3Al2Si3O12 (Prp)-Na2MgSi5O12 (NaGrt) modeling solid solutions of Na-bearing garnets, Prp-jadeite NaAlSi2O6 (Jd) in a simplified mode demonstrating melting relations of Na-rich eclogite, and Prp-Na2CO3 are presented. Prp-Na2MgSi5O12 join is a pseudobinary that results from the decomposition of NaGrt on to coesite and Na-pyroxene. Synthesized garnets are characterized by Na admixture (>0.32 wt % Na2O) and excess Si (3.05–3.15 f.u.). Maximal Na2O concentrations (1.5 wt % Na2O) are reached on the solidus of the system at 8.5 GPa. Clear correlation between Na and Si was established in synthesized garnets; this provides evidence for heterovalent isomorphism of the Mg + Al → Na + Si type with the appearance of Na2MgSi5O12 component as a mechanism of such garnet formation. The Prp-Jd join is also pseudobinary that results from the formation of two series of solid solutions: (1) garnet (Prp-NaGrt-majorite) and (2) pyroxene (Jd-clinoenstatite-Eskola molecule), and the appearance of kyanite at the solidus of the system, where garnets with the highest Na2O contents (>0.8 wt %) are formed. In spite of quite a wide field of garnet crystallization (20–100 mol % Prp), garnets with significant sodium concentration (>0.3 wt % Na2O) are formed in a Jd-rich part of the system (20–50 mol % Prp). In the Prp-Na2CO3 system at 8.5 GPa garnet crystallizes in a wide range of starting compositions as a liquidus mineral containing up to 0.9 wt % Na2O. Our experiments demonstrate that melt alkalinity, as well as PT-parameters control the crystallization of Na-bearing majoritic garnets. The results obtained provide evidence for the fact that the majority of natural diamonds with inclusions of Na-bearing majoritic garnets containing <0.4 wt % Na2O were formed in alkaline silicate (carbonate-silicate) melts at a pressure of <7 GPa. Only a small portion of garnets with higher sodium concentrations (>1 wt % Na2O) could be formed at a pressure of >8.5 GPa. 1 This article was translated by the authors.

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.

Mineral equilibria of diamond-forming carbonate-silicate systems

Based on experimental and mineralogical data, the model of mantle carbonate-silicate (carbonatite) melts as dominating parental media for natural diamonds was substantiated. It was demonstrated that the compositions of silicate constituents of parental melts were variable and saturated with respect to mantle rocks, namely pyrope peridotite, garnet pyroxenite, and eclogite. Based on concentration contributions and role in diamond genesis, major (carbonate and silicate) and minor (admixture) components were distinguished. The latter components may be both soluble (oxides, phosphates, chlorides, carbon dioxide, and water) and insoluble (sulfides, metals, and carbides) in silicate-carbonate melts. This paper presents the results of a study of diamond crystallization in multicomponent melts of variable composition with carbonate components (K2CO3, CaCO3 · MgCO3, and K-Na-Ca-Mg-Fe carbonatite) and silicate components represented by model peridotite (60 wt % olivine, 16 wt % orthopyroxene, 12 wt % clinopyroxene, and 12 wt % garnet) and eclogite (50 wt % garnet and 50 wt % clinopyroxene). Carbonate-silicate melts behave like completely miscible liquid phases in experiments performed under the P-T conditions of diamond stability. The concentration barriers of diamond nucleation (CBDN) in melts with variable proportions of silicates and carbonates were determined at 8.5 GPa. In the peridotite system with K2CO3, CaCO3 · MgCO3, and carbonatite, they correspond to 30, 25, and 30 wt % silicates, respectively, and in the eclogite system, the CBDN is shifted to 45, 30, and 35 wt % silicates. In the silicate-carbonate melts with higher silicate contents, diamond grows on seeds, which is accompanied by the crystallization of thermodynamically unstable graphite. At P = 7.0 GPa and T = 1200−1800°C, we studied and constructed phase diagrams for the multicomponent peridotite-carbonate and eclogite-carbonate systems as a physicochemical basis for revealing the syngenetic relationships between diamond and its silicate (olivine, ortho- and clinopyroxene, and garnet) and carbonate (aragonite and magnesite) inclusions depending on the physicochemical conditions of growth media. The results obtained allowed us to reconstruct the evolution of diamond-forming systems. The experiments revealed similarity between the compositions of synthetic silicate minerals and inclusions in natural diamonds (high concentrations of Na in garnets and K in clinopyroxenes). It was experimentally demonstrated that the formation of Na-bearing majoritic garnets is controlled by the P-T parameters and melt alkalinity. Diamonds with inclusions of such garnets can be formed in alkalic carbonate-silicate (aluminosilicate) melts. A mechanism was suggested for sodic end-member dissolution in majoritic garnets, and garnet with the composition Na2MgSi5O12 and tetragonal symmetry was synthesized for the first time.

Diamond Formation in Sulfide Pyrrhotite-Carbon Melts: Experiments at 6.0-7.1 GPa and Application to Natural Conditions

Experiments at 6.0–7.1 GPa and 1500–1700°C were carried out to explore the boundary conditions of diamond nucleation and growth in pyrrhotite-carbon melt-solutions. Pyrrhotite is one of the main sulfide minerals of the pyrrhotite-pentlandite-chalcopyrite assemblage of mantle rocks and primary inclusions in diamond. Solutions of carbon in sulfide melts oversaturated with respect to diamond at the expense of the dissolution of starting graphite (thermodynamically unstable phase) are formed owing to the difference between the solubilities of graphite and diamond, which increases under the influence of temperature gradients in experimental samples. We determined the fields of carbon solutions in pyrrhotite melt showing labile and metastable oversaturation with respect to diamond, which correspond to the spontaneous nucleation of the diamond phase and diamond growth on seeds, respectively. The linear growth rate of diamond in sulfide-carbon melts is rather high (on average, 10 μ/min during the first 1–2 min from the onset of spontaneous crystallization). The nucleation density is estimated as 180 grains per cubic centimeter. Diamonds crystallized from sulfide melts show octahedral and spinel twin shapes. Diamond polycrystals were synthesized for the first time from a sulfide medium as intergrowths of skeletal (edge) or “cryptocrystalline” microdiamonds, from 1 to 100 μm in size, their spinel twins and, occasionally, polysynthetic (star-shaped) twins. During diamond growth from sulfidecarbon melts on smooth faces of cuboctahedral diamond seeds synthesized in metal systems, smooth-faced layer-by-layer step-like growth was observed on their octahedral (111) faces, whereas growth on the (100) cubic faces produced rough-surfaced layers of intergrown micropyramids, whose axes were oriented normal to the (100) face. The obtained experimental results were applied to the problem of diamond genesis under the conditions of the Earth’s mantle in the framework of the model of carbonate-silicate parental melts with blebs of immiscible sulfide melts.