Carbonated Silicate Melt Research Articles

Reactive Infiltration of MORB-Eclogite-Derived Carbonated Silicate Melt into Fertile Peridotite at 3 GPa and Genesis of Alkalic Magmas

We performed experiments between two different carbonated eclogite-derived melts and lherzolite at 1375°C and 3 GPa by varying the reacting melt fraction from 8 to 50 wt %. The two starting melt compositions were (1) alkalic basalt with 11·7 wt % dissolved CO2 (ABC), (2) basaltic andesite with 2·6 wt % dissolved CO2 (BAC). The starting melts were mixed homogeneously with peridotite to simulate porous reactive infiltration of melt in the Earth’s mantle. All the experiments produced an assemblage of melt + orthopyroxene + clinopyroxene + garnet ± olivine; olivine was absent for a reacting melt fraction of 50 wt % for ABC and 40 wt % for BAC. Basanitic ABC evolved to melilitites (on a CO2-free basis, SiO2 ∼27–39 wt %, TiO2 ∼2·8–6·3 wt %, Al2O3 ∼4·1–9·1 wt %, FeO* ∼11–16 wt %, MgO ∼17–21 wt %, CaO ∼13–21 wt %, Na2O ∼4–7 wt %, CO2 ∼10–25 wt %) upon melt–rock reaction and the degree of alkalinity of the reacted melts is positively correlated with melt–rock ratio. On the other hand, reacted melts derived from BAC (on a CO2-free basis SiO2 ∼42–53 wt %, TiO2 ∼6·4–8·7 wt %, Al2O3 ∼10·5–12·3 wt %, FeO* ∼6·5–10·5 wt %, MgO ∼7·9–15·4 wt %, CaO ∼7·3–10·3 wt %, Na2O ∼3·4–4 wt %, CO2 ∼6·2–11·7 wt %) increase in alkalinity with decreasing melt–rock ratio. We demonstrate that owing to the presence of only 0·65 wt % of CO2 in the bulk melt–rock mixture (corresponding to 25 wt % BAC + lherzolite mixture), nephelinitic-basanite melts can be generated by partial reactive crystallization of basaltic andesite as opposed to basanites produced in volatile-free conditions. Post 20% olivine fractionation, the reacted melts derived from ABC at low to intermediate melt–rock ratios match with 20–40% of the population of natural nephelinites and melilitites in terms of SiO2 and CaO/Al2O3, 60–80% in terms of TiO2, Al2O3 and FeO, and <20% in terms of CaO and Na2O. The reacted melts from BAC, at intermediate melt–rock ratios, are excellent matches for some of the Mg-rich (MgO >15 wt %) natural nephelinites in terms of SiO2, Al2O3, FeO*, CaO, Na2O and CaO/Al2O3. Not only can these reacted melts erupt by themselves, they can also act as metasomatizing agents in the Earth’s mantle. Our study suggests that a combination of subducted, silica-saturated crust–peridotite interaction and the presence of CO2 in the mantle source region are sufficient to produce a large range of primitive alkalic basalts. Also, mantle potential temperatures of 1330–1350°C appear sufficient to produce high-MgO, primitive basanite–nephelinite if carbonated eclogite melt and peridotite interaction is taken into account.

Melting of clinopyroxene + magnesite in iron-bearing planetary mantles and implications for the Earth and Mars

The assemblage clinopyroxene + magnesite was observed in Earth’s high-pressure metamorphic samples, and its stability in subducting slabs was confirmed by experiments. Recent studies also suggested that the fO2 variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. Although there is no direct evidence for the stability of the cpx + mc assemblage in Mars mantle, its high-pressure–high-temperature decomposition to cpx + fo + CO2 makes it a good analogue for the source of carbon metasomatism, in particular, to study nakhlites formation. Iron, which is present in the Earth’s and Martian mantles, may, however, influence the speciation of carbon. We performed experiments on a clinopyroxene + magnesite assemblage at 1.8 and 3.0 GPa and temperatures corresponding to the Earth’s and Martian mantles. The role of iron and of fO2 was investigated by (1) replacing all or part of the magnesite by siderite FeCO3, (2) adding Fe0 and (3) using graphite C capsules. A carbonate-silicate melt forms at both Earth and Mars conditions. Clinopyroxene and olivine are the main solid phases in the iron-free experiments. Fe2+ and Fe0 decrease their melting temperatures and increase the silicate fraction in the melt. The produced carbonate-silicate melts may be involved in the formation of some carbon-rich lavas on Earth (e.g., carbonatites, ultramafic lamprophyres, or kamafugites). Our results may also be used to interpret ophiolite samples or inclusions. In particular, we show that wustite may form in equilibrium with carbonate-silicate melt in opx-(and silica-) poor regions of the mantle below 3 GPa. Our results also confirm the hypothesis of carbon metasomatism in the Martian nakhlites source. Immiscibility or reduction could explain the absence or rarity of C in Martian lavas.

Shonkinites and minettes of the Ryabinovyi massif (Central Aldan): composition and crystallization conditions

Dikes of biotitic shonkinites and minettes of the complex Ryabinovyi alkaline massif (Central Aldan) have been studied. The dikes are localized in a neck of K-picrites in the northeast of the massif, which intrudes gold-bearing microcline–muscovite metasomatites (Muscovitovyi site). The obtained data on the chemical and trace-element compositions of the rocks and minerals and study of melt inclusions in clinopyroxenes indicate that the biotitic shonkinites and minettes crystallized from the same deep-seated high-pressure alkaline ultrabasic magma during its evolution. Apparently, at the early stage of crystallization of diopside in the biotitic shonkinites, homogeneous carbonate–silicate melt was separated into immiscible fractions of silicate, carbonate–salt, and carbonate melts. The temperature of melt immiscibility was >1120–1190 °C, i.e., higher than the homogenization temperature of silicate inclusions in the diopside. The contents of trace elements in the biotitic shonkinites and rock-forming clinopyroxenes were one or two orders of magnitude higher than the mantle values. The Eu/Eu* ratios of both the considered rocks and the clinopyroxenes were close to those of chondrites, which testifies to their crystallization from mantle magma. The HREE/LREE ratio indicates that the magma source was localized at the depths where garnet-spinel assemblages existed. The negative Nb and Ti anomalies in the trace-element spectra and the high (>5) La/Nb ratios in the rocks and clinopyroxenes point to the influence of crustal material on the parental magma. Crystallization of magma took place in reducing conditions, which is evidenced by the low (4–7) Ti/V ratios in clinopyroxenes and the presence of chloride–sulfate inclusions in them. Since gold in the Ryabinovyi massif is associated with late sulfate–chloride and sulfate–carbonate fluids, it might have been transported by alkaline chloride–sulfate and carbonate (carbonatite) melts, found as inclusions in clinopyroxenes of the biotitic shonkinites, at the early stages of Mesozoic magmatism.

Minor and trace elements in olivines as probes into early igneous and mantle melting processes

The trace element composition of olivine is a rapidly growing research area that has several applications of great potential. Mantle olivines can be distinguished from volcanic olivines by lower concentrations of Ca (<700ppm), Ti (<70ppm), and often Cr. The melting of pyroxenites derived from recycled ocean crust can be recognized in volcanic olivines by correlations of Mn, Al, Sc and Co in addition to Ni. High Ni is characteristic of olivine derived from olivine-free source rocks, but alone it does not distinguish between recycling of ocean crust, continental crust, mantle wedge hybridization, and intra-mantle melt migration. Trace elements help to identify different types of non-peridotitic ultramafic rocks, including those not formed by ocean crust recycling. High Li may be caused by recycling of continental crust, as in Mediterranean post-collisional volcanics or by interaction with carbonatitic melts, and correlation with further elements such as Zn, Na, Ti and Ca will help to identify minerals in the source assemblages, such as phlogopite, spinel, garnet, amphiboles and carbonates, and thus the source of the olivine-free assemblages. Olivines often store the earliest chemical signals of melt loss in peridotites, but later absorb trace elements from passing melts, and are thus excellent monitors of the chemistry of metasomatic agents. Trace elements distinguish between Ti-enrichment by silicate melt metasomatism (high Ti, low Ca) and high-Ca signatures associated with plumes and rift regions that may be due to carbonate–silicate melts. Li may be enriched in olivine in the orogenic mantle, indicating the involvement of melted continental crustal material. Experimental data on element partitioning and diffusion currently partly conflicts with information from natural rocks.

Carbon-dioxide-rich silicate melt in the Earth’s upper mantle

The onset of melting in the Earth's upper mantle influences the thermal evolution of the planet, fluxes of key volatiles to the exosphere, and geochemical and geophysical properties of the mantle. Although carbonatitic melt could be stable 250 km or less beneath mid-oceanic ridges, owing to the small fraction (∼0.03 wt%) its effects on the mantle properties are unclear. Geophysical measurements, however, suggest that melts of greater volume may be present at ∼200 km (refs 3-5) but large melt fractions are thought to be restricted to shallower depths. Here we present experiments on carbonated peridotites over 2-5 GPa that constrain the location and the slope of the onset of silicate melting in the mantle. We find that the pressure-temperature slope of carbonated silicate melting is steeper than the solidus of volatile-free peridotite and that silicate melting of dry peridotite + CO(2) beneath ridges commences at ∼180 km. Accounting for the effect of 50-200 p.p.m. H(2)O on freezing point depression, the onset of silicate melting for a sub-ridge mantle with ∼100 p.p.m. CO(2) becomes as deep as ∼220-300 km. We suggest that, on a global scale, carbonated silicate melt generation at a redox front ∼250-200 km deep, with destabilization of metal and majorite in the upwelling mantle, explains the oceanic low-velocity zone and the electrical conductivity structure of the mantle. In locally oxidized domains, deeper carbonated silicate melt may contribute to the seismic X-discontinuity. Furthermore, our results, along with the electrical conductivity of molten carbonated peridotite and that of the oceanic upper mantle, suggest that mantle at depth is CO(2)-rich but H(2)O-poor. Finally, carbonated silicate melts restrict the stability of carbonatite in the Earth's deep upper mantle, and the inventory of carbon, H(2)O and other highly incompatible elements at ridges becomes controlled by the flux of the former.

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.

Melting experiments on the Udachnaya kimberlite at 6.3–7.5 GPa: Implications for the role of H2O in magma generation and formation of hydrous olivine

Melting experiments on kimberlite from the Udachnaya pipe have been performed at 6.3–7.5GPa and 1300–1600°C using a split-sphere multianvil apparatus. The water content in kimberlite varied from 2.5 to 11.6wt.% and the CO2/(CO2+H2O) molar ratio was from 0.61 to 0.23. The samples were placed in a graphite container inside a Pt capsule. The oxygen fugacity (fO2) during the experiment was controlled by the equilibrium between graphite and water-bearing carbonate–silicate melt. At relatively low temperatures, fO2 was close to the EMOG/D equilibrium, at higher temperatures, it shifted for approximately 1 log unit to more reduced conditions. An olivine+garnet+clinopyroxene assemblage was present at ⩽100°C below the liquidus of the Udachnaya kimberlite, with 6–8wt.% H2O at the pressure 6.3GPa and 6–10wt.% H2O at 7.5GPa. At 2.5wt.% H2O the same assemblage appeared at ⩾150°C below liquidus, both at 6.3 and 7.5GPa. Orthopyroxene did not form at any temperature and pressure of the experiments. The presence of clinopyroxene near the liquidus was due to the calcic nature and a high degree of silica undersaturation in the Udachnaya kimberlite. At the supra-solidus conditions, garnet and clinopyroxene compositionally distinct from minerals of the megacryst/macrocryst suite crystallized in equilibrium with low-H2O carbonated melt. Near the liquidus of high-H2O kimberlite, the stable olivine composition was from Fo91 to Fo98. The garnet composition (CaO ∼8wt.%, TiO2 <1wt.% and Cr2O3 up to 2.2wt.%) approached that of Ti-bearing garnet typical of Cr-poor garnet megacrysts while the clinopyroxene was an analog of clinopyroxene megacrysts in kimberlite. Infrared absorption measurements showed that crystallized olivines contained water in the form of Ti-clinohumite-like and OH-clinohumite-like defects. The H2O content of olivine was found to depend mainly on water content in kimberlite melt and pressure. Olivine with 120–170ppm H2O crystallized at 6GPa in equilibrium with the melt compositionally close to the archetypical kimberlite rather than a carbonate one, and water as high as 6wt.%. Olivine with 270–300ppm H2O crystallized near kimberlite liquidus only at 7.5GPa and 9.5–10.1wt.% H2O. The experimental results imply that hydrous olivine, which is typical to kimberlites, including the Udachnaya pipe, very unlikely can crystallize from anhydrous carbonated magma. Judging by the conditions for multiphase saturation of the Udachnaya kimberlite melt, its generation was possible by partial melting of carbonated garnet wehrlite at pressures from 6 to 7.5GPa and temperatures within 1450–1600°C in the presence of aqueous fluids. Thus, water must have been a trigger for generation of the primary kimberlite magma.

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.

In-situ geochemistry of sulfides in highly metasomatized mantle xenoliths from Kerguelen, southern Indian Ocean

Mantle xenoliths from the Kerguelen Archipelago record a complex multistage history involving a high degree (15 to 25%) partial melting that created a harzburgitic mantle completely stripped of Base Metal Sulfides (BMS), followed by pervasive melt-rock reaction with alkaline melts above the Kerguelen mantle plume. Subsequent reaction of the highly refractory protolith with small volumes of carbonate-rich silicate melts led to a re-enrichment in BMS (up to 0.05wt.%). Two BMS precipitation mechanisms are suggested: immiscibility from the silicate-carbonate melt and sulfidation reactions from a CO2-rich supercritical fluid. In-situ analyses of chalcophile and siderophile elements (major and trace levels) in the BMS shed new light on their origin. The BMS phases that precipitated via immiscibility are metal-rich sulfide melts which progressively evolved toward Ni and Cu-rich end-members by cumulate fractionation of monosulfide solid solution (mss) during percolation inside the peridotites. Some cumulate mss have elevated and fractionated IPGE contents (200–900× C1-Chondrite abundances), indicating random digestion of preexisting Os, Ir, Ru-rich PGM by the percolating sulfide melt. The BMS that precipitated by sulfidation reactions from a CO2-rich vapour phase are subsolidus exsolution products from Cu-bearing but Ni-poorer mss. They have the highest concentrations of PGEs and show selective enrichment in S, Pd, Pt and Os over Cu, S, Ir, Ru and Rh. Their PGE compositions confirm experimental data, which demonstrate that S, Pd, Pt and Os can be efficiently transported in a CO2-rich supercritical fluid. Superchondritic (S/Se), (Os/Ir) and (Pd/Pt) in both bulk-rocks and individual sulfides are inferred to be the geochemical fingerprints of sulfide crystallisation from a CO2-rich vapour exsolved from a highly evolved carbonate-rich metasomatic melt.

Carbonate-rich melt infiltration in peridotite xenoliths from the Eurasian–North American modern plate boundary (Chersky Range, Yakutia)

A suite of mainly spinel peridotite and subordinate pyroxenite xenoliths and megacrysts were studied in detail, enabling us to characterize upper mantle conditions and processes beneath the modern North American–Eurasian continental plate boundary. The samples were collected from 37-Ma-old basanites cropping out in the Main Collision Belt of the Chersky Range, Yakutia Republic (Russian Far East). The spinel lherzolites reflect a mantle sequence, equilibrated at temperatures of 890–1,025 °C at pressures of 1.1–2 GPa, with melt extraction estimated to be around 2–6 %. The spinel harzburgites are characterized by lower P–T equilibration conditions and estimated melt extraction up to 12 %. Minor cryptic metasomatic processes are recorded in the clinopyroxene trace elements, revealing that percolating hydrous fluid-rich melts and basaltic melts affected the peridotites. One of the lherzolites preserves a unique melt droplet with primary dolomite in perfect phase contact with Na-rich aluminosilicate glass and sodalite. On the basis of the well-constrained P–T frame of the xenolith suite, as well as the rigorously documented melt extraction and metasomatic history of this upper mantle section, we discuss how a carbonated silicate melt infiltrated the lherzolite at depth and differentiated into an immiscible carbonate and silicate liquid shortly before the xenolith was transported to the surface by the host basalt. Decreasing temperatures triggered crystallization of primary dolomite from the carbonate melt fraction and sodalite as well as quenched glass from the Na-rich aluminosilicate melt fraction. Rapid entrainment and transport to the Earth’s surface prevented decarbonatization processes as well as reaction phenomena with the host lherzolite, preserving this exceptional snapshot of upper mantle carbonatization and liquid immiscibility.

Experimental study in the Na2O–CaO–MgO–Al2O3–SiO2–CO2 system at 3 GPa: the effect of sodium on mantle melting to carbonate-rich liquids and implications for the petrogenesis of silicocarbonatites

AbstractMelt compositions in equilibrium with peridotite assemblages were determined in the analogue system Na2O–CaO–MgO–Al2O3–SiO2–CO2 at 3 GPa with Ca/Ca + Mg = 0.56–0.43 and up to 6 wt.% Na2O. There is a greater compositional range generated isobarically over a larger temperature interval than in a sodium-absent system: increasing sodium content drives liquids to compositions with lower CaO and higher SiO2 concentrations. A positive correlation between silica and Na2O content of liquids produced at constant temperature is due to the depolymerization of silicate tetrahedra in the presence of monovalent cations, as in the volatile-free system. Liquids with Na2O &gt;6 wt.% occur in association with wehrlites as the composition of diopsidic pyroxene expands towards enstatite with addition of Na2O, decreasing the orthopyroxene content of peridotite. The orthopyroxene-out curve intersects an enriched mantle solidus at 3 GPa where near-solidus liquids have Na2O = 7 1.5 wt.%. Sodium partitioning between a metaluminous liquid and clinopyroxene follows the jadeite partitioning models calculated for the dry silicate system but sodium partitions into peralkaline carbonated liquids as both the pyroxene and the carbonate molecules. The peralkaline liquids generated are essentially carbonated silicate melts that are analogous to silica-bearing carbonatites and silicocarbonatites from a range of possible metasomatized mantle sources.

Paragenetic relations of diamond with silicate and carbonate minerals in the carbonatite-diamond system: Experiments at 8.5 GPa

Phase relations of diamond and syngenetic minerals were experimentally investigated in the multicomponent system natural carbonatite-diamond at a pressure of 8.5 GPa and temperatures of 1300–1800°C (within the thermodynamic stability field of diamond). Under such conditions, the natural carbonatite of the Chagatai complex (Uzbekistan) acquires the mineralogy of Ca-rich eclogites (grospydites). The melting phase diagram of this system (syngenesis diagram) was constructed; an important element of this diagram is the diamond solubility curve in completely miscible carbonate-silicate melts (solubility values are 15–18 wt % C). The diamond solubility curve divides the phase diagram into two fields corresponding to (1) phase relations involving diamond-undersaturated melts-solutions of carbon with garnet as a liquidus phase (region of diamond dissolution) and (2) phase relations with diamond-saturated melts-solutions with diamond as a liquidus phase (region of diamond crystallization). During a temperature decrease in the region of diamond crystallization from carbonate-silicate melts, the crystallization of diamond is accompanied by the sequential formation of the following phase assemblages: diamond + garnet + melt, diamond + garnet + clinopyroxene + melt, and diamond + garnet + clinopyroxene + carbonate + melt, and the subsolidus assemblage diamond + garnet + clinopyroxene + carbonate is eventually formed. This is indicative of the paragenetic nature of silicate and carbonate minerals co-crystallizing with diamond and corresponding primary inclusions trapped by the growing diamond. A physicochemical mechanism was proposed for the formation of diamond in carbonate-silicate melts. The obtained results were used to analyze the physicochemical behavior of a natural diamond-forming magma chamber.

Review of melting experiments on carbonated eclogite and peridotite: insights into mantle metasomatism

Experimental studies on the partial melting of eclogite and peridotite provide important clues on mantle metasomatism. Here, we review results from some of the recent experiments and show that melting of carbonated eclogite and peridotite can produce carbonatitic to carbonated silicate melt, in which carbonates melt preferentially before Ti oxides and silicates. Low-degree melting results in carbonatitic melt coexisting with Ti oxides and silicates. This process also leads to the fractionation between some high-field strength elements (Nb, Ta, Zr, Hf, and HREE) and highly incompatible elements (U and Th) in the melt. When Ti oxides are nearly exhausted in eclogite, extremely high TiO2 contents (e.g. 19 wt.%) are present in the melt with marked concentration of Nb and Ta. These results help to explain the features of carbonatitic metasomatism and the Nb–Ta spike in oceanic island basalts as identified in experimental studies. These studies also explain the reducing conditions that stabilize diamond in the deep mantle (>150 km) as well as the occurrence of diamond at different depths reported in various studies. Melting in such a reduced mantle can happen through redox reaction between diamond, pyroxene, and olivine, in which the initial liquid is a carbonated silicate melt. However, the theoretical oxygen fugacity (fO2) in the asthenosphere is much lower than that predicted by the reaction and requires elevated fO2, which can be caused by the addition of relatively oxidized materials from the lower mantle, deep asthenospheric material, and various recycled components. A combination of these processes generates locally oxidized domains in the deep mantle.

An Experimental Study of Carbonated Eclogite at 3{middle dot}5-5{middle dot}5 GPa--Implications for Silicate and Carbonate Metasomatism in the Cratonic Mantle

We have experimentally investigated a K-bearing altered mid-ocean ridge basalt (MORB) composition to which 10% CaCO3 was added (GA1+10%cc), at temperatures of 1050-1400oC and pressures of 3•5-5•5 GPa. Experiments were conducted in piston-cylinder apparatus in Pt-Gr (Pt with inner graphite) and Au-Pd capsules. Sub-solidus assemblages for both sets of experiments contain clinopyroxene, garnet, carbonate, rutile, coesite and K-feldspar. Apatite was observed only in the Pt-Gr experiments. Melting behaviour in experiments using different capsule materials contrasted markedly. Experiments in Pt-Gr capsules showed the silicate solidus to be at temperatures less than 1100oC at 3•5GPa and less than 1050oC at 4•5-5•0 GPa.These are similar (3•5GPa) or lower (4•5-5•0 GPa) temperatures compared with the carbonate solidus (1075-1125oC at 3•5-5•0 GPa). Melts in the Pt-Gr runs evolve with increasing degree of melting from K-rich silicate melts at the lowest degree of melting to carbonate-silicate immiscible liquids and silicate-carbonate melts at intermediate degrees of melting, and finally to silicate melts at the highest degrees of melting. Experiments in Au-Pd capsules were performed only at 5•0GPa. The carbonate solidus is between 1200 and 1225oC (at least 100oC higher than in the experiments in Pt-Gr capsules at the same pressure-temperature conditions).The first melts to be produced are carbonatitic and exhibit increasing SiO2 content with increasing temperature.This contrast in melting behaviour is explained by the relatively rapid diffusion of H through the Pt-Gr capsules, resulting in formation of H2O, and thus dramatically depressing both the silicate and the carbonate solidi in the Pt-Gr experiments compared with those in the Au-Pd experiments. This presumably reflects the lower permeability of Au-Pd to H, resulting in a much lower H2O/CO2 ratio in the Au-Pd encapsulated experiments. The presence of water in the melt was demonstrated by Fourier transform infrared (FTIR) spectroscopic analysis of one Pt-Gr experiment, indicating ~0•5wt % H2O in the bulk composition. Further confirmation that H2O plays such a role in the Pt-Gr experiments was provided by an additional experiment performed in a Au-Pd capsule with ~10 wt % H2Ospecifically added. In this experiment immiscible carbonate and silicate melts were observed. Carbonate- silicate liquid immiscibility is considered to occur as a result of the H2O present in the system. These results can be applied to natural systems in several ways. First, the presence of a small amount of either silicate melt or H2O-fluid in the system will act as a ‘flux’, depressing the carbonate solidus to much lower temperatures than inanhydrous systems. Second, the full trend in melt evolution from silicate-rich to carbonate-rich melts, which is also observed in inclusions in diamonds, can be explained by melting of K- and CO2-bearing, water-undersaturated MORB compositions. In cratonic environments low-degree silicate and immiscible silicate and carbonate melts will metasomatize the overlying mantle in different ways, producing, in the first instance, Si enrichment and crystallization of additional orthopyroxene, phlogopite, pyrope-rich garnet and consuming olivine, and, in the second case, carbonate metasomatism, with additional magnesite-dolomite, clinopyroxene and apatite. Both metasomatic styles have been described in natural peridotite xenoliths from the cratonic lithosphere.

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.

The partial molar volume of carbon dioxide in peridotite partial melt at high pressure

The partial molar volume of CO 2 ( V ¯ C O 2 ) in silicate melt was determined for a komatiite composition using high pressure sink/float experiments in a multi-anvil press. The density of the experimental melt at pressure was determined by observing sinking and floating of pure forsterite (Fo100) and forsterite (Fo90) buoyancy markers. Values for V ¯ C O 2 were bracketed at 4.3 GPa (23.71 cm 3/mol) and at 5.5 GPa (22.06 cm 3/mol), normalized to 2123 K. Combining the current data with previous work we now more accurately constrain the compression curve of V ¯ C O 2 over the pressure range of 1.0 × 10 − 4 to 20 GPa. These data allow the calculation of density at pressure of carbonated silicate melts, such as kimberlite and silica undersaturated alkali basalts, and the determination of their buoyancy and eruptibility.

Conditions for the origin of oxidized carbonate-silicate melts: Implications for mantle metasomatism and diamond formation

An experimental study on the origin of ferric and ferrous carbonate-silicate melts, which can be considered as the potential metasomatic oxidizing agents and diamond forming media, was performed in the (Ca,Mg)CO 3-SiO 2-Al 2O 3-(Mg,Fe)(Cr,Fe,Ti)O 3 system, at 6.3 GPa and 1350–1650 °C. At 1350–1450 °C and ƒO 2 of FMQ + 2 log units, carbonate–silicate melt, coexisting with Fe 3 + -bearing ilmenite, pyrope-almandine and rutile, contained up to 13 wt.% of Fe 2O 3. An increase in the degree of partial melting was accompanied by decarbonation and melt enrichment with CO 2, up to 21 wt.%. At 1550–1650 °C excess CO 2 segregated as a separate fluid phase. The restricted solubility of CO 2 in the melt indicated that investigated system did not achieve the second critical point at 6.3 GPa. At 1350–1450 °C and ƒO 2 close to CCO buffer, Fe 2 + -bearing carbonate–silicate melt was formed in association with pyrope-almandine and Fe 3 + -bearing rutile. It was experimentally shown that CO 2-rich ferrous carbonate-silicate melt can be an effective waterless medium for the diamond crystallization. It provides relatively high diamond growth rates (3–5 μm/h) at P,T-conditions, corresponding to the formation of most natural diamonds.

The phase composition of crystal-fluid nanoinclusions in alluvial diamonds in the northeastern Siberian Platform

The phase composition of crystal-fluid nanoinclusions in two types of placer diamonds of unknown genesis from the northeastern Siberian Platform (Ebelyakh diamondiferous region) has been first studied by transmission electron microscopy including electron diffraction, analytical electron microscopy (AEM), electron energy loss spectroscopy (EELS), and chromatography. The type I diamonds are transparent dodecahedroids, and the type II ones, widespread in this region, are dark rounded crystals assigned to variety V according to Orlov’s mineralogical classification. Isotopic and IR-Fourie spectroscopic studies showed that the type II diamonds have a strongly light carbon isotope composition (δ 13C av = –22.4‰) and high concentrations of nitrogen admixture (1100–1800 ppm). Nitrogen is present mainly as an aggregate. It is shown that all inclusions no larger than 400 nm are polyphase particles consisting of solid (silicate, oxide, carbonate, salt) and fluid phases. The type I diamonds bear high-Mg carbonatite inclusions (up to 100 nm) consisting of magnesite, dolomite, Fe-spinel, and clinohumite. The fluid phase has high concentrations of K, Cl, and O. The inclusions are similar in composition to the near-solidus melts of saturated carbonatized peridotites; thus, they might have resulted either from the crystallization of the parental melt or from the quenching and crystallization of deep-seated carbonate-silicate melt. The type II diamonds bear low-Mg carbonatite polyphase nanoinclusions consisting of Ba-, Sr-, and Ca,Fe-carbonatites, K,Ba-phosphates, Ti,Si- and Ti,Al-phases, and abundant fluid segregations filled mainly with CO 2, N, and hydrocarbons. These melts/solutions might have been supplied from subducted rocks of the oceanic and, partly, continental Earth’s crust. The enrichment of these inclusions in incompatible elements might evidence the percolation of salt fluids enriched in Ba, Sr, P, Ti, K, and Cl through carbonatized eclogites.

Parental media for diamonds and primary inclusions by evidence of physicochemical experiment

The mantle-carbonatite conception of genesis of diamond (Litvin, 2007, 2009) is briefly outlined. A generalized of compositions of the multi-component heterogeneous parental medium for diamond and primary inclusions therein is first developed. Boundary compositions of the parental medium are represented by mineral components of the peridotitic and eclogitic parageneses, mantle carbonatites and C-O-H-fluids, phases of accessory type both soluble in the carbonate-silicate melts (chlorides, phosphates, etc.) and insoluble in them (sulfides), as well as carbon. Phase relations of the multi-component eclogite-carbonatite-sulfide-diamond are studied at 7 GPa. Syngenesis diagram for diamond, paragenetic and xenogenetic minerals (including the solubility curves of diamond in carbonate-silicate and sulfide melts) is constructed. Physicochemical mechanism of formation of diamond and paragenetic minerals is revealed. Genetic classification of primary inclusions in natural diamonds is worked out. Analysis of physicochemical history of diamond formation in the mantle chamber of carbonatite magma is accomplished. Introduction .The mantle-carbonatite conception of genesis of diamond of kimberlite deposits (Litvin, 2007 a, b , 2009) is justified by the complex of mineralogical, experimental and theoretical data. Completely miscible carbonate-silicate growth melts with dissolved elemental carbon (carbon source for diamond) form a basis for the parental media for the dominating mass of natural diamonds and paragenetic minerals. The parental carbonate-silicate-carbon melts are multi-component heterogeneous media with strongly changeable compositions. So, silicate constituents are presented by minerals and components both peridotite and eclogite parageneses (Sobolev, 1974). It is established in the high- pressure high-temperature experiments that both peridotite-carbonatite-carbon and eclogite-carbonatite- carbon melts are represented as highly efficient diamond-forming media. An example of diamond crystallization in melt oversaturated in dissolved carbon of the eclogite-carbonatite system is demonstrated in the fig. 1. Composition of parental medium for diamond and primary inclusions. A generalized of compositions of the multi-component heterogeneous parental medium for diamond and primary inclusions therein is developed (Fig. 2).The major composition tetrahedron of the system peridotite-eclogite-carbonatite-soluble admixture componens is its basic element. Belonging of the mineral assemblage of syngenetic inclusions in natural diamonds to two major parageneses, - peridotitic and eclogitic, - is took into consideration. The boundary compositions of the parental medium are determined with mineral components of the auxiliary tetrahedrons - peridotitic (Ol-Opx-Cpx-Grt), eclogitic (Cpx-Grt-Crn-Coes), mantle carbonatite (Mg, Fe, Ca, K, Na, etc. carbonates), phases and components of admixtured accessory sort - soluble in carbonate-silicate melts (chlorides, phosphates, etc.) including the components of C-O-H-volatile compounds, and carbon too. All the components of the boundary tetrahedrons mentioned above are responsible for formation of paragenetic mineral phases together with diamond and, correspondingly, for capture of the paragenetic inclusions by natural diamonds. At the same time due to physicochemical experiment it turned out that xenogenetic mineral phases are presented within the assemblage of so called syngenetic inclusions. Sulfide minerals which are not soluble in diamond-forming carbonate-silicate melts as well as sulfide melts which are completely immiscible with these are among the xenogenetic phases. In the fig. 2, the auxiliary boundary tetrahedron for sulfide components is positioned out of the major tetrahedron and is

Diamond-forming efficiency of chloride-silicate-carbonate melts

According to the carbonatite model of the diamond formation [Litvin, 2007] based on the large volume of mineralogical and physicochemical experimental information, carbon-silicate-carbonate (carbonatitic) melts with widely variable compositions are the growth medium for most mantle diamonds and inclusions in them. In addition to the major completely miscible carbonate and silicate components (minerals of peridotite and eclogite assemblages), such melts contain minor soluble components (oxides, phosphates, chlorides, C-O-H-N fluids, and others), as well as minor completely immiscible and insoluble solid and melt phases (sulfides, metals). The diamond-forming efficiency of silicate-carbonate melts clearly corresponds to the important criterion of syngenesis of diamond with its silicate and carbonate inclusions. High-pressure experimental associations not only comprise the whole set of minerals typical for inclusions in diamonds of peridotitic (olivine, garnet, clino-, and orthopyroxenes) and eclogitic (garnet and clinopyroxene) type, but demonstrate the characteristic features of minerals of diamond paragenesis. These comprise significant admixtures of Na in garnets and K in clinopyroxenes, which are the reliable indicators of crystallization of these minerals from alkaline silicate-carbonate melts. Experimental investigations of multicomponent peridotite-carbonatite and eclogite-carbonatite systems at a standardized pressure of 8.5 GPa within the narrow pressure range of 1760–1820°C demonstrated that the diamond-forming efficiency of their carbon-bearing melts had concentration limitations [Bobrov and Litvin, 2009]. The compositions effective for the diamond nucleation comprise only significantly carbonatite parts of the systems and are limited by the concentration barriers of diamond nucleation (CBDN) in the cases of K-Na-Ca-Mg-Fe-carbonatite, Ca-Mg-, and Kcarbonate compositions (at the concentrations of 30, 25, and 30 wt % of peridotite components and 35, 30, and 45 wt % of eclogite component, respectively). This means that the inhibitory influence of peridotite and eclogite components dissolved in carbon-bearing carbonatite melts on diamond nucleation is observed only at their relatively low concentrations. We established the diamond-forming efficiency of chloride [Litvin, 2003] and chloride