Oxygen potential of diamond formation in the lower mantle

Thermodynamic calculations have shown that when a metallic phase arising due to ferroan ion disproportionation is contained in lower-mantle rocks, carbon occurs as iron carbide and the oxygen fugacity corresponds to the equilibrium of ferropericlase with Fe-Ni alloy. The typical values of oxygen fugacity in zones of diamond formation in the lower mantle lie between the iron-wüstite buffer and six logarithmic units above this level. The processes that proceed in the lower mantle give rise to variation of $f_{O_2 }$ within several orders of magnitude above the elevated $f_{O_2 }$ values, which are necessary for the formation of diamond, as compared with a common level typical of the lower mantle. The mechanisms responsible for redox differentiation in the lower mantle comprise the subduction of oxidized crustal material, mechanical separation of metallic phase and silicate-oxide mineral assemblage enriched in ferric ions, as well as transfer of fused silicate material presumably enriched in Fe³⁺ through the mantle.     

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 parameters of deep-seated mantle plumes

Thermodynamic analysis of experimental data has demonstrated that FeO activity in silicate melts identical in composition to natural magmas can be described by the regular-solution model, which takes into account interactions of all cations with Si and interaction of Ca with Al. Using this model, we propose an oxygen barometer for spinel + magma phase association. In contrast to the earlier proposed methods for estimation of oxygen chemical potential, this barometer can work in the PJ-domain close to the liquidus of magmatic process. The new oxygen barometer has been applied to magmas related to mantle plume activity, including Siberian meimechites, Hawaiian picrites, and picrites from the Emeishan large igneous province (LIP) and Greenland. We have shown that most magmas related to the activity of deep-seated mantle plumes are characterized by a higher relative chemical potential of oxygen than magmas of mid-ocean ridges. Thermodynamically calculated stability fields of rocks with different carbon-containing phases show that under PJ-conditions of the lower mantle, the ascending mantle plumes are characterized by relatively high oxygen fugacity. Formation of diamond in the lower mantle requires more oxidizing conditions as compared with the major part of this geosphere, where the presence of Fe-Ni alloy is predicted. We have put forward a hypothesis that the main reason for the oxygen fugacity increase in particular domains of the lower mantle is a shift of redox equilibria toward a decrease in the amount of Fe-Ni alloy, up to its disappearance, with temperature growth.     

Oxygen fugacity constraints on the southern African lithosphere

Oxygen fugacities are calculated for olivine—spinel ±orthopyroxene assemblages recovered from diamonds and the concentrate of the Dokolwayo kimberlite, Swaziland. In addition thermobarometric oxygen fugacities are obtained for chrome spinel-garnet peridotites and diamonds from several other southern African kimberlites. The southern African lithosphere appears to be laterally homogeneous with respect to oxygen fugacity. Vertically the oxygen fugacity of the lithospheric upper mantle decreases with an increase in pressure. Locally, oxygen fugacities calculated for Dokolwayo mineral assemblages are indicative of an upper mantle characterised by diverse redox conditions within the range FMQ-IW. Reduced oxygen fugacities, calculated for the majority of the Dokolwayo samples, suggest that CH₄ may be the dominant carbon volatile species in the lower lithosphere. These reduced conditions also suggest that the Dokolwayo kimberlite is unlikely to be a product of redox melting, but may be the product of a thermal anomaly. Calculated equilibrium temperatures for olivine-spinel pairs from Dokolwayo diamonds and concentrate indicate that the upper mantle in the vicinity of Dokolwayo was characterised by cool subsolidus conditions.     

Experimental and thermodynamic study of the crystallization of diamond and silicates in a metal-silicate-carbon system

Silicate inclusions are widespread in natural diamonds, which also may contain rare inclusions of native iron. This suggests that some natural diamonds crystallized in metal-silicate-carbon systems. We experimentally studied the crystallization of diamond and silicate phases from the starting composition Fe_0.36Ni_0.64 + silicate glass + graphite and calculated the Fe mole fractions of the silicate phases crystallizing under these conditions. The silicates synthesized together with diamond had low Fe mole fractions [Fe/(Fe + Mg + Ca)] in spite of strong Fe predominance in the system. The Fe mole fractions of the silicates decreased in the sequence garnet-pyroxene-olivine, which is consistent with the results of our thermodynamic calculations. The Fe mole fraction of silicates under various redox conditions under which metal-carbon melts are stable drastically decreases with decreasing fo₂. The low Fe mole fractions of silicate inclusions in diamond from the Earth’s mantle can be explained by the highly reducing crystallization conditions, under which Fe was concentrated as a metallic phase of the magmatic melts and could be only insignificantly incorporated in the structures of silicates.     

Inclusions in diamonds from the K14 and K10 kimberlites, Buffalo Hills, Alberta, Canada: diamond growth in a plume?

Analyses of mineral inclusions, carbon isotopes, nitrogen contents and nitrogen aggregation states in 29 diamonds from two Buffalo Hills kimberlites in northern Alberta, Canada were conducted. From 25 inclusion bearing diamonds, the following paragenetic abundances were found: peridotitic (48%), eclogitic (32%), eclogitic/websteritic (8%), websteritic (4%), ultradeep? (4%) and unknown (4%). Diamonds containing mineral inclusions of ferropericlase, and mixed eclogitic-asthenospheric-websteritic and eclogitic-websteritic mineral associations suggests the possibility of diamond growth over a range of depths and in a variety of mantle environments (lithosphere, asthenosphere and possibly lower mantle).

Eclogitic diamonds have a broad range of C-isotopic composition (δ¹³C=−21‰ to −5‰). Peridotitic, websteritic and ultradeep diamonds have typical mantle C-isotope values (δ¹³C=−4.9‰ av.), except for two ¹³C-depleted peridotitic (δ¹³C=−11.8‰, −14.6‰) and one ¹³C-depleted websteritic diamond (δ¹³C=−11.9‰). Infrared spectra from 29 diamonds identified two diamond groups: 75% are nitrogen-free (Type II) or have fully aggregated nitrogen defects (Type IaB) with platelet degradation and low to moderate nitrogen contents (av. 330 ppm-N); 25% have lower nitrogen aggregation states and higher nitrogen contents (30% IaB; <1600 ppm-N).

The combined evidence suggests two generations of diamond growth. Type II and Type IaB diamonds with ultradeep, peridotitic, eclogitic and websteritic inclusions crystallised from eclogitic and peridotitic rocks while moving in a dynamic environment from the asthenosphere and possibly the lower mantle to the base of the lithosphere. Mechanisms for diamond movement through the mantle could be by mantle convection, or an ascending plume. The interaction of partial melts with eclogitic and peridotitic lithologies may have produced the intermediate websteritic inclusion compositions, and can explain diamonds of mixed parageneses, and the overlap in C-isotope values between parageneses. Strong deformation and extremely high nitrogen aggregation states in some diamonds may indicate high mantle storage temperatures and strain in the diamond growth environment. A second diamond group, with Type IaA–IaB nitrogen aggregation and peridotitic inclusions, crystallised at the base of the cratonic lithosphere. All diamonds were subsequently sampled by kimberlites and transported to the Earth's surface.     

Peridotitic diamonds from the Slave and the Kaapvaal cratons—similarities and differences based on a preliminary data set

A comparison of the diamond productions from Panda (Ekati Mine) and Snap Lake with those from southern Africa shows significant differences: diamonds from the Slave typically are un-resorbed octahedrals or macles, often with opaque coats, and yellow colours are very rare. Diamonds from the Kaapvaal are dominated by resorbed, dodecahedral shapes, coats are absent and yellow colours are common. The first two features suggest exposure to oxidizing fluids/melts during mantle storage and/or transport to the Earth's surface, for the Kaapvaal diamond population.

Comparing peridotitic inclusions in diamonds from the central and southern Slave (Panda, DO27 and Snap Lake kimberlites) and the Kaapvaal indicates that the diamondiferous mantle lithosphere beneath the Slave is chemically less depleted. Most notable are the almost complete absence of garnet inclusions derived from low-Ca harzburgites and a generally lower Mg-number of Slave inclusions.

Geothermobarometric calculations suggest that Slave diamonds originally formed at very similar thermal conditions as observed beneath the Kaapvaal (geothermal gradients corresponding to 40–42 mW/m² surface heat flow), but the diamond source regions subsequently cooled by about 100–150 °C to fall on a 37–38 mW/m² (surface heat flow) conductive geotherm, as is evidenced from touching (re-equilibrated) inclusions in diamonds, and from xenocrysts and xenoliths. In the Kaapvaal, a similar thermal evolution has previously been recognized for diamonds from the De Beers Pool kimberlites. In part very low aggregation levels of nitrogen impurities in Slave diamonds imply that cooling occurred soon after diamond formation. This may relate elevated temperatures during diamond formation to short-lived magmatic perturbations.

Generally high Cr-contents of pyrope garnets (inside and outside of diamonds) indicate that the mantle lithosphere beneath the Slave originally formed as a residue of melt extraction at relatively low pressures (within the stability field of spinelperidotites), possibly during the extraction of oceanic crust. After emplacement of this depleted, oceanic mantle lithosphere into the Slave lithosphere during a subduction event, secondary metasomatic enrichment occurred leading to strong re-enrichment of the deeper (>140 km) lithosphere. Because of the extent of this event and the occurrence of lower mantle diamonds, this may be related to an upwelling plume, but it may equally just reflect a long term evolution with lower mantle diamonds being transported upwards in the course of “normal” mantle convection.     

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.     

地幔岩中流体包裹体研究

地幔岩石中的流体包裹体代表地幔流体的样品。地幔流体包裹体可以存在从地幔来的金刚石,地幔捕虏体和岩浆碳酸岩中。研究这些岩石和矿物中的流体包裹体可以得出其所代表的地幔流体的温度、压力、成分和同位素。我们目前见到的这三类地幔岩石的包裹体主要可在橄榄石、辉石、金刚石、方解石和磷灰石中见到。这些包裹体可以粗略地分为CO2包襄体和硅酸盐熔融体包裹体。又可细分为四类包裹体：（1）富碳酸盐的硅酸盐熔融包裹体。这种包裹体在金刚石、地幔岩捕虏体和岩浆碳酸盐岩中见到,它又可分为结晶质熔融包裹体和玻璃包裹体。（2）CO2包裹体。这种包裹体大多见于地幔捕虏体中,在金刚石和岩浆碳酸岩中也可见到。（3）含硫化物的包裹体。这种包裹体见于地幔捕虏体中,与纯CO2包裹体和含CO2的熔融包裹体共存。（4）高密度的流体包裹体。这种包裹体见于金刚石中,是一种高盐度、高密度的含K、Cl和H2O的流体包裹体,又可分为高卤水包裹体和含卤水的富硅的碳酸盐岩浆包裹体。从对金刚石、地幔捕虏体和岩浆碳酸盐岩中流体包裹体的研究表明,地幔流体存在不均匀性和不混溶性。     

The mineralogy of Ca-rich inclusions in sublithospheric diamonds

This paper discusses mineralogy of Ca-rich inclusions in ultra-deep (sublithospheric) diamonds. It was shown that most of the Ca-rich majoritic garnets are of metabasic (eclogitic) affinity. The observed variation in major and trace element composition is consistent with variations in the composition of the protolith and the degree of enrichment or depletion during interaction with melts. Major and trace element compositions of the inclusions of Ca minerals in ultra-deep diamonds indicate that they crystallized from Ca-carbonatite melts that were derived from partial melting of eclogite bodies in deeply subducted oceanic crust in the transition zone or even the lower mantle. The occurrence of merwinite or CAS inclusions in ultra-deep diamonds can serve as mineralogical indicators of the interaction of metaperidotitic and metabasic mantle lithologies with alkaline carbonatite melts. The discovery of the inclusions of carbonates in association with ultra-deep Ca minerals can not only provide additional support for their role in the diamond formation process but also help to define additional mantle reservoirs involved in global carbon cycle.     

The Inclusions in Superdeep Diamonds: Indication and Response to Deep Mantle Physical and Chemical Environment

Superdeep diamonds and their inclusions are important samples to probe the physical and chemical environment and constitution of Earth’s deep mantle. By combining the studies of high-precision in-situ analysis and HPHT synthetic diamond experiments, and by reviewing the new discovery of classical mineral inclusions and their combinations, the ranges of different inclusion combinations, as well as the relationship between trace elements and temperature-pressure conditions were reoriented. The so-called nominally anhydrous minerals combinations, metal phases and redox environments in superdeep mantle were also affirmed. Meanwhile,the recent findings of inclusions and isotopes in superdeep diamonds support the fact that the remaining subduction ocean crust may be a significant reservoir of the deep mantle’s water and the deep mantle carbon cycle is closely related to oceanic subduction. Furthermore, although Chinese scholars have discovered some kinds of superdeep inclusions in diamonds from North China Craton and Yangtze Craton, and made considerable progress in the study of the formation of UHP diamonds and the genesis of ophiolite diamonds, there are still many scientific questions about superdeep diamonds that require further research.     

Ferropericlase—a lower mantle phase in the upper mantle

Experiments on compositions along the join MgO–NaA³⁺Si₂O₆ (A=Al, Cr, Fe³⁺) show that sodium can be incorporated into ferropericlase at upper mantle pressures in amounts commonly found in natural diamond inclusions. These results, combined with the observed mineral parageneses of several diamond inclusion suites, establish firmly that ferropericlase exists in the upper mantle in regions with low silica activity. Such regions may be carbonated dunite or stalled and degassed carbonatitic melts. Ferropericlase as an inclusion in diamond on its own is not indicative of a lower mantle origin or of a deep mantle plume. Coexisting phases have to be taken into consideration to decide on the depth of origin. The composition of olivine will indicate an origin from the upper mantle or border of the transition zone to the lower mantle and whether it coexisted with ferropericlase in the upper mantle or as ringwoodite. The narrow and flat three phase loop at the border transition zone—lower mantle together with hybrid peridotite plus eclogite/sediments provides an explanation for the varying and Fe-rich nature of the diamond inclusion suite from Sao Luiz, Brazil.     

Review on Lithospheric Diamonds and Their Mineral Inclusions

Diamonds and their mineral inclusions are valuable for studying the genesis of diamonds, the characteristics and processes of ancient lithospheric mantle and deeper mantle. This has been paid lots of attentions by geologists both at home and abroad. Most diamonds come from lithospheric mantle. According to their formation preceded, accompanied or followed crystallization of their host diamonds, mineral inclusions in diamonds are divided into three groups: protogenetic, syngenetic and epigenetic. To determine which group the mineral inclusions belong to is very important because it is vital for understanding the data’s meaning. According to the type of mantle source rocks, mineral inclusions in diamonds are usually divided into peridotitic (or ultramafic) suite and eclogitic suite. The mineral species of each suite are described and mineralogical characteristics of most common inclusions in diamonds, such as olivine, clinopyroxene, orthopyroxene, garnet, chromite and sulfide are reviewed in detail. In this paper, the main research fields and findings of diamonds and their inclusions were described: ①getting knowledge of mineralogical and petrologic characteristics of diamond source areas, characteristics of mantle fluids and mantle dynamics processes by studying the major element and trace element compositions of mineral inclusions; ②discussing deep carbon cycle by studying carbon isotopic composition of diamonds; ③determining forming temperature and pressure of diamonds by using appropriate assemblages of mineral inclusions or single mineral inclusion as geothermobarometry, by using the abundance and aggregation of nitrogen impurities in diamonds and by measuring the residual stress that an inclusion remains under within a diamond ; ④estimating the crystallization ages of diamonds by using the aggregation of nitrogen impurities in diamonds and by determine the radiometric ages of syngenetic mineral inclusions in diamonds. Genetic model of craton lithospheric diamonds and their mineral inclusion were also introduced. In the end, the research progress on diamonds and their inclusions in China and the gap between domestic and international research are discussed.     

Mineral inclusions in fibrous diamonds: constraints on cratonic mantle refertilization and diamond formation

We analyzed mineral microinclusions in fibrous diamonds from the Wawa metaconglomerate (Superior craton) and Diavik kimberlites (Slave craton) and compared them with published compositions of large mineral inclusions in non-fibrous diamonds from these localities. The comparison, together with similar datasets available for Ekati and Koffiefontein kimberlites, suggest a general pattern of metasomatic alteration imposed on the ambient mantle by formation of fibrous diamond. Calcium and Fe enrichment of peridotitic garnet and pyroxenes and Fe enrichment of olivine associated with fibrous diamond-forming fluids contributes to refertilization of the cratonic mantle. Saline—carbonatitic—silicic fluid trapped by fibrous diamonds may represent one of the elusive agents of mantle refertilization. Calcium enrichment of peridotitic garnet and pyroxenes is expected in local mantle segments during fibrous diamond production, as Ca in the carbonatitic fluids is deposited into the surrounding mantle when oxidized carbon is reduced to diamond. Harzburgitic garnet evolves towards Ca-rich compositions even when it interacts with Ca-poor saline fluids. An unusual trend of Mg enrichment to Fo_95–98 is observed in some olivine inclusions in Wawa fibrous diamonds. The trend may result from the carbonatitic composition of the fluid that promotes crystallization of magnesian olivine and preferentially oxidizes the fayalite component. We propose a generic model of fibrous and non-fibrous diamond formation from carbonatitic fluids that explains enrichment of the mantle in mafic magmaphile and incompatible elements and accounts for locally metasomatized compositions of diamond inclusions.     

An alternative interpretation of lower mantle mineral associations in diamonds

Diamonds containing ferropericlase (Mg,Fe)O and other silicate (enstatite [(Mg,Fe)SiO₃], in particular) assemblages are generally believed to be derived from the Earth's lower mantle. On the basis of the observed ratio between ferropericlase and enstatite inclusions and the FeO content of these ferropericlases, it is concluded that most of these minerals entrapped in diamonds may not represent the lithology of the lower mantle itself as has been suggested by many investigators. Instead, ferropericlases in these diamonds represent most likely the disproportionate product of ferromagnesite [(Mg,Fe)CO₃], which underwent a decarbonation reaction to form both diamond and ferropericlase simultaneously in the lower mantle. The wide variation in the Mg# of ferropericlase inclusions in diamonds is attributed to the decarbonation "loop" of the MgCO₃-FeCO₃ solid solutions. Some of the enstatite inclusions coexisting with these ferropericlases in the same diamond may represent the most abundant mineral species of (Mg,Fe)SiO₃-perovskite in the lower mantle. The latter mineral phase experienced a retrogressive transition into enstatite during the transport of diamonds to the Earth's surface.     

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.     

Trace elements in sulfide inclusions from Yakutian diamonds

 Sulfide inclusions in diamonds may provide the only pristine samples of mantle sulfides, and they carry important information on the distribution and abundances of chalcophile elements in the deep lithosphere. Trace-element abundances were measured by proton microprobe in >50 sulfide inclusions (SDI) from Yakutian diamonds; about half of these were measured in situ in polished plates of diamonds, providing information on the spatial distribution of compositional variations. Many of the diamonds were identified as peridotitic or eclogitic from the nature of coexisting silicate or oxide inclusions. Known peridotitic diamonds contain SDIs with Ni contents of 22–36%, consistent with equilibration between olivine, monosulfide solid solution (MSS) and sulfide melt, whereas SDIs in eclogitic diamonds contain 0–12% Ni. A group of diamonds without silicate or oxide inclusions has SDIs with 11–18% Ni, and may be derived from pyroxenitic parageneses. Eclogitic SDIs have lower Ni, Cu and Te than peridotitic SDIs; the ranges of the two parageneses overlap for Se, As and Mo. The Mo and Se contents range up to 700 and 300 ppm, respectively; the highest levels are found in peridotitic diamonds. Among the in-situ SDIs, significant Zn and Pb levels are found in those connected by cracks to diamond surfaces, and these elements reflect interaction with kimberlitic melt. Significant levels of Ru (30–1300 ppm) and Rh (10–170 ppm) are found in many peridotitic SDIs; SDIs in one diamond with wustite and olivine inclusions and complex internal structures have high levels of other platinum-group elements (PGEs) as well, and high chondrite-normalized Ir/Pd. Comparison with experimental data on element partitioning between crystals of monosulfide solid solution (MSS) and sulfide melts suggests that most of the inclusions in both parageneses were trapped as MSS, while some high-Cu SDIs with high Pd±Rh may represent fractionated sulfide melts. Spatial variations of SDI composition within single diamonds are consistent with growth histories shown by cathodoluminescence images, in which several stages of growth and resorption have occurred within magmatic environments that evolved during diamond formation. Received: 5 July 1995 / Accepted: 21 February 1996     

The characterisation and origin of graphite in cratonic lithospheric mantle: a petrological carbon isotope and Raman spectroscopic study

Graphite-bearing peridotites, pyroxenites and eclogite xenoliths from the Kaapvaal craton of southern Africa and the Siberian craton, Russia, have been studied with the aim of: 1) better characterising the abundance and distribution of elemental carbon in the shallow continental lithospheric mantle; (2) determining the isotopic composition of the graphite; (3) testing for significant metastability of graphite in mantle rocks using mineral thermobarometry. Graphite crystals in peridotie, pyroxenite and eclogite xenoliths have X-ray diffraction patterns and Raman spectra characteristic of highly crystalline graphite of high-temperature origin and are interpreted to have crystallised within the mantle. Thermobarometry on the graphite-peridotite assemblages using a variety of element partitions and formulations yield estimated equilibration conditions that plot at lower temperatures and pressures than diamondiferous assemblages. Moreover, estimated pressures and temperatures for the graphite-peridotites fall almost exclusively within the experimentally determined graphite stability field and thus we find no evidence for substantial graphite metastability. The carbon isotopic composition of graphite in peridotites from this and other studies varies from δ¹³ C_PDB = ? 12.3 to ? ?3.8%o with a mean of-6.7‰, σ=2.1 (n=22) and a mode between-7 and-6‰. This mean is within one standard deviation of the-4‰ mean displayed by diamonds from peridotite xenoliths, and is identical to that of diamonds containing peridotite-suite inclusions. The carbon isotope range of graphite and diamonds in peridotites is more restricted than that observed for either phase in eclogites or pyroxenites. The isotopic range displayed by peridotite-suite graphite and diamond encompasses the carbon isotope range observed in mid-ocean-ridge-basalt (MORB) glasses and ocean-island basalts (OIB). Similarity between the isotopic compositions of carbon associated with cratonic peridotites and the carbon (as CO₂) in oceanic magmas (MORB/OIB) indicates that the source of the fluids that deposited carbon, as graphite or diamond, in catonic peridotites lies within the convecting mantle, below the lithosphere. Textural observations provide evidence that some of graphite in cratonic peridotites is of sub-solidus metasomatic origin, probably deposited from a cooling C-H-O fluid phase permeating the lithosphere along fractures. Macrocrystalline graphite of primary appearance has not been found in mantle xenoliths from kimberlitic or basaltic rocks erupted away from cratonic areas. Hence, graphite in mantle-derived xenoliths appears to be restricted to Archaean cratons and occurs exclusively in low-temperature, coarse peridotites thought to be characteristic of the lithospheric mantle. The tectonic association of graphite within the mantle is very similar to that of diamond. It is unlikely that this restricted occurrence is due solely to unique conditions of oxygen fugacity in the cratonic lithospheric mantle because some peridotite xenoliths from off-craton localities are as reduced as those from within cratons. Radiogenic isotope systematics of peridotite-suite diamond inclusions suggest that diamond crystallisation was not directly related to the melting events that formed lithospheric peridotites. However, some diamond (and graphite?) crystallisation in southern Africa occurred within the time span associated with the stabilisation of the lithospheric mantle (Pearson et al. 1993). The nature of the process causing localisation of carbon in cratonic mantle roots is not yet clearly understood.     

Metasomatic Eclogitic Diamond Growth: Evidence from Multiple Diamond Inclusions

Diamond formation from metasomatic fluids, rather than from igneous melts, remains controversial but is paramount to our understanding of diamonds' mantle origin(s). Physical and chemical properties of diamonds, their inclusions, and host eclogites from the Mir kimberlite, Yakutia, Russia form the basis for our evaluation of diamond origin. Mir eclogitic diamonds and their multiple inclusions show a definite break in time and temperature between the formation of the core zones and the rims of the diamonds. Extreme changes in chemistry for multiple diamond inclusions (DIs) between the cores and the rims cannot be accounted for by magmatic fractional crystallization. Evidence also exists for large temperature decreases (40° to 140°C) from the cores to the rims of some diamonds. The distinct changes in nitrogen contents and aggregation states from cores to rims of diamonds would appear to reflect different residence times for these portions of the diamonds in the mantle- i.e., formation of cores and rims at vastly different times (e.g., 2 Gy). Many of the mineral-chemical characteristics, including C and N isotopes and N aggregation states of the diamond, can best be explained by crystallization of the diamonds after formation of the eclogite host. This suggests that the formation of the eclogite and the nucleation and growth of some diamonds are not coeval and possibly not cogenetic.

Most diamondiferous eclogite xenoliths probably have never experienced a major magmatic episode (i.e., complete melt stage) after subduction of their crustal protoliths into the mantle. Carbon isotopes in diamond, sulfur isotopes from sulfide DIs, and oxygen isotopes from eclogite minerals all point to crustal protoliths for many eclogites.

All of the factors above, taken as a whole, indicate that many eclogitic diamonds are the result of petrogenesis by metasomatism over a prolonged period of time. Introduction of metasomatic fluids facilitates the precipitation of the diamonds, either in tolo or as rims on previously formed diamonds. Inasmuch as some eclogites are considered to be igneous in origine.g., Group-A eclogites of Taylor and Neal (1989)-it is entirely possible that these eclogites may contain truly igneous diamonds. However, even some of these diamonds may have later metasomatic overgrowths.     

Inclusions in diamonds from Snap Lake kimberlites (Slave Craton,Canada): Geochemical features of crystallization

The results of integrated studies of inclusion-containing diamonds from kimberlites of the Snap Lake dike complex (Canada) are presented. Features of the morphology, defect–impurity composition, and internal structure of the diamonds were determined by optic and scanning microscopy. The chemical composition of crystalline inclusions (olivine, garnet, and pyroxene) in diamonds was studied using a microanalyzer with an electronic probe. The inclusions of ultramafic paragenesis in the diamond (87%) are predominant. Carbonates, sulfide and hydrated silicate phases were found only in multiphase microinclusions. The large phlogopite inclusion studied was similar in composition to earlier studied nanosize inclusions of high-silica mica in diamonds from Snap Lake kimberlites. Revealed features of studied diamonds and presence of high-silica mica suggest that diamonds from Snap Lake have formed as the result of interaction between enriched in volatile and titanium high-potassium carbonate–silicate melts and peridotitic substrate at the base of thick lithospheric mantle.