Inclusions In Diamonds Research Articles

A combined cathodoluminescence and electron backscatter diffraction examination of the growth relationships between Jwaneng diamonds and their eclogitic inclusions

To fully understand the implications of the compositional information recorded by inclusions in diamond it is vital to know if their growth was syn- or protogenetic and the extent to which they have equilibrated with diamond forming agents. The current paradigm is that the majority of inclusions in diamond are syngenetic but recently this assumption has been questioned. This study presents an integrated cathodoluminescence (CL) and electron backscatter diffraction (EBSD) study of 8 diamonds containing eclogitic inclusions: 19 pyrope-almandine garnets, 12 omphacitic clinopyroxenes, 4 sulphides, 1 coesite and 1 rutile from the Jwaneng diamond mine, Botswana. Diamond plates were sequentially polished to expose inclusions at different levels and CL imaging and EBSD were performed to constrain the relationship between diamond and inclusion growth. Despite complex growth and resorption, individual diamonds are single crystals with a homogeneous crystallographic orientation. All individual inclusions have homogeneous crystallographic orientation and no resolvable compositional zonation. The combined CL and EBSD data suggest that epitaxial inclusion-diamond growth is rare (none of 24 inclusions) and that the imposition of cubo-octahedral faces on inclusions does not necessarily result in epitaxy. Individual diamonds contain inclusions that record evidence of both syngentic and protogenetic relationships with the host diamond and in one case an inclusion appears syngenetic to the diamond core but protogenetic to the growth zone that surrounds 70% of the inclusion. These findings emphasise that inclusions in diamonds have multiple modes of origin and that in order to validate the significance of geochronological studies, further work is needed to establish that there is rapid chemical equilibration of protogenetic inclusions with diamond forming agents at mantle temperatures.

Making Cratonic Lithospheric Mantle

AbstractThe origin of cratonic lithospheric mantle has been attributed to either high‐pressure (5–7 GPa) melting in hot mantle plumes or low‐pressure (<5 GPa) melting in mid‐ocean ridges or suprasubduction zones. To resolve this long‐standing debate, it is necessary to confirm under what depths the incipient cratonic mantle melted. Compared with most cratonic mantle xenoliths and xenocrysts, which commonly experienced metasomatic modification after melt extraction, diamond inclusions with predominantly harzburgitic compositions can better track the compositional signature of pristine cratonic mantle. This paper presents thermodynamic calculations performed with THERMOCALC software to establish a quantitative relationship between garnet and cratonic peridotite compositions. Along the normal cratonic geotherm (40 mW/m2), the XCa [atomic Ca/(Ca + Mg + Fe2+)] and Cr# [atomic Cr/(Cr + Al) × 100] values in garnet depend mainly on the bulk CaO/Al2O3 and Cr# values, respectively. Furthermore, mantle melting modeling shows that the Cr# of the residue displays a negative correlation with melting pressure at melt fractions of greater than ~15%. Therefore, the high Cr# values (mostly 12–36) of global garnet inclusions in diamond support a low‐pressure (<4 GPa) origin for cratonic lithospheric mantle. More importantly, the incipient cratonic mantle calculated from the garnet inclusions exhibits similar bulk CaO/Al2O3 and Cr# compositions to oceanic lithosphere but different values from arc lithosphere with higher CaO/Al2O3 and Cr# values. These results imply that cratonic mantle was initially formed by the extensive melting of hot ambient mantle in the Archean ocean ridge environments. The shallow oceanic lithosphere was subsequently stacked to generate the thick and stable cratonic lithospheric mantle.

Carbon and nitrogen isotope, and mineral inclusion studies on the diamonds from the Pozanti–Karsanti chromitite, Turkey

The Pozanti–Karsanti ophiolite (PKO) is one of the largest oceanic remnants in the Tauride belt, Turkey. Micro-diamonds were recovered from the podiform chromitites, and these diamonds were investigated based on morphology, color, cathodoluminescence, nitrogen content, carbon and nitrogen isotopes, internal structure and inclusions. The diamonds recovered from the PKO are mainly mixed-habit diamonds with sectors of different brightness under the cathodoluminescence images. The total δ13C range of the PKO diamonds varies between − 18.8 and − 28.4‰, with a principle δ13C mode at − 25‰. Nitrogen contents of the diamonds range from 7 to 541 ppm with a mean value of 171 ppm, and the δ15N values range from − 19.1 to 16.6‰, with a δ15N mode of − 9‰. Stacking faults and partial dislocations are commonly observed in the Transmission Electron Microscopy foils whereas inclusions are rather rare. Combinations of (Ca0.81Mn0.19)SiO3, NiMnCo-alloy and nano-sized, quenched fluid phases were observed as inclusions in the PKO diamonds. We believe that the 13C-depleted carbon signature of the PKO diamonds derived from previously subducted crustal matter. These diamonds may have crystallized from C-saturated fluids in the asthenospheric mantle at depth below 250 km which were subsequently carried rapidly upward by asthenospheric melts.

Toward a Robust Elastic Geobarometry of Kyanite Inclusions in Eclogitic Diamonds

AbstractHere we report the first results from elastic geobarometry applied to a kyanite inclusion entrapped within an eclogitic diamond (from Voorspoed mine, South Africa) using micro‐Raman and Fourier transform infrared spectroscopy, electron microprobe analysis, ab initio calculations, and finite element modeling. Application of elastic geobarometry to very elastically anisotropic kyanite inclusions is challenging, as current models do not allow for elastic anisotropy. In order to minimize the effects of anisotropy, we have explored the effects of deviatoric stress on Raman modes via ab initio density functional theory. The results allowed us to select the Raman mode (at ca. 638 cm−1) that is the least sensitive to deviatoric stress. The shift of this band in the inclusion while still trapped within the diamond relative to the inclusion in air (once liberated) was used under hydrostatic approximation to determine a residual pressure on the inclusion of 0.184 ± 0.045 GPa and an entrapment pressure of 5.2 ± 0.3 GPa (~160 km depth) for an FTIR N‐aggregation residence temperature of 1119 ± 50 °C. This is the first geothermobarometric determination for a diamond from the Voorspoed kimberlite. It overlaps with P–T estimates obtained by traditional chemical geobarometry for diamonds from other kimberlites from the Kaapvaal craton, suggesting that the hydrostatic approximation does not introduce significant errors in the geobarometric evaluation. Our protocol of Raman peak selection can be used for geobarometry of further kyanite‐bearing diamonds and may provide a guide for more robust geobarometry of other types of mineral inclusions in diamonds, both eclogitic and peridotitic.

Mineral inclusions in diamonds from Karowe Mine, Botswana: super-deep sources for super-sized diamonds?

Mineral inclusions in diamonds play a critical role in constraining the relationship between diamonds and mantle lithologies. Here we report the first major and trace element study of mineral inclusions in diamonds from the Karowe Mine in north-east Botswana, along the western edge of the Zimbabwe Craton. From a total of 107 diamonds, 134 silicate, 15 oxide, and 22 sulphide inclusions were recovered. The results reveal that 53% of Karowe inclusion-bearing diamonds derived from eclogitic sources, 44% are peridotitic, 2% have a sublithospheric origin, and 1% are websteritic. The dominant eclogitic diamond substrates sampled at Karowe are compositionally heterogeneous, as reflected in wide ranges in the CaO contents (4–16 wt%) of garnets and the Mg# (69–92) and jadeite contents (14–48 mol%) of clinopyroxenes. Calculated bulk rock REEN patterns indicate that both shallow and deep levels of the subducted slab(s) were sampled, including cumulate-like protoliths. Peridotitic garnet compositions largely derive from harzburgite/dunite substrates (~90%), with almost half the garnets having CaO contents <1.8 wt%, consistent with pyroxene-free (dunitic) sources. The highly depleted character of the peridotitic diamond substrates is further documented by the high mean and median Mg# (93.1) of olivine inclusions. One low-Ca garnet records a very high Cr2O3 content (14.7 wt%), implying that highly depleted cratonic lithosphere at the time of diamond formation extended to at least 220 km depth. Inclusion geothermobarometry indicates that the formation of peridotitic diamonds occurred along a 39–40 mW/m2 model geotherm. A sublithospheric inclusion suite is established by three eclogitic garnets containing a majorite component, a feature so far unique within the Orapa cluster. These low- and high-Ca majoritic garnets follow pyroxenitic and eclogitic trends of majoritic substitution, respectively. The origin of the majorite-bearing diamonds is estimated to be between 330 to 420 km depth, straddling the asthenosphere–transition zone boundary. This new observation of superdeep mineral inclusions in Karowe diamonds is consistent with a sublithospheric origin for the exceptionally large diamonds from this mine.

Noble gas geochemistry of fluid inclusions in South African diamonds: implications for the origin of diamond-forming fluids

Fibrous diamond growth zones often contain abundant high-density fluid (HDF) inclusions and these provide the most direct information on diamond-forming fluids. Noble gases are incompatible elements and particularly useful in evaluating large-scale mantle processes. This study further constrains the evolution and origin of the HDFs by combining noble gas systematics with δ13C, N concentrations, and fluid inclusion compositions for 21 individual growth zones in 13 diamonds from the Finsch (n = 3), DeBeers Pool (n = 7), and Koffiefontein (n = 3) mines on the Kaapvaal Craton. C isotope compositions range from −2.8 to −8.6‰ and N contents vary between 268 and 867 at.ppm, except for one diamond with contents of <30 at.ppm N. Nine of the thirteen studied diamonds contained saline HDF inclusions, but the other four diamonds had carbonatitic or silicic HDF inclusions. Carbonatitic and silicic HDFs yielded low He concentrations, R/Ra (3He/4Hesample/3He/4Heair) values of 3.2–6.7, and low 40Ar/36Ar ratios of 390–1940. Noble gas characteristics of carbonatitic-silicic HDFs appear consistent with a subducted sediment origin and interaction with eclogite. Saline HDFs are characterised by high He concentrations, with R/Ra mostly between 3.9 and 5.7, and a wide range in 40Ar/36Ar ratios (389–30,200). The saline HDFs likely originated from subducted oceanic crust with low He but moderate Ar contents. Subsequent interaction of these saline HDFs with mantle peridotite could explain the increase in He concentrations and mantle-like He isotope composition, with the range in low to high 40Ar/36Ar ratios dependent on the initial 36Ar content and extent of lithosphere interaction. The observed negative correlation between 4He contents and R/Ra values in saline HDFs indicates significant in situ radiogenic 4He production.

Super-reducing conditions in ancient and modern volcanic systems: sources and behaviour of carbon-rich fluids in the lithospheric mantle

Oxygen fugacity (ƒO2) is a key parameter of Earth’s mantle, because it controls the speciation of the fluids migrating at depth; a major question is whether the sublithospheric mantle is metal-saturated, keeping ƒO2 near the Iron-Wustite (IW) buffer reaction. Cretaceous basaltic pyroclastic rocks on Mt. Carmel, Israel erupted in an intraplate environment with a thin, hot lithosphere. They contain abundant aggregates of hopper-shaped crystals of Ti-rich corundum, which have trapped melts with phenocryst assemblages (Ti2O3, SiC, TiC, silicides, native V) requiring extremely low ƒO2. These assemblages are interpreted to reflect interaction between basaltic melts and mantle-derived fluids dominated by CH4 + H2. Similar highly reduced assemblages are found associated with volcanism in a range of tectonic situations including subduction zones, major continental collisions, intraplate settings, craton margins and the cratons sampled by kimberlites. This distribution, and the worldwide similarity of δ13C in mantle-derived SiC and associated diamonds, suggest a widespread process, involving similar sources and independent of tectonic setting. We suggest that the common factor is the ascent of abiotic (CH4 + H2) fluids from the sublithospheric mantle; this would imply that much of the mantle is metal-saturated, consistent with observations of metallic inclusions in sublithospheric diamonds (e.g. Smith et al. 2016). Such fluids, perhaps carried in rapidly ascending deep-seated magmas, could penetrate high up into a depleted cratonic root, establishing the observed trend of decreasing ƒO2 with depth (e.g. Yaxley et al. in Lithos 140:142–151, 2012). However, repeated metasomatism (associated with the intrusion of silicate melts) will raise the FeO content near the base of the craton over time, developing a carapace of oxidizing material that would prevent the rise of CH4-rich fluids into higher levels of the subcontinental lithospheric mantle (SCLM). Oxidation of these fluids would release CO2 and H2O to drive metasomatism and low-degree melting both in the carapace and higher in the SCLM. This model can explain the genesis of cratonic diamonds from both reduced and oxidized fluids, the existence of SiC as inclusions in diamonds, and the abundance of SiC in some kimberlites. It should encourage further study of the fine fractions of heavy-mineral concentrates from all types of explosive volcanism.

Ferropericlase inclusions in ultradeep diamonds from Sao Luiz (Brazil): high Li abundances and diverse Li-isotope and trace element compositions suggest an origin from a subduction mélange

The most remarkable feature of the inclusion suite in ultradeep alluvial and kimberlitic diamonds from Sao Luiz (Juina area in Brazil) is the enormous range in Mg# [100xMg/(Mg + Fe)] of the ferropericlases (fper). The Mg-richer ferropericlases are from the boundary to the lower mantle or from the lower mantle itself when they coexist with ringwoodite or Mg- perovskite (bridgmanite). This, however, is not an explanation for the more Fe-rich members and a lowermost mantle or a “D” layer origin has been proposed for them. Such a suggested ultra-deep origin separates the Fe-rich fper-bearing diamonds from the rest of the Sao Luiz ultradeep diamond inclusion suite, which also contains Ca-rich phases. These are now thought to have an origin in the uppermost lower mantle and in the transition zone and to belong either to a peridotitic or mafic (subducted oceanic crust) protolith lithology. We analysed a new set of more Fe-rich ferropericlase inclusions from 10 Sao Luiz ultradeep alluvial diamonds for their Li isotope composition by solution MC-ICP-MS (multi collector inductively coupled plasma mass spectrometry), their major and minor elements by EPMA (electron probe micro-analyser) and their Li-contents by SIMS (secondary ion mass spectrometry), with the aim to understand the origin of the ferropericlase protoliths. Our new data confirm the wide range of ferropericlase Mg# that were reported before and augment the known lack of correlation between major and minor elements. Four pooled ferropericlase inclusions from four diamonds provided sufficient material to determine for the first time their Li isotope composition, which ranges from δ7Li + 9.6 ‰ to −3.9 ‰. This wide Li isotopic range encompasses that of serpentinized ocean floor peridotites including rodingites and ophicarbonates, fresh and altered MORB (mid ocean ridge basalt), seafloor sediments and of eclogites. This large range in Li isotopic composition, up to 5 times higher than ‘primitive upper mantle’ Li-abundances, and an extremely large and incoherent range in Mg# and Cr, Ni, Mn, Na contents in the ferropericlase inclusions suggests that their protoliths were members of the above lithologies. This melange of altered rocks originally contained a variety of carbonates (calcite, magnesite, dolomite, siderite) and brucite as the secondary products in veins and as patches and Ca-rich members like rodingites and ophicarbonates. Dehydration and redox reactions during or after deep subduction into the transition zone and the upper parts of the lower mantle led to the formation of diamond and ferropericlase inclusions with variable compositions and a predominance of the Ca-rich, high-pressure silicate inclusions. We suggest that the latter originated from peridotites, mafic rocks and sedimentary rocks as redox products between calcite and SiO2.

Fate of water transported into the deep mantle by slab subduction

The roles of water in the mantle transition zone, lower mantle, and the core-mantle boundary are investigated. The evidence for a wet mantle transition zone has been suggested based on hydrous mineral inclusions in diamond. Seismic wave velocity and electrical conductivity profiles together with mineral physics data are consistent with existence of stagnant slabs in a wet mantle transition zone. The transition zone may contain continental crustal components in these stagnant slabs. Dense hydrous magmas may exist at the base of the upper mantle. Fluids or volatile-rich magmas may also exist at the top of the lower mantle due to the large contrast in water contents between the mineral assemblages in the mantle transition zone and the lower mantle, and the crossing of the convective descent of the cold hydrated materials. Dense magmas are not likely to be formed at the top of the lower mantle and hydrous magmas generated in this region move upwards and metasomatize the overlying mantle transition zone. Water can be transported deeper into the lower mantle by gravitational collapse of the stagnant slabs, which supply water into the lower mantle, including the core-mantle boundary. Hydrous δ-H solid solution may be the most important hydrous phase in lower mantle, and existence of this phase reduces the aluminum content in coexisting bridgmanite and post-perovskite, and thus modifies the physical properties of the lower mantle. Hydrous δ-H solid solution can accumulate at the base of the lower mantle. The iron-water reaction at the core-mantle boundary can also create pyrite-type FeOOH which can be a potential candidate material for the ultralow velocity zone (ULVZ).

A large planetary body inferred from diamond inclusions in a ureilite meteorite

Planetary formation models show that terrestrial planets are formed by the accretion of tens of Moon- to Mars-sized planetary embryos through energetic giant impacts. However, relics of these large proto-planets are yet to be found. Ureilites are one of the main families of achondritic meteorites and their parent body is believed to have been catastrophically disrupted by an impact during the first 10 million years of the solar system. Here we studied a section of the Almahata Sitta ureilite using transmission electron microscopy, where large diamonds were formed at high pressure inside the parent body. We discovered chromite, phosphate, and (Fe,Ni)-sulfide inclusions embedded in diamond. The composition and morphology of the inclusions can only be explained if the formation pressure was higher than 20 GPa. Such pressures suggest that the ureilite parent body was a Mercury- to Mars-sized planetary embryo.

Inclusions in diamonds constrain thermo-chemical conditions during Mesozoic metasomatism of the Kaapvaal cratonic mantle

Fluid/melt inclusions in diamonds, which were encapsulated during a metasomatic event and over a short period of time, are isolated from their surrounding mantle, offering the opportunity to constrain changes in the sub-continental lithospheric mantle (SCLM) that occurred during individual thermo-chemical events, as well as the composition of the fluids involved and their sources. We have analyzed a suite of 8 microinclusion-bearing diamonds from the Group I De Beers Pool kimberlites, South Africa, using FTIR, EPMA and LA-ICP-MS. Seven of the diamonds trapped incompatible-element-enriched saline high density fluids (HDFs), carry peridotitic mineral microinclusions, and substitutional nitrogen almost exclusively in A-centers. This low-aggregation state of nitrogen indicates a short mantle residence times and/or low mantle ambient temperature for these diamonds. A short residence time is favored because, elevated thermal conditions prevailed in the South African lithosphere during and following the Karoo flood basalt volcanism at ∼180 Ma, thus the saline metasomatism must have occurred close to the time of kimberlite eruptions at ∼85 Ma. Another diamond encapsulated incompatible-element-enriched silicic HDFs and has 25% of its nitrogen content residing in B-centers, implying formation during an earlier and different metasomatic event that likely relates to the Karoo magmatism at ca. 180 Ma.Thermometry of mineral microinclusions in the diamonds carrying saline HDFs, based on Mg–Fe exchange between garnet–orthopyroxene (Opx)/clinopyroxene (Cpx)/olivine and the Opx–Cpx thermometer, yield temperatures between 875–1080 °C at 5 GPa. These temperatures overlap with conditions recorded by touching inclusion pairs in diamonds from the De Beers Pool kimberlites, which represent the mantle ambient conditions just before eruption, and are altogether lower by 150–250 °C compared to P–T gradients recorded by peridotite xenoliths from the same locality. Oxygen fugacity (fO2) differs as well. The fO2 calculated for the saline HDF compositions (Δlog⁡fO2(FMQ)=−2.47 to −1.34) are higher by about a log unit compared with that recorded by xenoliths at 4–7 GPa.We conclude that enriched saline HDFs mediated the metasomatism that preceded Group I kimberlite eruptions in the southwestern Kaapvaal craton, and that their ‘cold and oxidized’ nature reflects their derivation from a deep subducting slab. This event had little impact on the temperature and redox state of the Kaapvaal lithosphere as a reservoir, however, it likely affected its properties along limited metasomatized veins and their wall rock. To reconcile the temperature and oxygen fugacity discrepancy between inclusions in diamonds and xenoliths, we argue that xenoliths did not equilibrate during the last saline metasomatic event or kimberlite eruption. Thus the P–T–fO2 gradients they record express pre-existing lithospheric conditions that were likely established during the last major thermal event in the Kaapvaal craton (i.e. the Karoo magmatism at ca. 180 Ma).

Carbonate–Silicate–Sulfide Polyphase Inclusion in Diamond from the Komsomolskaya Kimberlite Pipe, Yakutia

An aragonite inclusion in natural diamond was identified using techniques of transmission electron microscopy, electron microdiffraction, and microprobe analysis. The inclusion is hosted in a colorless octahedral diamond crystal from the Komslomolskaya pipe in Yakutia. The diamond crystal shows a zoned distribution of its admixtures and defects. The structure parameters of the inclusion (∠[001]/[201] = 66° and certain lattice spacings) correspond to the calculated parameters of the orthorhombic unit cell of a Ca carbonate polymorph. The aragonite inclusion contains admixtures of MgO (0.81), MnO (0.58), and FeO (0.13 wt %). The find of a syngenetic aragonite inclusion in diamond is unique and proves that diamond can be formed in carbonatized mantle peridotite at depths of at least 300 km. The inclusion hosts identifiable microphases of Ni-rich sulfides (37–41 wt % Ni), titanite, hydrous silicate, magnetite, and fluid. This association indicates that the diamond and aragonite crystallized from a carbonate–silicate–sulfide melt or highdensity fluid.

Ice-VII inclusions in diamonds: Evidence for aqueous fluid in Earth's deep mantle.

Water-rich regions in Earth's deeper mantle are suspected to play a key role in the global water budget and the mobility of heat-generating elements. We show that ice-VII occurs as inclusions in natural diamond and serves as an indicator for such water-rich regions. Ice-VII, the residue of aqueous fluid present during growth of diamond, crystallizes upon ascent of the host diamonds but remains at pressures as high as 24 gigapascals; it is now recognized as a mineral by the International Mineralogical Association. In particular, ice-VII in diamonds points toward fluid-rich locations in the upper transition zone and around the 660-kilometer boundary.

Encapsulating Earth's deep water filter

Geochemistry Small inclusions in diamonds brought up from the mantle provide valuable clues to the mineralogy and chemistry of parts of Earth that we cannot otherwise sample. Tschauner et al. found inclusions of the high-pressure form of water called ice-VII in diamonds sourced from between 410 and 660 km depth, the part of the mantle known as the transition zone. The transition zone is a region where the stable minerals have high water storage capacity. The inclusions suggest that local aqueous pockets form at the transition zone boundary owing to the release of chemically bound water as rock cycles in and out of this region. Science , this issue p. [1136][1] [1]: /lookup/doi/10.1126/science.aao3030

STRUCTURAL SURFACE TRANSFORMATIONS OF COPPER COATING WITH INCLUSIONS OF UDD AND DS ADDITIVES IN CITRATE COPPER COATING ELECTROLYTE

The properties of composite copper coatings with inclusions of ultradispersed diamonds (UDD) and diamond soot (DS) in copper citrate electrolyte have been investigated. The concentrations of diamond-containing additives have been varied in the range of 0.2–2 g/l. Sizes of copper microcrystals, UDD and DS particles were determined from the scanning electron microscopy images. By means of the X-ray fluorescent analysis, the interrelation between concentration of diamondbearing additives in electrolyte and their content in the obtained coatings has been established. The minimal microporosity and the maximal microhardness correspond to concentration of 1.0 g/l for both UDD and DS suspensions in citrate copper coating electrolytes. Copper-UDD coating has increased protective properties (porosity 2 time/cm2 ) and uniformity of distribution of diamond-bearing particles on a surface in comparison with a monocoating and copper-DS coating. Using UDD in citrate copper coating electrolyte with a concentration of diamond-bearing additive of 1.0 g/l is more preferable for production of composite electrochemical coatings.

Mineral inclusions in diamonds from Chapada Diamantina, Bahia, Brazil: a Raman spectroscopic characterization

Abstract The Chapada Diamantina, located in the central region of the State of Bahia, is of important historical significance due to its diamond occurrences. Discovered in the nineteenth century, comprehensive research about the regional diamonds and their origins are still limited, demanding more investigation in the matter. Looking for insights about their genesis, mineral inclusions in 23 alluvial diamonds from 4 garimpos located in the Chapada Diamantina were analyzed through the use of Raman micro spectroscopy. Additionally, the characteristics of nitrogen aggregation of the host diamonds were measured using Fourier-transform infrared spectroscopy (FTIR). The diamonds from Chapada Diamantina consist mainly of well-formed crystals, with dominant dodecahedral habits, characterized by faint to very light yellow body colors, typically with green and brown radiation spots on their surface. The main surface textures observed are related to processes that took place in the late stage resorption and during the residence of the diamonds in placer environments. The diamonds are predominantly type IaAB, with a significant occurrence of poorly aggregated nitrogen (Type IaA diamond). The main mineral assemblages of the studied peridotitic inclusions refer to a harzburgitic paragenesis.

Why are diamonds preserved in UHP metamorphic complexes? Experimental evidence for the effect of pressure on diamond graphitization

ABSTRACTThe preservation of metastable diamond in ultrahigh-pressure metamorphic (UHPM) complexes challenges our understanding of the processes taking place during exhumation of these subduction zone complexes. The presence of diamonds in UHPM rocks implies that diamonds remained metastable during exhumation, and within thermodynamic stability of graphite for an extended period. This work studies the influence of pressure on the surface graphitization rate of diamond monocrystals in carbonate systems to understand the preservation of microdiamond during exhumation of UHP subduction complexes. Experiments were performed with 2–3 mm synthetic diamond monocrystals at 2–4 GPa in СаСО3 (1550°С) and К2СО3 (1450°С) melts using a high-pressure multi-anvil apparatus. The highest rate of surface graphitization took place at 2 GPa; diamond crystals were almost completely enveloped by a graphite coating. At 4 GPa, only octahedron-shaped pits formed on flat {111} diamond crystal faces. Our results demonstrate that the surface graphitization rate of diamonds in the presence of carbonate melts at 1450–1550°C increases with decreasing pressure. Decreased pressure alone can graphitize diamond regardless of exhumation rate. Metastable diamond inclusions survive exhumation with little or no graphitization because of excess pressure up to 2 GPa acting on them, and because inclusions are protected from interaction with C-O-H fluid.

Interaction of peridotite with Ca-rich carbonatite melt at 3.1 and 6.5 GPa: Implication for merwinite formation in upper mantle, and for the metasomatic origin of sublithospheric diamonds with Ca-rich suite of inclusions

We performed an experimental study, designed to reproduce the formation of an unusual merwinite + olivine-bearing mantle assemblage recently described as a part of a Ca-rich suite of inclusions in sublithospheric diamonds, through the interaction of peridotite with an alkali-rich Ca-carbonatite melt, derived from deeply subducted oceanic crust. In the first set of experiments, we studied the reaction between powdered Mg-silicates, olivine and orthopyroxene, and a model Ca-carbonate melt (molar Na:K:Ca = 1:1:2), in a homogeneous mixture, at 3.1 and 6.5 GPa. In these equilibration experiments, we observed the formation of a merwinite + olivine-bearing assemblage at 3.1 GPa and 1200 °C and at 6.5 GPa and 1300–1400 °C. The melts coexisting with this assemblage have a low Si and high Ca content (Ca# = molar 100 × Ca/(Ca + Mg) > 0.57). In the second set of experiments, we investigated reaction rims produced by interaction of the same Ca-carbonate melt (molar Na:K:Ca = 1:1:2) with Mg-silicate, olivine and orthopyroxene, single crystals at 3.1 GPa and 1300 °C and at 6.5 GPa and 1400 °C. The interaction of the Ca-carbonate melt with olivine leads to merwinite formation through the expected reaction: 2Mg2SiO4 (olivine) + 6CaCO3 (liquid) = Ca3MgSi2O8 (merwinite) + 3CaMg(CO3)2 (liquid). Thus, our experiments confirm the idea that merwinite in the upper mantle may originate via interaction of peridotite with Ca-rich carbonatite melt, and that diamonds hosting merwinite may have a metasomatic origin. It is remarkable that the interaction of the Ca-carbonate melt with orthopyroxene crystals does not produce merwinite both at 3.1 and 6.5 GPa. This indicates that olivine grain boundaries are preferable for merwinite formation in the upper mantle.

The uniquely high-temperature character of Cullinan diamonds: A signature of the Bushveld mantle plume?

The mantle beneath the Cullinan kimberlite (formerly known as “Premier”) is a unique occurrence of diamondiferous cratonic mantle where diamonds were generated contemporaneously and shortly following a mantle upwelling that led to the formation of a Large Igneous Province that produced the world's largest igneous intrusion – the 2056 Ma Bushveld Igneous Complex (BIC). We studied 332 diamond inclusions from 202 Cullinan diamonds to investigate mantle thermal effects imposed by the formation of the BIC. The overwhelming majority of diamonds come from three parageneses: (1) lithospheric eclogitic (69%), (2) lithospheric peridotitic (21%), and (3) sublithospheric mafic (9%). The lithospheric eclogitic paragenesis is represented by clinopyroxene, garnet, coesite and kyanite. Main minerals of the lithospheric peridotitic paragenesis are forsterite, enstatite, Cr-pyrope, Cr-augite and spinel; the sublithospheric mafic association includes majorite, CaSiO3 phases and omphacite. Diamond formation conditions were calculated using an Al-in-olivine thermometer, a garnet-clinopyroxene thermometer, as well as majorite and Raman barometers. The Cullinan diamonds may be unique on the global stage in recording a cold geotherm of 40 mW/m2 in cratonic lithosphere that was in contact with underlying convecting mantle at temperatures of 1450–1550 °C. The studied Cullinan diamonds contain a high proportion of inclusions equilibrated at temperatures exceeding the ambient 1327 °C adiabat, i.e. 54% of eclogitic diamonds and 41% of peridotitic diamonds. By contrast, ≤1% of peridotitic diamond inclusions globally yield equally high temperatures. We propose that the Cullinan diamond inclusions recorded transient, slow-dissipating thermal perturbations associated with the plume-related formation of the ~2 Ga Bushveld igneous province. The presence of inclusions in diamond from the mantle transition zone at 300–650 km supports this view. Cullinan xenoliths indicative of the thermal state of the cratonic lithosphere at ~1.2 Ga are equilibrated at the relatively low temperatures, not exceeding adiabatic. The ability of diamonds to record super-adiabatic temperatures may relate to their entrainment from the deeper, hotter parts of the upper mantle un-sampled by the kimberlite in the form of xenoliths or their equilibration in a younger lithosphere after a decay of the thermal disturbance.

Interaction of Titanium Minerals and Their Melts with Diamond-Forming Media (Experiments at 7–8 GPa)

Melting relations in the multicomponent diamond-forming systems of the upper mantle with a boundary of K–Na–Mg–Fe–Ca carbonate, phases of the model peridotite and eclogite, carbon, and titanium minerals from kimberlite (ilmenite FeTiO3, perovskite CaTiO3, and rutile TiO2) were studied experimentally at 7–8 GPa and 1600–1650°C. Perovskite reacts with the formation of rutile in the diamond-forming silicate–carbonate melts. We discovered liquid immiscibility between melts of titanium minerals, on the one hand, and carbonate–carbon, peridotite–carbonate–carbon, and eclogite–carbonate–carbon diamond-forming melts, on the other. The solubility of titanium mineral in diamond-forming melts is negligible independent of their concentration in the experimental systems. Growth melts retain high diamond-forming efficiency. In general, the experimental results are evident for the xenogenic nature of titanium minerals in inclusions in diamond and, therefore, in diamond-forming melts. It is shown that the physicochemical factors that may correlate the diamond content with the concentration of Ti in kimberlite do not occur during the diamond genesis in silicate–carbonate–carbon parental melts containing titanium minerals and their melts.