Kimberlite Ascent Research Articles

40Ar diffusion in phlogopite: [formula omitted] atomistic calibration and implications for Ar–melt–solid kinetic interactions and ascent dynamics of mantle xenoliths and kimberlites

40Ar/39Ar ages of phlogopite from kimberlite-hosted mantle xenoliths are commonly older than the kimberlite eruption, despite the fact that argon is supposed not to be retained by phlogopite at temperatures above hydrothermally-derived Ar closure temperatures (<500°C). Combining Molecular Dynamics (MD) with Nudged Elastic Band (NEB) and Transition State Theory (TST), we investigate 40Ar−PVT (Pressure−Volume−Temperature) relationships in pristine, defect-free, phlogopite and show that 40Ar diffusivity is several orders of magnitude slower than existing estimates with a strong effect of pressure on diffusion rates and retention of 40Ar at mantle conditions. These results imply to fundamentally revise residence- and transit-time estimates based on Ar kinetics in phlogopite assuming simple diffusive relaxation during upwelling. When accounting for pressure, 40Ar retention trends in phlogopite predict substantially slower kimberlite ascent rates than documented by independent chronometers, indicating that 40Ar resetting during ascent in phlogopite does not result from simple decompression-driven diffusive relaxation. We argue that 40Ar remobilization probably involves secondary structural–textural modifications induced by reaction-driven recrystallization or rim overgrowth. These findings have far-reaching consequences in terms of argon isotopic mobility at mantle depths as well as for dating and tracing metasomatic events during crust−mantle interactions in the evolution of the subcontinental mantle.

Reaction Rims on Ilmenite and Chromite: Implications for Volatile Behavior and Crystallization Conditions of Kimberlite Magma

Abstract Significant uncertainty surrounds the crystallization conditions and the composition of kimberlite melts, including the role of volatiles (H2O and CO2) due to their hybrid nature, intense alteration, and volatile loss during emplacement. In this study, we address these uncertainties by investigating the interaction between oxides (ilmenite and chromite) and kimberlite magma. During kimberlite ascent, mantle minerals react with the magma and develop dissolution textures, compositional zoning, and rims of secondary mineral phases in response to crystallization conditions and the composition of kimberlite magma. We examined oxides from several lithologies within the BK1 and AK15 kimberlites of the Orapa cluster in Botswana, where diamonds demonstrate distinct dissolution styles in each lithological unit owing to differences in magma saturation with volatiles. Here we discovered a strong correlation of the reaction products on ilmenite and chromite with the dissolution style of diamonds in the same kimberlite unit. Diamonds with glossy, low-relief surface features indicative of fluid-rich magma occur in the kimberlite units where ilmenite and chromite develop reaction rims of Ti-bearing phases. Diamonds with corrosion sculptures implying a volatile-undersaturated magma occur in kimberlite units with heavily resorbed chromite and ilmenite completely replaced by a MUM (magnesio-ulvöspinel-magnetite)–perovskite symplectite. Furthermore, the composition of ilmenite reaction rims depends on kimberlite lithology, where MUM co-exists with perovskite or its break-down product anatase in the two coherent kimberlite units, or with perovskite and titanite in the massive volcaniclastic unit. We examine how decompression, cooling, degassing, or assimilation of crustal rocks by kimberlite magma could have shifted conditions from perovskite to titanite stability in the volcaniclastic kimberlite unit. We propose perovskite replacement by anatase-calcite pseudomorphs in the top coherent unit, from which diamonds exhibit an overprint of fluid resorption with a melt resorption. Composition of ilmenite reaction rims provides estimates of kimberlite crystallization temperatures of 730–1275 °C and oxygen fugacities of +0.5 to −3.5 relative to the nickel-nickel oxide buffer, which are validated through controlled experiments. Our study shows that preservation of ilmenite, the type of Ti-phase in its reaction rim, the relative rate of chromite dissolution, and compositional re-equilibration with kimberlite can help model the eruption process as well as the style and rate of diamond dissolution.

Confocal Raman spectroscopic study of melt inclusions from peridotite xenoliths in economic and barren kimberlites from Kaapvaal Craton

AbstractMelt inclusions trapped in minerals inside xenoliths from kimberlites can help to examine the composition of kimberlite melt and/or metasomatic processes in the subcratonic lithospheric mantle as well as shed more light on the role of these melts in diamond destruction. In this study, confocal Raman spectroscopy of secondary melt inclusions in olivine from xenoliths in five different Kaapvaal Craton kimberlites was used for testing any compositional differences between melt inclusions from economically productive (Bultfontein and Frank Smit) and uneconomic diamond barren (Matsoku, Thaba Putsoa, and Pipe 200) kimberlite pipes. The xenoliths represent a range of pressures (37–45 kbar) and temperatures (1000–1300°C). The 26 daughter minerals identified within melt inclusions include Ca–Mg (±Na, K, P, Cl)‐bearing carbonates, alkali (±Ca, Ba, Cl, F, H2O, CO2)‐bearing sulfates, phosphates, oxides, silicates, and a rare nitrate. The mineral assemblages in melt inclusions are similar in both economic and barren kimberlite pipes from the interior and the edge of the craton, indicating the similar composition of the entrapped melts in all studied samples. However, the petrographic study revealed different metasomatic processes recorded by xenoliths from barren and economic kimberlites. Metasomatism by a melt enriched in K, Ca, and H2O could be instrumental in diamond destruction and the low diamond grade of the three barren kimberlites from Lesotho. Our study revealed no effect of kimberlite melt composition on diamond preservation in the studied kimberlites: instead, diamond grade is most likely affected by diamond destruction in the mantle source prior to kimberlite emplacement with kimberlite ascent.

The capturing and decompression of melt inclusions in olivine and ilmenite megacrysts from the Monastery kimberlite, South Africa

Ilmenite and olivine megacrysts from the 89 Ma Monastery kimberlite (Kaapvaal Craton, South Africa) captured abundant and large melt inclusions containing quenched Si-Mg-rich melt, calcite, spinel, perovskite, phlogopite, and serpentine. Textural observations and 3D X-ray tomography of ilmenite and olivine megacrysts show melt inclusion shapes, sizes and distribution patterns indicative of melt capture during primary crystal growth near the base of the subcontinental lithospheric mantle (SCLM). Patterns supporting secondary melt injection along fractures or veins, such as planar arrays of melt inclusions, are absent. Melt inclusions in olivine, in some examples reaching the dimension of centimetres, likely were captured in skeletal voids forming in fast growing, up to decimetre-sized olivine megacrysts. These large melt inclusions commonly decrepitated, forming apophyses, radial fractures, and veins, along which residual volatile- and Si-Mg-rich melt was extracted. We attribute the decrepitation of melt inclusions in olivine to the rapidly increasing difference between the melt pressure in the inclusions, captured at mantle depth, and the decreasing confining stress to which the host olivines were exposed during magma ascent and after emplacement. In ilmenite, melt inclusions up to ∼ 6 mm in diameter remained commonly intact during the kimberlite ascent from its mantle source to the shallow crust. The quenched silicate melt in olivine- and ilmenite-hosted melt inclusions, in some places preserved as unaltered hydrous and CO3-bearing glass, shows systematic major element compositional variations that suggest that this melt formed by similar fractionation and depletion processes, irrespective of the hosting megacryst phase. Apparent modal variations in quenched silicate melt, calcite, and oxide contents suggest that the melt batches captured as inclusions in ilmenite and olivine either record different evolution stages in the megacryst magma, or document compositional heterogeneities in this magma at the time of megacryst growth.

Mantle-Derived Cargo vs Liquid Line of Descent: Reconstructing the P–T–fO2–X Path of the Udachnaya–East Kimberlite Melts during Ascent in the Siberian Sub-Cratonic Lithosphere

Abstract Disentangling the physico-chemical evolution of the melts that give rise to kimberlites during their genesis, ascent through the sub-cratonic lithosphere and emplacement in the crust is challenging. This is because the extensive entrainment and assimilation of, and reaction with, mantle-derived material makes kimberlites mixtures of xenocrystic, magmatic components and alteration minerals, rarely preserving evidence of their original melt composition. Here, a detailed textural and compositional study of coherent and volcaniclastic kimberlite units from the Udachnaya–East pipe (Siberian craton) was performed to reconstruct the pressure–temperature–oxygen fugacity-compositional (P–T–fO2–X) path of kimberlite melts during their ascent through the sub-cratonic lithosphere. Routine and high-precision electron microprobe analyses of olivine, phlogopite and Fe–Ti oxides enabled to discriminate the mantle-derived cargo from the magmatic components, and thus make inferences on the liquid line of descent (LLD) of proto-kimberlite to kimberlite melts. Most of the olivine cores in Udachnaya–East kimberlite are xenocrystic and record conditions of last equilibration in the Siberian sub-cratonic lithospheric mantle at T–P ranging from 812–1227°C at 3.1–5.4 GPa, to 871–1170°C at 4.6–7.0 GPa, depending on the chosen model geotherm (35 mW/m2 vs 40 mW/m2). Based on their Ni, Cr, Mn, Al and P vs Mg/Fe systematics, olivine core populations were associated to the sheared, granular garnet-bearing or spinel-bearing cratonic peridotites. The occurrence of olivine Internal Zones (I) having the same composition as Fe-rich cores, as well as rare mantle-derived xenocrystic cores of phlogopite, bear witness of mantle metasomatism preceding kimberlite ascent. The assimilation of mantle material by initially H2O- and P-rich proto-kimberlitic melts is recorded by the cotectic formation of magmatic olivine Internal Zones (II) and phlogopite Internal Zones around resorbed xenocrystic cores. The LLD then evolved by inducing cotectic precipitation of olivine, phlogopite rims and Cr-spinel at P of 1.5–3.0 GPa, T of 1120–1250°C and fO2 from −2.8 to −1.6 ΔFMQ. Ilmenite–magnetite pairs in the groundmass record the later conditions of crystallization that occurred at P of ~1.0 GPa, T from 1133°C down to 1000°C and fO2 of +0.3 to +0.9 ΔFMQ. These results confirm the progressive oxidation of the melt that finally led to the formation of calcite, apatite and Mg-rich olivine and phlogopite rinds. The F-enrichment of phlogopite rinds reflects a late decrease of the H2O/CO2 activity of the melt that evolved toward alkali-carbonated composition. Our results showed that the crystal cargo of kimberlites can be used to track all processes acting in between the melt-rock reactions in the mantle and the emplacement in the crust.

Kimberlitic olivine – a proxy to kimberlite petrogenesis and ascent process

In kimberlite, olivine is an important constituent and it is found as mineral grains of different sizes, which can be of xenocrystic and magmatic origin. To know the processes, that are involved and controls the compositional variations of olivine, can provide distinct understanding into the genesis and evolution of kimberlites. In addition to this the textural features of kimberlitic olivine, which are recorded as textural events during magma assent constrains the ascent of kimberlite and the processes involved.Unambiguous identification of kimberlitic olivine and its textural features require careful petrographic examination combined with mineral compositional analysis and use of high magnification images (BSE-SEM), all this is integrated to know the origin of olivine grain which in turn constrain the process involved in ascent of kimberlite and its petrogenesis. In this study we review the use of kimberlitic olivine in deducing the upper mantle conditions and process for kimberlite petrogenesis.

Experimental Modeling of Diamond Resorption during Mantle Metasomatism

The morphology of resorbed diamond crystals is a valuable source of information on the composition and ascent rate of kimberlite magmas, as well as on possible redox conditions in protolith. Previously, diamond resorption was thoroughly investigated at P–T–fO2 parameters of the kimberlite magma ascent. In this study, we investigated diamond resorption using unaltered group I kimberlite and model carbonatite at P–T–fO2 parameters that are typical of the peridotite source of kimberlite magmas in the subcontinental lithospheric mantle. An analysis of previous studies made it possible to determine the rate of diamond octahedron transformation into a spherical tetrahexahedron depending on the composition of the carbonate–silicate melt. It was shown that the rate of diamond resorption at 6.3 GPa increases in all the investigated systems as fO2 and temperature rise. There is a steady decrease in the diamond resorption rate as pressure increases from 1 GPa to 6.3 GPa. The morphology comparison of the experimentally produced samples with natural diamonds is indicative of the significant contribution of metasomatic alteration of protolith by the oxidized agent and at the initial stages of kimberlite magma ascent to the resorption of natural diamonds.

Diamond resorption and immiscibility of C-O-H fluid in kimberlites: Evidence from experiments in H2O – CO2 – SiO2 – MgO – CaO system at 1–3 GPa

Kimberlites are the deepest sourced magmas emplaced at the Earth's surface. They provide a “window” into the processes at the base of the subcratonic mantle. A better understanding of the origin, composition, and emplacement mechanisms of kimberlites is hampered by uncertainties in the contents of the two main volatiles, H2O and CO2. Diamond dissolution in H2O and in CO2 fluids produces distinct resorption features offering an opportunity to determine the composition of the magmatic fluid in kimberlites. Here we examined the relationship between H2O:CO2 ratio of the fluid and the style of diamond resorption by conducting experiments in C-O-H fluid saturated with silicates with variable H2O:CO2 ratios at the conditions of kimberlite ascent of 1–3 GPa and 1150–1350 °C. Our results showed that the geometry of etch pits on diamond and the resorption style evolve consistently as bulk CO2 content of the fluid changes from 0 to 50 to 50–90 and 90–100 mol%. The fluid composition at the run conditions was monitored by entrapment of synthetic fluid inclusions in olivine and quartz. The inclusions demonstrated the existence of a fluid miscibility gap at 1–3 GPa and 1250 °C with two fluid endmembers, an aqueous and a carbonic phase, which H2O:CO2 ratio at 1 GPa determined with confocal Raman microscopy is (H2O)0.62(CO2)0.38 and (H2O)0.12(CO2)0.88 respectively. Hence, diamond resorption morphology depends on the proportions of the end-member aqueous and carbonic fluids, which vary with the bulk composition of the fluid. The different density and ability of aqueous and carbonic fluids to dissolve silicates (olivine) would promote their separation in the rising magma column. Concentration of the lower density aqueous fluid towards the tip of the propagating dyke would facilitate more efficient fracturing of the country rocks and faster ascent of the kimberlite magma causing explosive eruption. We propose that preferential attachment of aqueous fluid bubbles would help to increase the buoyancy of olivine xenocrysts and possibly diamond in the kimberlite magma offering a mechanism for transporting the heavy mantle cargo.

Multi-stage evolution of kimberlite melt as inferred from inclusions in garnet megacrysts in the Grib kimberlite (Arkhangelsk region, Russia)

To provide new insights into the origin of garnet megacrysts and evolution of kimberlite melts, we studied in detail the polymineralic and monomineralic inclusions and their host garnets from the Grib kimberlite (Arkhangelsk diamond province, Russia). Low-Cr and high-Cr garnet megacrysts and eclogitic garnets contain abundant polymineralic and rare monomineralic inclusions. Monomineralic inclusions presented by clinopyroxene, ilmenite, olivine replaced by serpentine, were found exclusively within the low-Cr megacrysts. The composition of clinopyroxene exhibits geochemical equilibrium with the host garnet, indicating its primary origin during the formation of the megacryst assemblage. The low-Cr garnet–clinopyroxene mineral assemblage formed as a result of high-temperature, melt-associated mantle metasomatism by failed kimberlite within the lithospheric mantle (T = 1150 °C and P = 5.5 GPa). Polymineralic inclusions are characterised by a silicate or silicate-sulphate matrix. The central part of the silicate inclusions is filled by serpentine and contains ilmenite, spinel, perovskite, calcite and apatite. At the contact with host garnets, phlogopite, spinel and amphibole occur as reaction minerals. Composition of spinel and other minerals within inclusions with silicate matrix suggests that kimberlite melt was trapped at mantle pressures. Inclusions with silicate matrix were found in all garnets. The matrix of silicate-sulphate inclusions consists of silicate cryptocrystalline phases and sulphate minerals (celestine–barite) and contains calcite grains. The inclusions are distributed in some low-Cr garnet megacrysts and eclogitic garnet. The silicate-sulphate inclusions were crystallised from the late-stage kimberlite melt. Diverse reaction textures are evidences of disequilibrium between the host crystals and polymineralic inclusions and indicate that garnet and the hosted inclusions reacted with the ascending kimberlite melt. The silicate-sulphate inclusions with a thin rim of epidote within eclogitic garnets indicate that a kimberlite melt invaded the garnet and induced partial melting. The studied inclusions allow us to propose three stages of the Grib kimberlite evolution: 1) generation of garnet megacrysts and primary inclusions due to melt metasomatism, 2) reaction of the high-Ti kimberlite melt with garnet megacrysts (including their dissolution) and 3) alteration of the inclusions in garnet after kimberlite ascent.

Modification of Mantle Cargo by Turbulent Ascent of Kimberlite

Kimberlite magmas provide transport for cratonic mantle xenoliths and diamonds to the Earth's surface. However, the mechanisms supporting the successful and efficient ascent of these dense cargo-laden magmas remains enigmatic due to the absence of historic eruptions, uncertainties in melt composition, and questions concerning their rheology. Mantle-derived xenocrystic olivine is the most abundant component in kimberlite and is uniquely rounded and ellipsoidal in shape. Here, we present data from a series of novel attrition experiments designed to inform on the transport of low-viscosity melts through the mantle lithosphere. The experimental data suggest that the textural properties of the mantle-derived olivine are records of the flow regime, particle concentration, and transport duration of ascent for kimberlitic magmas. Specifically, our results provide evidence for the rapid and turbulent ascent of kimberlite during their transit through the lithosphere; this transport regime creates particle-particle interactions that continually modify the mantle cargo and facilitate mineral assimilation.

New constraints on archetypal South African kimberlite petrogenesis from quenched glass-rich melt inclusions in olivine megacrysts

The evaluation of primary kimberlite compositions is hindered by significant melt modifications during ascent through the lithosphere by entrainment of xenolithic material, volatile degassing, and near surface alteration. Consequently, hypabyssal kimberlite emplaced in the upper crust may not provide a true reflection of the primary kimberlite magma. This contribution places new constraints on kimberlite melt composition by providing an assessment of quenched glass-rich polymineralic melt inclusions hosted in olivine megacrysts from the Monastery kimberlite, South Africa. Melt inclusions predominantly contain variable proportions of euhedral or skeletal grains of calcite, phlogopite, spinel, perovskite, serpentine, and fresh to devitrified glass. Estimates of the bulk compositions of melt inclusions, and the compositions of crystalline phases present therein, are compatible to those of hypabyssal kimberlites worldwide and show a volatile-rich (CO2 + H2O ~10–17 wt%) carbonated silicate (SiO2 ~27–41 wt%) composition. The glass component has a Si-Mg-Fe-rich and largely CaO-, K2O- and TiO2-free major element composition and is REE-depleted. It also contains approximately 10 wt% H2O but is CO2−free. The glass represents a residual melt that existed after crystallization of the observed mineral assemblage. From some, but not all melt inclusions, apophyses radiate outwards. These fractures typically contain partially devitrified glass that is compositionally identical to the fresh residual glass within the melt inclusions, indicating fracture formation during decompression of the hosting megacryst and at a stage after the melt had evolved. These features are consistent with a trapping of the melt inclusions at high pressure, prior to kimberlite ascent to the surface, in the SCLM at a depth corresponding to 4.5–6 GPa. Textures and compositions of phases within the melt inclusions represent stages of the kimberlite melt and magma evolution. They provide evidence in support of high-pressure experimental studies suggesting a carbonated silicate primary melt rather than a carbonatite. Furthermore, the composition of fresh glass in the melt inclusions, which is compositionally similar to serpentine, suggests that much groundmass serpentine in hypabyssal kimberlites may have formed from similar silicate melt or devitrified glass.

Diamond destruction and growth during mantle metasomatism: An experimental study of diamond resorption features

Most diamonds found in kimberlites show complex patterns of growth and dissolution (resorption) surface features. Populations of diamonds from within single kimberlite bodies commonly contain a large diversity of diamond surface forms, some of which are a result of dissolution in kimberlite magma and others are inherited from the mantle. Morphological studies of natural diamonds differentiated features produced during dissolution in kimberlite magma and during mantle metasomatism. The former features were experimentally reproduced at 1–3 GPa and used to infer the presence and composition of magmatic fluid in different kimberlites. However, the mantle-derived resorption features have not been reproduced experimentally and the composition and origins of their formative solvents are unknown. Here we report the results of diamond dissolution experiments conducted in a multi-anvil apparatus at 6 GPa and 1200 to 1500°C in synthetic CaO–MgO–SiO2–CO2–H2O system. The experiments produced very different diamond resorption morphologies in COH fluid, in silicate-saturated fluid, and in silicate and carbonate melts. Dissolution in SiO2-free COH fluid developed rounded crystal forms with shallow negative trigons, striations and hillocks, which are commonly observed on natural diamonds and are similar in 6 GPa and in 1–3 GPa experiments. However, silicate-saturated fluid produced very different resorption features that are rarely observed on natural diamonds. This result confirms that natural, SiO2-poor fluid-induced resorption develops under the comparatively low-pressures of kimberlite ascent, because at mantle pressures the high content of SiO2 in fluids would produce features like those from the silicate-saturated experiments. Comparison of the experimental products from this study to natural diamond resorption features from the literature suggests that natural diamonds show no record of dissolution by fluids during mantle metasomatism. Diamond resorption morphologies developed in experiments with silicate–carbonate melts closely resemble many of the mantle-derived resorption features of natural diamonds, whose diversity can result from variable SiO2 concentration in carbonatitic melts and temperature variation. The experimental results imply that metasomatism by fluids does not dissolve diamond, whereas metasomatism by melts is diamond-destructive. The repetitive growth-dissolution patterns of natural diamonds could be due to diamond growth from fluids in harzburgitic lithologies followed by its dissolution in partial melts.

Preservation of systematic Ni and Cr heterogeneity in otherwise homogeneous mantle olivine: Implications for timescales of post-metasomatism re-equilibration

The flux of elements into Earth's sub-continental lithospheric mantle is facilitated by the passage of small-fraction melts that either crystallise new phases or react with pre-existing minerals.Metasomatised peridotite records the end product of this exchange but rarely captures the process in the act due to subsolidus re-equilibration. We present the results of a systematic investigation of a metasomatic melt channel preserved in a mantle peridotite from the Late Cretaceous Bultfontein kimberlite (Kaapvaal craton) that shows rare direct evidence of the melt-rock reaction processes. We show that the metasomatic proto-kimberlite melt underwent variable crystallisation of clinopyroxene, sulfides, phlogopite, spinel and zircon together with interaction and diffusive exchange with the surrounding olivine-rich mantle.Element profiles across large olivine porphyroclasts (Fo88) show significant core-to-rim variations in Ni (NiO = 0.18–0.32 wt%) and Cr (Cr = 35–60 ppm), while concentrations of all other elements (e.g. Mg, Fe, Mn, Co, V)are remarkably homogeneous. Electron backscatter diffraction analysis shows that the disequilibrium of Ni and Cr is greatest where the crystal contains large components of the [100] and [010] axes. The disequilibrium is preserved in certain orientations because diffusion of Ni and Cr in olivine is more anisotropic than Fe-Mg and Mn, and slower in the [100] and [010] directions. We present the first observations of Ni and Cr decoupling from other elements in mantle olivine and suggest that this is a consequence of: (i)changing mineral-melt concentration gradients associated with the reactive percolation of a precursory kimberlite melt; and (ii) late-stage sulfide and spinel precipitation.We use the diffusion limited re-equilibration of Ni in olivine to quantify the timing of metasomatism prior to xenolith entrainment by the host kimberlite. Our modelling indicates that reactive percolation occurred on the order of 103–105 years prior to entrainment; this provides an additional line of support for the hypothesis that a period of metasomatism by proto-kimberlite melts precedes the final kimberlite ascent to the surface. The broader implication of our finding of variable rates of minor element diffusion in natural olivine is that it highlights the importance of anisotropy and the impact of changing local concentration gradients during subsolidus re-equilibration.

Diffusion of helium, hydrogen and deuterium in diamond: Experiment, theory and geochemical applications

Diffusivities of helium, deuterium and hydrogen have been characterized in diamond. Polished CVD diamond was implanted with either 3He, 2H, or 1H. Implanted samples were sealed under vacuum in silica glass capsules, and annealed in 1-atm furnaces. 3He, 2H and 1H distributions were measured with Nuclear Reaction Analysis. We obtain these Arrhenius relations:DHe = 4.00 × 10−15 exp(−138 ± 14 kJ mol−1/RT) m2 s−1.D2H = 1.02 × 10−4 exp(−262 ± 17 kJ mol−1/RT) m2 s−1.D1H = 2.60 × 10−4 exp(−267 ± 15 kJ mol−1/RT) m2 s−1.Diffusivities of 1H and 2H agree within experimental uncertainties, indicating little diffusive mass fractionation of hydrogen in diamond.To complement the experimental measurements, we performed calculations using a first-principles quantum mechanical description of diffusion in diamond within the Density Functional Theory (DFT). Differences in 1H and 2H diffusivities from calculations are found to be ∼4.5%, reflected in differences in the pre-exponential factor. This small difference in diffusivities, despite the large relative mass difference between these isotopes, is due to the fact that the atomistic process involved in the transition along the diffusion pathway is dictated by local changes to the diamond structures rather than to vibrations involving 1H/2H. This finding is consistent with the experimental results given experimental uncertainties. In contrast, calculations for helium diffusion in diamond indicate a difference of 15% between diffusivities of 3He and 4He.Calculations of diffusion distances for hydrogen using our data yield a distance of 50 μm in diamond in 300,000 years at 500 °C and ∼30 min at 1400 °C. Diffusion distances for He in diamond are shorter than for H at all temperatures above ∼350 °C, but differences increase dramatically with temperature because of the higher activation energy for H diffusion. For example, a 50 μm diffusion distance for He would be attained in ∼40 Myr at 500 °C and 400 yr at 1400 °C. For comparison, a 50 μm diffusion distance for N in diamond would require nearly 1 billion years at 1400 °C.The experimental data indicate that diamonds equilibrate with ambient H and He in the mantle on timescales brief relative to most geological processes and events. However, He diffusion in diamond is slower than in any other mineral measured to date, including other kimberlite-hosted minerals. Under some circumstances, diamond may provide information about mantle He not recoverable from other minerals. One possibility is diamonds entrained in kimberlites. Since the ascent of kimberlite from the mantle to near-surface is very rapid, entrained diamonds may retain most or all of the H and He acquired in mantle environments. Calculations using reasonable ascent rates and T-t paths indicate that He diffusive loss from kimberlite-hosted diamonds is negligible for grains of 1.0–0.2 mm radius, with fractional losses <0.15% for all ascent rates considered. If the host kimberlite magma is effectively quenched in the near-surface (or is erupted), diamonds should contain a faithful record of [He] and He isotopes from the mantle source region. Preservation of H in kimberlite-hosted diamonds is less clear-cut, with model outcomes depending critically upon rates of ascent and cooling.

Timescales between mantle metasomatism and kimberlite ascent indicated by diffusion profiles in garnet crystals from peridotite xenoliths

Rare garnet crystals from a peridotite xenolith from the Wesselton kimberlite, South Africa, have distinct zones related to two separate episodes of mantle metasomatism. The garnet cores were firstly depleted through melt extraction, then equilibrated during metasomatism by a potentially diamond-forming carbonate-bearing or proto-kimberlitic fluid at 1100–1300 °C and 4.5–5.5 GPa. The garnet rim chemistry, in contrast, is consistent with later overgrowth in equilibrium with a kimberlite at around 1025±25°C and 4.2±0.5 GPa. This suggests that the rock was physically moved upwards by up to tens of kilometres between the two metasomatic episodes. Preserved high Ca, Al and Cr contents in orthopyroxenes suggest this uplift was tectonic, rather than magmatic. Diffusion profiles were measured over the transitions between garnet cores and rims using electron microprobe (Mg, Ca, Fe for modelling, plus Cr, Mn, Ti, Na, Al) and nano Secondary Ion Mass Spectrometry (NanoSIMS; 89Y, along with 23Na, Ca, Cr, Fe, Mn and Ti) analyses. The short profile lengths (generally <10 μm) and low Y concentrations (0.2–60 ppm) make the NanoSIMS approach preferable. Diffusion profiles at the interface between the zones yield constraints on the timescale between the second metasomatic event and eruption of the kimberlite magma that brought the xenolith to the surface. The time taken to form the diffusion profiles is on the order of 25 days to 400 yr, primarily based on modelling of Y diffusion along with Ca, Fe and Mg (multicomponent diffusion) profiles. These timescales are too long to be produced by the interaction of the mantle xenolith with the host kimberlite magma during a single-stage ascent to the crust (hours to days). The samples offer a rare opportunity to study metasomatic processes associated with failed eruption attempts in the cratonic lithosphere.

Orthopyroxene survival in deep carbonatite melts: implications for kimberlites

Kimberlites are rare diamond-bearing volcanic rocks that originate as melts in the Earth’s mantle. The original composition of kimberlitic melt is poorly constrained because of mantle and crustal contamination, exsolution of volatiles during ascent, and pervasive alteration during and after emplacement. One recent model (Russell et al. in Nature 481(7381):352–356, 2012. doi: 10.1038/nature10740 ) proposes that kimberlite melts are initially carbonatitic and evolve to kimberlite during ascent through continuous assimilation of orthopyroxene and exsolution of CO2. In high-temperature, high-pressure experiments designed to test this model, assimilation of orthopyroxene commences between 2.5 and 3.5 GPa by a reaction in which orthopyroxene reacts with the melt to form olivine, clinopyroxene, and CO2. No assimilation occurs at 3.5 GPa and above. We propose that the clinopyroxene produced in this reaction can react with the melt at lower pressure in a second reaction that produces olivine, calcite, and CO2, which would explain the absence of clinopyroxene phenocrysts in kimberlites. These experiments do not confirm that assimilation of orthopyroxene for the entirety of kimberlite ascent takes place, but rather two reactions at lower pressures (<3.5 GPa) cause assimilation of orthopyroxene and then clinopyroxene, evolving carbonatitic melts to kimberlite and causing CO2 exsolution that drives rapid ascent.

Constraints on kimberlite ascent mechanisms revealed by phlogopite compositions in kimberlites and mantle xenoliths

Kimberlite magmas are of economic and scientific importance because they represent the major host to diamonds and are probably the deepest magmas from continental regions. In addition, kimberlite magmas transport abundant mantle and crustal xenoliths, thus providing fundamental information on the composition of the sub-continental lithosphere. Despite their importance, the composition and ascent mechanism(s) of kimberlite melts remain poorly constrained. Phlogopite is one of the few minerals that preserves a history of fluid migration and magmatism in the mantle and crust and is therefore an invaluable petrogenetic indicator of kimberlite magma evolution.Here we present major and trace element compositional data for phlogopite from the Bultfontein kimberlite (Kimberley, South Africa; i.e. the kimberlite type-locality) and from entrained mantle xenoliths. Phlogopite macrocrysts (~>0.3–0.5mm) and microcrysts (between ~0.1 and 0.3mm) in the Bultfontein kimberlite display concentric compositional zoning patterns. The cores of these phlogopite grains exhibit compositions typical of phlogopite contained in peridotite mantle xenoliths. However, the rims of some grains show compositions analogous to kimberlite groundmass phlogopite (i.e. high Ti, Al and Ba; low Cr), whereas other rims and intermediate zones (between cores and rims) exhibit unusually elevated Cr and lower Al and Ba concentrations. The latter compositions are indistinguishable from matrix phlogopite in polymict breccia xenoliths (considered to represent failed kimberlite intrusions) and from Ti-rich overgrowth rims on phlogopite in other mantle xenoliths. Consequently, it is likely that these phlogopite grains crystallized from kimberlite melts and that the high Ti-Cr zones originated from earlier kimberlite melts at mantle depths.We postulate that successive pulses of ascending kimberlite magma progressively metasomatised the conduit along which later kimberlite pulses ascended, producing progressively decreasing interaction with the surrounding mantle rocks. In our view, these processes represent the fundamental mechanism of kimberlite magma ascent. Our study also indicates that, in addition to xenoliths/xenocrysts and magmatic phases, kimberlite rocks incorporate material crystallized at various mantle depths by previous kimberlite intrusions (mantle-derived ‘antecrysts’).

A model for the activity of silica along the carbonatite–kimberlite–mellilitite–basanite melt compositional joint

Carbon dioxide and water, being present in the Earth's mantle at concentration levels of tens to hundreds of ppm, greatly lower the peridotite solidus temperature and drastically modify the composition of produced melts. The presence of CO2 produces silica-poor, carbonate-rich liquids at the onset of melting, and these liquids shift toward silica rich compositions as the degree of melting increases. Numerous geochemical observations and experimental studies have revealed the complexity of the transition between carbonate-rich and silicate-rich melts. It is characterized by a strongly non-linear evolution and, under specific conditions, by immiscibility. To better constrain this transition, we have used the thermodynamic activity of silica as a probe of the mixing properties between molten carbonate and molten silicate. The activity of silica aSiO2l was calculated for a large number of experimental liquids from two equilibria: olivine–orthopyroxene–melt and immiscible silicate-rich melt–carbonate-rich melt (491 data points ranging from 1 to 14GPa and 1090 to 1800°C). We modelled aSiO2l during incipient melting of the peridotite in presence of CO2 with a generalized Margules function. Our model reproduces well the silica activity–composition relationships of the experimental database, and can be used to predict the silica content of the melts coexisting with olivine and orthopyroxene. We show that water content and Ca/Mg ratio in the melts have an important influence on the aSiO2l. In contrast to a recent empirical model (Dasgupta et al., 2013), the analysis of the experimental database reveals that the transition from carbonate to silicate melt with decreasing depth should occur abruptly in oceanic mantle. Our model predicts that carbonatitic melts with ~5wt.% SiO2 can be stabilized from ~150km depth, at the onset of incipient melting by “redox melting”, up to ~75km, above which the liquid evolves abruptly to a carbonated silicate composition (> ~25wt.% SiO2). In the cratonic mantle lithosphere, our model predicts that carbonatitic melts are prevailing up to shallow depth, and conflicts the recent model (Russell et al., 2012) of CO2-saturation triggered by orthopyroxene assimilation during kimberlite ascent.

The ascent of kimberlite: Insights from olivine

Olivine xenocrysts are ubiquitous in kimberlite deposits worldwide and derive from the disaggregation of mantle-derived peridotitic xenoliths. Here, we provide descriptions of textural features in xenocrystic olivine from kimberlite deposits at the Diavik Diamond Mine, Canada and at Igwisi Hills volcano, Tanzania. We establish a relative sequence of textural events recorded by olivine during magma ascent through the cratonic mantle lithosphere, including: xenolith disaggregation, decompression fracturing expressed as mineral- and fluid-inclusion-rich sealed and healed cracks, grain size and shape modification by chemical dissolution and abrasion, late-stage crystallization of overgrowths on olivine xenocrysts, and lastly, mechanical milling and rounding of the olivine cargo prior to emplacement. Ascent through the lithosphere operates as a “kimberlite factory” wherein progressive upward dyke propagation of the initial carbonatitic melt fractures the overlying mantle to entrain and disaggregate mantle xenoliths. Preferential assimilation of orthopyroxene (Opx) xenocrysts by the silica-undersaturated carbonatitic melt leads to deep-seated exsolution of CO2-rich fluid generating buoyancy and supporting rapid ascent. Concomitant dissolution of olivine produces irregular-shaped relict grains preserved as cores to most kimberlitic olivine. Multiple generations of decompression cracks in olivine provide evidence for a progression in ambient fluid compositions (e.g., from carbonatitic to silicic) during ascent. Numerical modelling predicts tensile failure of xenoliths (disaggregation) and olivine (cracks) over ascent distances of 2–7 km and 15–25 km, respectively, at velocities of 0.1 to >4 m s−1. Efficient assimilation of Opx during ascent results in a silica-enriched, olivine-saturated kimberlitic melt (i.e. SiO2 >20 wt.%) that crystallizes overgrowths on partially digested and abraded olivine xenocrysts. Olivine saturation is constrained to occur at pressures <1 GPa; an absence of decompression cracks within olivine overgrowths suggests depths <25 km. Late stage (<25 km) resurfacing and reshaping of olivine by particle–particle milling is indicative of turbulent flow conditions within a fully fluidized, gas-charged, crystal-rich magma.

Retention of radiation damage in zircon xenocrysts from kimberlites, Northern Yakutia

Abstract We have studied zircon xenocrysts from Mesozoic kimberlites from the Kuoika and Ary–Mastakh fields in Northern Yakutia. Zircon xenocrysts are assumed to originate from crustal rocks. Our SHRIMP (Sensitive High mass Resolution Ion MicroProbe) analyses yielded predominantly concordant U–Th–Pb ages (up to ~ 3570 Ma; Paleoarchean) that clearly predate kimberlite formation. The general U–Th–Pb concordance observed excludes notable disturbance of the zircon xenocrysts U–Th–Pb isotope system during kimberlite ascent and emplacement. In addition, zircon xenocrysts were found to be significantly more radiation-damaged than would correspond to damage accumulation only since the time of kimberlite formation. This observation first indicates that zircon crystals were sampled by the kimberlite magma at comparably shallow depths not exceeding 10–12 km. If, in contrast, zircon crystals originated from deeper levels of the Earth's crust, they would have been exposed to temperatures of 250–300 °C or more. This in turn would have caused long-term thermal annealing of the radiation damage, which was however not observed in our study. Second, our observation contradicts the hypothesis that high temperatures experienced by zircon xenocrysts during kimberlite ascent will cause notable structural reconstitution by short-term thermal annealing. Consequently, zircon crystals cannot have spent more than a few hours at temperatures exceeding ca. 700–800 °C, or more than a few days at temperatures exceeding ca. 500–600 °C. This in turn suggests that (i) temperatures of the ascending kimberlite magmas were rather moderate, and (ii) kimberlite ascent is a comparably short process followed by rapid cooling.