Kankan diamonds (Guinea) III: δ13C and nitrogen characteristics of deep diamonds

Diamonds from the Kankan area in Guinea formed over a large depth profile beginning within the cratonic mantle lithosphere and extending through the asthenosphere and transition zone into the lower mantle. The carbon isotopic composition, the concentration of nitrogen impurities and the nitrogen aggregation level of diamonds representing this entire depth range have been determined. Peridotitic and eclogitic diamonds of lithospheric origin from Kankan have carbon isotopic compositions ('¹³C: peridotitic -5.4 to -2.2‰; eclogitic -19.7 to -0.7‰) and nitrogen characteristics (N: peridotitic 17-648 atomic ppm; eclogitic 0-1,313 atomic ppm; aggregation from IaA to IaB) which are generally typical for diamonds of these two suites worldwide. Geothermobarometry of peridotitic and eclogitic inclusion parageneses (worldwide sources) indicates that both suites formed under very similar conditions within the cratonic lithosphere, which is not consistent with a derivation of diamonds with light carbon isotopic composition from subducted organic matter within subducting oceanic slabs. Diamonds containing majorite garnet inclusions fall to the isotopically heavy side ('¹³C: -3.1‰ to +0.9‰) of the worldwide diamond population. Nitrogen contents are low (0-126 atomic ppm) and one of the two nitrogen-bearing diamonds shows such a low level of nitrogen aggregation (30% B-centre) that it cannot have been exposed to ambient temperatures of the transition zone (̿,400 °C) for more than 0.2 Ma. This suggests rapid upward transport and formation of some Kankan diamonds pene-contemporaneous to Cretaceous kimberlite activity. Similar to these diamonds from the asthenosphere and the transition zone, lower mantle diamonds show a small shift towards isotopic heavy compositions (-6.6 to -0.5‰, mode at -3.5‰). As already observed for other mines, the nitrogen contents of lower mantle diamonds were below detection (using FTIRS). The mutual shift of sublithospheric diamonds towards isotopic heavier compositions suggests a common carbon source, which may have inherited an isotopic heavy composition from a component consisting of subducted carbonates.     

Kankan diamonds (Guinea) I: from the lithosphere down to the transition zone

Peridotitic inclusions in alluvial diamonds from the Kankan region of Guinea in West Africa are mainly of lherzolitic paragenesis. Nevertheless, extreme Cr₂O₃ contents (max. 17 wt%) in some of the exclusively lherzolitic garnets document that the diamond source experienced a previous stage of melt extraction in the spinel stability field. This initial depletion was followed by at least two metasomatic stages: (1) enrichment of LREE and Sr and (2) introduction mainly of MREE–HREE and other HFSE (Ti, Y, Zr, Hf). The Ti- and HFSE-poor character of stage (1) points towards a CHO-rich fluid or carbonatitic melt, the high HFSE in stage (2) favour silicate melts as enriching agent. Eclogitic inclusions are derived from a large depth interval ranging from the lithosphere through the asthenosphere into the transition zone. The occurrence of negative Eu anomalies in garnet and clinopyroxene from both lithosphere and transition zone suggests a possible relationship to subducted oceanic crust. Lithospheric eclogitic inclusions are derived from heterogeneous sources, that may broadly be divided into a low-Ca group with LREE depleted trace element patterns and a high-Ca group representing a source with negative LREE–HREE slope that is moderately enriched in incompatible elements relative to primitive mantle. High-Ca inclusions of majoritic paragenesis are significantly more enriched in incompatible elements, such as in Sr and LREE. Calculated whole rock compositions require metasomatic enrichment even if a derivation from MORB is assumed. Received: 26 January 2000 / Accepted: 18 May 2000     

Genesis of diamonds in the lower mantle

The “forbidden” assemblage (ferropericlase + enstatite) as inclusions in diamonds has been taken as evidence to imply that these inclusions and their host diamonds formed initially in the lower mantle. Magnesite is probably the only stable carbonate at depths greater than ∼220 km. Like dehydration reactions, the reaction boundary for the decarbonation of magnesite has a positive dT/dP slope at lower pressures, which becomes negative at higher pressures, if no other phase intervenes. This reaction boundary probably intersects the geotherm between ∼900 and ∼1100 km, below which magnesite decomposes into an assemblage periclase + diamond + oxygen. Thus, ferropericlase is the most likely inclusion in diamond formed in the lower mantle. The high frequency of sole occurrence of ferropericlase in diamonds from Sao Luiz, Brazil seems to substantiate the present speculation. Received: 8 June 1998 / Accepted: 28 September 1998     

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.     

Lower mantle diamonds from Rio Soriso (Juina area,Mato Grosso,Brazil)

The morphology, colour, fluorescence, cathodoluminescence, nitrogen content and aggregation state, internal structure and mineral inclusions have been studied for 69 alluvial diamonds from the Rio Soriso (Juina area, Mato Grosso State, Brazil). Nitrogen in most diamonds (53%) is fully aggregated as B centres, but there is also a large proportion of N-free stones (38%). A strong positive correlation between nitrogen and IR-active hydrogen concentrations is observed. The diamonds contain (in order of decreasing abundance) ferropericlase, CaSi-perovskite, magnetite, MgSi-perovskite, pyrrhotite, olivine, SiO₂, perovskite, tetragonal almandine-pyrope phase and some other minerals represented by single grains. The Rio Soriso diamond suite is subdivided into several subpopulations that originated in upper and lower mantle of ultramafic and mafic compositions, with the largest subgroup forming in the ultramafic lower mantle. Analysed ferropericlase grains are enriched in Fe (Mg#=0.43–0.89), which is ascribed to their origin in the lowermost mantle. The Juina kimberlites may be unique in sampling the material from depths below 1,700 km that ascended in a plume formed at the core–mantle boundary.Electronic Supplementary Material  Supplementary material is available for this article at

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Origin of sub-lithospheric diamonds from the Juina-5 kimberlite (Brazil): constraints from carbon isotopes and inclusion compositions

Forty-one diamonds sourced from the Juina-5 kimberlite pipe in Southern Brazil, which contain optically identifiable inclusions, have been studied using an integrated approach. The diamonds contain <20 ppm nitrogen (N) that is fully aggregated as B centres. Internal structures in several diamonds revealed using cathodoluminescence (CL) are unlike those normally observed in lithospheric samples. The majority of the diamonds are composed of isotopically light carbon, and the collection has a unimodal distribution heavily skewed towards δ¹³C ~ ?25 ‰. Individual diamonds can display large carbon isotope heterogeneity of up to ~15 ‰ and predominantly have isotopically lighter cores displaying blue CL, and heavier rims with green CL. The light carbon isotopic compositions are interpreted as evidence of diamond growth from abiotic organic carbon added to the oceanic crust during hydrothermal alteration. The bulk isotopic composition of the oceanic crust, carbonates plus organics, is equal to the composition of mantle carbon (?5 ‰), and we suggest that recycling/mixing of subducted material will replenish this reservoir over geological time. Several exposed, syngenetic inclusions have bulk compositions consistent with former eclogitic magnesium silicate perovskite, calcium silicate perovskite and NAL or CF phases that have re-equilibrated during their exhumation to the surface. There are multiple occurrences of majoritic garnet with pyroxene exsolution, coesite with and without kyanite exsolution, clinopyroxene, Fe or Fe-carbide and sulphide minerals alongside single occurrences of olivine and ferropericlase. As a group, the inclusions have eclogitic affinity and provide evidence for diamond formation at pressures extending to Earth’s deep transition zone and possibly the lower mantle. It is observed that the major element composition of inclusions and isotopic compositions of host Juina-5 diamonds are not correlated. The diamond and inclusion compositions are intimately related to subducted material and record a polybaric growth history across a depth interval stretching from the lower mantle to the base of the lithosphere. It is suggested that the interaction of slab-derived melts and mantle material combined with subsequent upward transport in channelised networks or a buoyant diapir explains the formation of Juina-5 diamonds. We conclude that these samples, despite originating at great mantle depths, do not provide direct information about the ambient mantle, instead, providing a snapshot of the Earth’s deep carbon cycle.     

The secondary origin of diamonds: multi-modal radiation tomography of diamondiferous mantle eclogites

Three-dimensional neutron and X-ray tomography reveals the textural and spatial relationship of diamonds and associated minerals in situ, in a unique suite of 17 diamondiferous eclogites. We emphasize the reporting of X-ray imaging on mantle xenoliths, which in combination with neutron imaging enables the clear identification of diamonds and interstitial metasomatic secondary minerals. In particular, neutrons are highly sensitive to hydrogen (H), allowing for the identification of OH- and H₂O-bearing metasomatic minerals. The identification of metasomatic minerals allows for the delineation of distinct metasomatic pathways through the eclogite xenoliths. Diamonds are readily identified as the darkest greyscales due to their low attenuation, and are typically surrounded by secondary minerals, never in contact with primary minerals, and always confined within metasomatic pathways. The ubiquitous occurrence of diamonds in association with pathways suggests a potential genetic link. Both octahedral and dodecahedral diamonds are observed within individual xenoliths, suggesting multiple heterogeneous growth and dissolution processes at small scales. The distinct age dichotomy between eclogite xenoliths and metasomatic mineral assemblages implies that the observed textural relationship of diamonds and late-stage metasomatic pathways for this suite of 17 eclogites casts doubt on the theory that eclogitic diamonds formed billions of years ago. Diamonds are interpreted to have formed from multiple growth episodes, with the last of these episodes represented by the metasomatic assemblages observed in this study. This further indicates that eclogitic diamond inclusions may span large time scales from ancient ages (>2 Ga) all the way to the last growth event, perhaps even close to the time of kimberlite emplacement (~360 Ma), which has significant implications for age-dating of diamonds and the study of diamonds as a whole.     

Nitrogen isotopes in peridotitic diamonds from Fuxian, China: the mantle signature

Nitrogen isotopes in peridotitic diamonds from Fuxian, China, suggest that the upper mantle δ¹⁵N-value has been globally homogeneous since at least the Proterozoic (−5 to −8‰/ATM), with similar values for subcontinental and MORB mantle.
  In addition, Fuxian diamonds retain the memory of a primary nitrogen lower in δ¹⁵N (down to −25‰). For the first time δ¹⁵N- values in diamonds match those of enstatite chondrites, supporting a formation of the Earth from such meteorites and the idea of a heterogeneous accretion of the Earth's volatiles.
  Nitrogen concentrations in diamonds are believed to depend strongly on the rate of the diamond growth and not to be an indicator of C/N ratios of the fluids from which they grew.     

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.     

Peridotitic diamonds from Namibia: constraints on the composition and evolution of their mantle source

About half the diamonds studied from the Cenozoic placer deposits along the Namibian coast belong to the peridotitic suite. The peridotitic mantle source is heterogeneous ranging from lherzolitic to strongly Ca depleted (down to 0.24 wt.% CaO in garnet) and shows large variations in Cr/Al ratio, illustrated by very low to very high Cr₂O₃ contents in garnet (2.6–17.3 wt.%). The Cr-rich end of this range includes exceptionally high Cr₂O₃ contents in Mg-chromite (70.7 wt.%) and clinopyroxene (3.6 wt.%). Garnet-olivine thermometry appears to indicate two groups, one that equilibrated at temperatures between 1200 and 1220°C and a second between 960 and 1100°C. Combined estimates of pressure and temperature based on garnet-orthopyroxene pairs indicate a large variance in geothermal gradients, corresponding to 38–42 mW/m² surface heat flow.

The trace-element composition of peridotitic garnet inclusions (determined by SIMS) also indicates large diversity. Two principal groups, corresponding to different styles of metasomatic source enrichment, are recognized. The first group ranges from extremely LREE_N-depleted patterns, through trough-shaped REE_N to sinusoidal patterns with the position of the first peak gradually moving from the LREE_N to the MREE_N. This series of REE patterns is interpreted to reflect a range of metasomatic agents with decreasing LREE/HREE. Only in the case of the two garnets with REE_N peaking at Sm–Eu is this process connected with enrichment in Zr, without significant introduction of Y and Ti. The metasomatism responsible is interpreted as reflecting percolation of CHO-fluids through harzburgite under sub-solidus conditions. A second group of garnets shows an increase from LREE_N–MREE_N and almost flat (lherzolitic garnet) to moderately declining MREE_N–HREE_N at super-chondritic levels. This second style of metasomatism is caused by an agent carrying HFSE and showing only moderate enrichment in LREE over HREE, which points towards silicate melts.     

A classification scheme for mantle-derived garnets in kimberlite: a tool for investigating the mantle and exploring for diamonds

A new empirical method has been devised for classification of mantle-derived garnets in kimberlite. Simple chemical screens have been developed to distinguish between garnets from different parageneses, based on Mg, Fe, Ca, Cr, Ti and Na values of published analyses of garnets from >2000 ultramafic xenoliths in kimberlite. Although crustal garnets are typically uncommon as xenocrysts in kimberlite, the first step in the classification is to screen these from the mantle population, using data from >600 garnet-bearing crustal rocks. Such a screen may also prove useful in evaluating the source (crust vs. mantle) of garnet in kimberlite exploration samples. Subsequent steps divide mantle garnets into eclogite, peridotite and Cr-poor megacryst groupings, and sub-groups of the peridotite (lherzolite, harzburgite, wehrlite) and eclogite (Groups I and II and A, B, C and grospydite) populations. Important features of this classification include the fact that it is based on distinctions between groups of fundamental geological significance (e.g., peridotite vs. eclogite) and it is based on a large, well-documented and well-understood xenolith database. As it utilizes oxide values and molar ratios of major and minor elements, the rationale for the screens is readily understood and it is simple to use.     

Luminescence in diamonds of the Sao Luiz placer (Brazil)

Plates made of diamonds from the Sao Luiz province (Brazil) were investigated by confocal scanning luminescence microscopy. The samples have many macroinhomogeneities (cracks and inclusions), but there is a quasi-uniform distribution of luminescence centers in the bulk. At all investigated points of the crystals, the same group of centers was observed: N3, H4, 575, and a red band with a maximum at 690-700 nm. The visible nonuniformities in the distribution of luminescence over the area of the plates are determined by relatively small fluctuations in the ratio of the intensities of individual bands in the spectra. Nitrogen centers of different degrees of aggregation (H4, N3, and 575 nm, with four, three, and one nitrogen atom, respectively) coexist in these crystals. In the same zones of the samples, the distribution of blue luminescence (N3 centers) is diffuse (uniform), but the distribution of yellow-green luminescence is characterized by layering on (111). This might be a consequence of the tangential growth of octahedron faces or a result of plastic deformation of the crystals and dislocations along (111).     

Layered mantle structure beneath the western Guyana Shield, Venezuela: Evidence from diamonds and xenocrysts in Guaniamo kimberlites

Mantle xenoliths and xenocrysts from Guaniamo, Venezuela kimberlites record equilibration conditions corresponding to a limited range of sampling in the lithosphere (100-150 km). Within this small range, however, compositions vary considerably, but regularly, defining a strongly layered mantle sequence. Major and trace element compositions suggest the following lithologic sequence: highly depleted lherzolite from 100 to 115 km, mixed ultra-depleted harzburgite and lherzolite from 115 to 120 km, relatively fertile lherzolite from 120 to 135 km, and mixed depleted harzburgite and relatively fertile lherzolite from 135 to 150 km. Based on comparison with well-documented mantle peridotites and xenocrysts from elsewhere, we conclude that the Meso-proterozoic Cuchivero Province (host to the Guaniamo kimberlites) is underlain by depleted and ultra-depleted shallow Archean mantle that was underplated, and uplifted, by Proterozoic subduction, perhaps more than once. These Proterozoic subduction events introduced less-depleted oceanic lithosphere beneath the Archean section, which remains there and is the source of the abundant Guaniamo eclogite-suite diamonds that have ocean-floor geochemical signatures. Although diamond-indicative low-Ca Cr-pyrope garnets are abundant, they are derived primarily from the shallow depleted layer within the field of graphite stability, and the rare peridotite-suite diamonds are either metastably preserved at these shallow depths, or were derived from the small amount of depleted lithosphere sampled by these kimberlites that remains within the diamond stability field (the mixture of Archean and Proterozoic mantle in the depth range 135-150 km).     

Typomorphic characteristics of the Ural diamonds (from FTIR spectroscopy data)

Natural diamonds from the Ural alluvial deposits have been studied by FTIR spectroscopy. It is shown that these diamonds are similar in some typomorphic features, such as nitrogen content and aggregation state, to the diamonds of the Coromandel (Brazil) and Verkhnee Molodo (Lena region, Yakutia) placers and to the diamonds from kimberlites of the Arkhangel’sk Region but differ significantly in lower contents of hydrogen and higher contents of platelets. The high contents of hydrogen (5–20 cm–1) determined in some diamonds are due to the specific formation of their internal structure and to the presence of inclusions. The nonuniform distribution of nitrogen A- and B-centers throughout the crystal testifies to the zonal structure of diamonds. The temperature conditions of formation of the Ural diamonds have been estimated.     

Compositional control on the polymorphism (2M1-3T) of phengitic white mica from high pressure parageneses of the Sesia Zone (lower Aosta valley,Western Alps; Italy)

The polymorphism (2M₁ or 3T modification) of phengites coexisting with Jadeite+quartz+K-feldspar in gneisses of granitic composition from the internal part of the Sesia Zone correlates with their Mg/(Al+Fe+Mg) ratio. For values 0.015 the 2M₁ modification, for values 0.025 the 3T modification is formed. For Mg/(Al+Fe+Mg) values between these limits both polymorphs coexist as distinct grains; less than 1% of a large number of separated grains show an intergrowth of both modifications. In these cases the predominant phase boundaries are (hkO) planes, rational at least with respect to the 2M₁ lattice; boundaries parallel (001) occur as subordinate steps in (hkO) boundaries. Extensive intergrowth parallel (001) is not observed. As far as revealed by optical microscopy, the stacking sequence once established in a nucleus is retained during growth of the crystal.     

Fluid-bearing alkaline carbonate melts as the medium for the formation of diamonds in the Earth''s mantle: an experimental study

We have experimentally studied the formation of diamonds in alkaline carbonate–carbon and carbonate–fluid–carbon systems at 5.7–7.0 GPa and 1150–1700 °C, using a split-sphere multi-anvil apparatus (BARS). The starting carbonate and fluid-generating materials were placed into Pt and Au ampoules. The main specific feature of the studied systems is a long period of induction, which precedes the nucleation and growth of diamonds. The period of induction considerably increases with decreasing P and T, but decreases when adding a C–O–H fluid to the system. In the range of P and T corresponding to the formation of diamonds in nature, this period lasts for tens of hours. The reactivity of the studied systems with respect to the diamond nucleation and growth decreases in this sequence: Na₂CO₃–H₂C₂O₄·2H₂O–C>K₂CO₃–H₂C₂O₄·2H₂O–C>>Na₂CO₃–C>K₂CO₃–C. The diamond morphology is independent of P and T, and is mainly governed by the composition of the crystallization medium. The stable growth form is a cubo-octahedron in the Na₂CO₃ melt, and an octahedron in the K₂CO₃ melt. Regardless of the composition of the carbonate melt, only octahedral diamond crystals formed in the presence of the C–O–H fluid. The growth rates of diamond varied in the range from 1.7 μm/h at 1420 °C to 0.1–0.01 μm/h at 1150 °C, and were used to estimate, for the first time, the possible duration of the crystallization of natural diamonds. From the analysis of the experimental results and the petrological evidence for the formation of diamonds in nature, we suggest that fluid-bearing alkaline carbonate melts are, most likely, the medium for the nucleation and growth of diamonds in the Earth's upper mantle.     

The first finding of graphite inclusion in diamond from mantle rocks: The result of the study of eclogite xenolith from Udachnaya pipe (Siberian craton)

A xenolith of eclogite from the kimberlite pipe Udachnaya–East, Yakutia Grt+Cpx+Ky + S + Coe/Qtz + Dia + Gr has been studied. Graphite inclusions in diamond have been studied in detail by Confocal Raman (CR) mapping. The graphite inclusion in diamond has a highly ordered structure and is characterized by a substantial shift in the band (about 1580 cm^–1) by 7 cm^–1, indicating a significant residual strain in the inclusion. According to the results of FTIR spectroscopic studies of diamond crystals, a high degree of nitrogen aggregation has been detected: it is present mainly in form A, which means an “ancient” age of the diamonds. In the xenolith studied, the diamond formation occurred about 1 Byr, long before their transport by the kimberlite melt, and the conditions of the final equilibrium were temperatures of 1020 ± 40°C at 4.7 GPa. Thus, these graphite inclusions found in a diamond are the first evidence of crystallization of metastable graphite in a diamond stability field. They were formed in rocks of the upper mantle significantly below (≥20 km) the graphite-diamond equilibrium line.