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.     

EINSTEIN and MICHELSON The Context of Discovery and the Context of Justification

The philosopher of science is not much intersted in the thought processes which lead to scientific discoveries; he looks for a logical analysis of the completed theory, including the relationships establishing its validity. That is, he is not interested in the context of discovery, but in the context of justification … it appears amazing to what extent the logical analysis of relativity coincides with the original interpretation by its author, as far as it can be constructed from the scanty remarks in EINSTEIN 's publications. In contradistinction to some developments in quantum theory, the logical schema of the theory of relativity corresponds surprisingly with the program which controlled its discovery.     

Diamond formation and source carbonation: mineral associations in diamonds from Namibia

Mineral inclusions in diamonds from Namibia document a range of mantle sources, including eclogitic, websteritic and peridotitic parageneses. Based on unusual textural features a group of inclusions showing websteritic, peridotitic and transitional chemical features is assigned to an 'undetermined suite' (12% of the studied diamonds). The mutual characteristic of this group is the occurrence of lamellar intergrowths of clinopyroxene and orthopyroxene. In addition, the 'undetermined suite' is associated with a number of uncommon phases: in one diamond MgCO₃ is enclosed by clinopyroxene. Other minerals that form touching inclusions with the pyroxene lamellae are (1) a SiO₂ phase observed in three diamonds, together with CaCO₃ in one of them, (2) phlogopite and a Cr-rich 'titanate' (probably lindsleyite). The inclusions document a metamorphic path of decreasing pressures and temperatures after entrapment in diamond. First, homogeneous low-Ca clinopyroxenes were entrapped at high temperatures. They subsequently exsolved orthopyroxene and probably also SiO₂ (coesite) on cooling along a P,T trajectory that did not allow garnet to be exsolved as well. Phlogopite, carbonates and LIMA phases are the result of overprint of a peridotitic source rock by a carbon-rich agent. The resulting unusual, olivine-free mineral association and the host diamonds are interpreted as products of extensive carbonation of the peridotite.     

Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism

The oxidation state, reflected in the oxygen fugacity (fO₂), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO₂ FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO₂ trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record redox conditions extending up to Δlog fO₂ = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized and oxidized to an extent that conversion of diamond into carbonate should have occurred. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Iron oxidation state in lower mantle mineral assemblages: II. Inclusions in diamonds from Kankan, Guinea

Inclusions of ferropericlase and former (Mg,Fe)(Si,Al)O₃ perovskite in diamonds from Kankan, Guinea believed to originate in the lower mantle were studied using Mössbauer spectroscopy to determine Fe³⁺/ΣFe. Fe³⁺ concentration in the (Mg,Fe)(Si,Al)O₃ inclusion is consistent with empirical relations relating Fe³⁺/ΣFe to Al concentration, supporting the inference that it crystallised in the perovskite structure at lower mantle conditions. In ferropericlase there is a nearly linear variation of trivalent cation abundance with monovalent cation abundance, suggesting a substitution of the form Na_0.5M_0.5³⁺O (M=Fe³⁺, Cr³⁺, Al³⁺). Excess positive charge is likely balanced by cation vacancies, where their abundance is observed to increase with increasing iron concentration, consistent with high-pressure experiments. The abundance of cation vacancies is related to oxygen fugacity, where ferropericlase inclusions from Kankan and São Luiz (Brazil) are inferred to have formed at conditions more oxidising than Fe-(Mg,Fe)O equilibrium, but more reducing than Re-ReO₂ equilibrium. Fe²⁺/Mg partition coefficients between (Mg,Fe)(Si,Al)O₃ and ferropericlase were calculated for inclusions co-existing in the same diamond using Mössbauer data and empirical relations based on high-pressure experimental work. Most values are consistent with high-pressure experiments, suggesting that these inclusions equilibrated at lower mantle conditions. The measured ferropericlase Fe³⁺ concentrations are consistent with diamond formation in a region of redox gradients, possibly arising from the subduction of oxidised material into reduced lower mantle. Reduction of carbonate to form ferropericlase and diamond is consistent with a slight shift of Kankan δ¹³C values to isotopically heavy compositions compared to the worldwide dataset, and could supply the oxygen necessary to satisfy the high Fe³⁺ concentration in (Mg,Fe)(Si,Al)O₃ perovskite, as well as account for the high proportion of ferropericlase in the lower mantle paragenesis. The heterogeneity of lower mantle diamond sources indicates that the composition of lower mantle diamonds do not necessarily reflect those of the bulk mantle.     

Rare and unusual mineral inclusions in diamonds from Mwadui, Tanzania

Syngenetic diamond inclusions from the Mwadui kimberlite reveal that an unusually fertile section of lithospheric mantle beneath the Central African Craton was sampled. This is shown by a very high ratio of lherzolitic to harzburgitic garnet inclusions (1:2) and low Mg/Fe-ratios in olivine and orthopyroxene. Geothermometry applied to the peridotitic inclusions indicates disequilibrium between non-touching inclusion pairs to be common. Disequilibrium between garnet-olivine and garnet-orthopyroxene pairs suggests successive iron enrichment during diamond formation, e.g. leading to the presence of harzburgitic garnet and lherzolitic olivine in the same diamond. Apart from the dominant peridotitic inclusion suite (88%), rare eclogitic inclusions occur (2%) and a number of uncertain paragenesis. Two diamonds, one with eclogitic garnets with moderate pyroxene solid solution and the other with a single ferro-periclase inclusion, suggest the contribution of a small sub-lithospheric component. The finding of the association Fe-FeO-Fe₃O₄ in one single diamond indicates diamond formation over a large range of f _O2 conditions, possibly along redox fronts. Steep compositional gradients may also be reflected by the joint occurrence of harzburgitic garnet and a SiO₂-phase in the same diamond. Alternatively the formation of the SiO₂-phase may be due to extreme carbonation of the peridotitic source. Further unusual findings include the exsolution of a silicate phase from magnetite inclusions, (i.e. primary solution of γ-olivine) and an ilmenite inclusion with an eskolaite (Cr₂O₃) component of 14.5 mol%, the latter together with harzburgitic paragenesis silicate inclusions. Received: 23 August 1997 / Accepted: 7 January 1998     

The trace element composition of silicate inclusions in diamonds: a review

On a global scale, peridotitic garnet inclusions in diamonds from the subcratonic lithosphere indicate an evolution from strongly sinusoidal REE_N, typical for harzburgitic garnets, to mildly sinusoidal or “normal” patterns (positive slope from LREE_N to MREE_N, fairly flat MREE_N–HREE_N), typical for lherzolitic garnets. Using the Cr-number of garnet as a proxy for the bulk rock major element composition it becomes apparent that strong LREE enrichment in garnet is restricted to highly depleted lithologies, whereas flat or positive LREE–MREE slopes are limited to less depleted rocks. For lherzolitic garnet inclusions, there is a positive relation between equilibration temperature, enrichment in MREE, HREE and other HFSE (Ti, Zr, Y), and decreasing depletion in major elements. For harzburgitic garnets, relations are not linear, but it appears that lherzolite style enrichment in MREE–HREE only occurs at temperatures above 1150–1200 °C, whereas strong enrichment in Sr is absent at these high temperatures. These observations suggest a transition from melt metasomatism (typical for the lherzolitic sources) characterized by fairly unfractionated trace and major element compositions to metasomatism by CHO fluids carrying primarily incompatible trace elements. Melt and fluid metasomatism are viewed as a compositional continuum, with residual CHO fluids resulting from primary silicate or carbonate melts in the course of fractional crystallization and equilibration with lithospheric host rocks.

Eclogitic garnet inclusions show “normal” REE_N patterns, with LREE at about 1× and HREE at about 30× chondritic abundance. Clinopyroxenes approximately mirror the garnet patterns, being enriched in LREE and having chondritic HREE abundances. Positive and negative Eu anomalies are observed for both garnet and clinopyroxene inclusions. Such anomalies are strong evidence for crustal precursors for the eclogitic diamond sources. The trace element composition of an “average eclogitic diamond source” based on garnet and clinopyroxene inclusions is consistent with derivation from former oceanic crust that lost about 10% of a partial melt in the garnet stability field and that subsequently experienced only minor reenrichment in the most incompatible trace elements. Based on individual diamonds, this simplistic picture becomes more complex, with evidence for both strong enrichment and depletion in LREE.

Trace element data for sublithospheric inclusions in diamonds are less abundant. REE in majoritic garnets indicate source compositions that range from being similar to lithospheric eclogitic sources to strongly LREE enriched. Lower mantle sources, assessed based on CaSi–perovskite as the principal host for REE, are not primitive in composition but show moderate to strong LREE enrichment. The bulk rock LREE_N–HREE_N slope cannot be determined from CaSi–perovskites alone, as garnet may be present in these shallow lower mantle sources and then would act as an important host for HREE. Positive and negative Eu anomalies are widespread in CaSi–perovskites and negative anomalies have also been observed for a majoritic garnet and a coexisting clinopyroxene inclusion. This suggests that sublithospheric diamond sources may be linked to old oceanic slabs, possibly because only former crustal rocks can provide the redox gradients necessary for diamond precipitation in an otherwise reduced sublithospheric mantle.     

Diamondiferous lithospheric roots along the western margin of the Kalahari Craton—the peridotitic inclusion suite in diamonds from Orapa and Jwaneng

The Orapa and Jwaneng kimberlites are located along the western margin of the Kalahari Craton and the prevalence of eclogitic over peridotitic diamonds in both mines has recently been linked to lower P-wave velocities in the deep mantle lithosphere (relative to the bulk of the craton) to suggest a diamond formation event prompted by mid-Proterozoic growth and modification of preexisting Archean lithosphere (Shirey et al. 2002). Here we study peridotitic diamonds from both mines, with an emphasis on the style of metasomatic source enrichment, to evaluate their relationship with this major eclogitic diamond formation event. In their major element chemistry, the peridotitic inclusions compare well with a world-wide database but reveal differences to diamond sources located in the interior of the Western Terrane of the Kaapvaal block, where the classical mines in the Kimberley region are located. The most striking difference is the relative paucity of low-Ca (<2 wt% CaO in garnet) harzburgites and a low ratio of harzburgitic to lherzolitic garnets (2:1). This suggests that lithospheric mantle accreted to the rim of the Zimbabwe and Kaapvaal blocks was overall chemically less depleted. Alternatively, this more fertile signature may be assigned to stronger metasomatic re-enrichment but the trace element signature of garnet inclusions is not in favor of strong enrichment in major elements. For both mines the majority of lherzolitic and harzburgitic garnet inclusions are characterized by moderately sinusoidal REE_N patterns and low Ti, Zr and Y contents, indicative of a metasomatic agent with very high LREE/HREE and low HFSE. This is consistent with metasomatism by a CHO-fluid or, as modeled by Burgess and Harte (2003), a highly fractionated, low-volume silicate melt from the MORB-source. In both cases, changes in the major element chemistry of the affected rocks will be limited. In a few garnets from Orapa preferential MREE enrichment is observed, suggesting that the percolating fluid/melt fractionated a LREE-phyllic phase (such as crichtonite). The overall moderate degree of metasomatism reflected by the inclusion chemistry is in stark contrast to lithospheric sections for Orapa and Jwaneng based on mantle xenocrysts and xenoliths, revealing extensive mantle metasomatism (Griffin et al. 2003). This suggests that the formation of peridotitic diamonds predates the intensive modification of the subcratonic lithosphere during Proterozoic rifting and compression, implying that diamonds may survive major tectonothermal events.Editorial responsibility: J. Hoefs     

FTIR spectroscopy of OH in olivine: A new tool in kimberlite exploration

Our study of olivines from Canadian kimberlites shows that the application of FTIR spectroscopy significantly improves the reliability of olivine as a kimberlite indicator mineral (KIM). We have developed an algorithm that yields the water concentration and the normalized intensity of the OH IR absorption band at 3572 cm⁻¹ from unpolished olivine grains of unknown thickness. For 80% of kimberlitic olivines these two parameters are significantly higher than those for olivines from non-kimberlitic magmas and consequently, olivines with water concentrations >60 ppm and a strong absorption band at 3572 cm⁻¹ can be reliably classified as being kimberlitic.We have identified two major spectral features in the OH absorption bands of kimberlitic olivines that allow for a more detailed classification: (a) the presence of three types of high-requency OH absorption bands (Group 1A, 1B and 1C) and (b) the proportion of low-frequency OH absorption bands (Group 2) relative to high-frequency bands (Group 1). Comparison of our results with experimental studies suggests that differences within Group 1 OH absorption bands are due to different pressures of crystallization or hydrogenation. The three identified types of Group 1 OH absorption bands approximately correspond to high (P > 2 GPa, Group 1A), moderate (2-1 GPa, Group 1B), and low (<1 GPa, Group 1C) pressures of hydrogenation. Group 2 OH IR absorption bands in olivines with NiO > 3500 ppm are interpreted to reflect olivine-orthopyroxene equilibria and hence are indicative of xenocrystic olivine derived from lherzolitic or harzburgitic mantle sources. Interaction of xenocrystic olivine with hydrous kimberlitic melts with low silica activity likely will cause a gradual increase in Group 1 absorption bands. Therefore, FTIR spectra of olivine can be used to obtain qualitative estimates of the duration of interaction between mantle material and a kimberlitic melt.In addition to applications in kimberlite and diamond exploration, FTIR spectra of olivine phenocrysts, combined with mineral chemical data, may also provide insights into kimberlite evolution. Our data suggest that in some instances the ascent of kimberlitic magmas could have been interrupted at or near the Moho, followed by olivine crystallization and exsolution of aqueous fluids.     

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