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Distinguishing syngenetic from protogenetic inclusions in natural diamonds is one of the most debated issues in diamond research. Were the minerals that now reside in inclusions in diamonds born before the diamond that hosts them (protogenesis)? Or did they grow simultaneously and by the same reaction (syngenesis)? Once previously published data on periclase [(Mg,Fe)O] and magnesiochromite (MgCr 2 O 4 ) inclusions in diamond have been re-analysed, we show that the main arguments reported so far to support syngenesis between diamond and its mineral inclusions, definitely failed. Hence: (a) the epitaxial relationships between diamond and its mineral inclusion should no longer be used to support syngenesis, because only detecting an epitaxy does not tell us which was the nucleation substrate (there are evidences that in case of epitaxy, the inclusion acts as a nucleation substrate); (b) the morphology of the inclusion should no longer be used as well, as inclusions could be protogenetic regardless their shapes. Finally, we advance the hypothesis that the majority of inclusions in diamonds are protogenetic, e.g., they are constituent of rocks in which diamonds were formed and not products of reactions during diamond growth.

We studied diamond inclusions in the 133 Ma Lace kimberlite of the Kroonstad Group II kimberlite cluster (Kaapvaal craton) to compare them to diamonds beneath the adjacent coeval Voorspoed kimberlite. The studied 288 Lace diamonds are mostly colorless dodecahedral Type IaAB. Based on diamond inclusions (DI), 38 Lace diamonds were classified as eclogitic (44%, 19 samples), peridotitic (35%, 15 samples), and websteritic (9%, 4 samples). The diamonds formed from mantle carbon (δ 13 C = − 9.1 to − 2.5 ‰ for 18 samples), with the exception of one eclogitic diamond (δ 13 C = − 19.2 ‰). A rare zircon inclusion provides age constraints for the Lace eclogite protolith at 3.2 ± 0.4 Ga (Lu–Hf model age) and Lace eclogite diamond formation at 188 ± 37 Ma (U–Pb age). The eclogite protolith age suggests its formation contemporaneous with the lower crustal magmatism and metamorphism in the Central Kaapvaal craton, complementary to the tonalite–trondhjemite–granodiorite magmatism in the region and synchronous with the consolidation of the Eastern Kaapvaal Block. Two distinct kinds of eclogites are found to host Lace diamonds, (1) Fe-rich eclogites located at 160–190 km, and (2) more calcic–magnesian eclogites with mineral compositions identical to websteritic DIs, that derive from shallower lithospheric depths. Various thermobarometric methods applied to Lace diamonds and DIs constrain the Lace geotherm as reflecting a surface heat flow below or equal to 38 mW/m 2 and a lithosphere thickness of at least 220 km, at the time of kimberlite eruption. These thermal parameters demonstrate an excellent match between the thermal state of the Voorspoed and Lace mantle segments that persisted from the Archean to Cretaceous times. The Lace peridotitic-to-eclogitic diamond ratio (5/4) does not differ much from the Voorspoed DI ratio (6/4), but a hot and spatially restricted carbonatitic metasomatism event affected the Voorspoed peridotitic mantle to create the majority of Voorspoed diamonds. The contrast in the mineralogy of DIs in Lace and Voorspoed diamonds highlights the very local (ca. 10 km) extent of the metasomatism and heating, as well as the variability of the diamond-forming processes at the same spatial scale.

Trace-element concentrations in olivine and coexisting garnets included in diamonds from the Akwatia Mine (Ghana, West African Craton) were measured to show that olivine can provide similar information about equilibration temperature, diamond paragenesis and mantle processes as garnet. Trace-element systematics can be used to distinguish harzburgitic olivines from lherzolite ones: if Ca/Al ratios of olivine are below the mantle lherzolite trend (Ca/Al < 2.2), they are derived from a harzburgitic mantle source, and syngenetic garnets are without exception subcalcic G10 garnets. For harzburgitic olivines that cannot be identified this way, Na and Ca contents can be used: olivine inclusions with < 60 µg/g Na and Na/Al < 0.7 are all harzburgitic, whereas those with > 300 µg/g Ca or > 60 µg/g Na are lherzolitic. Conventional geothermobarometry indicates that Akwatia diamonds formed and resided close to a 39 mW/m2 conductive geotherm. A similar value can be derived from Al in olivine geothermometry, with TAl-ol ranging from 1020 to 1325 °C. Ni in garnet temperatures is on average somewhat higher (TNi-grt = 1115–1335 °C) and the correlation between the two thermometers is weak, which may be not only due to the large uncertainties in the calibrations, but also due to disequilibrium between inclusions from the same diamond. Calcium in olivine should not be used as a geothermobarometer for harzburgitic olivines, and often gives unrealistic P–T estimates for lherzolitic olivine as well. Diamond-hosted olivine inclusions indicate growth in an extremely depleted (low Ti, Ca, Na, high Cr#) environment with no residual clinopyroxene. They are distinct from olivines from mantle xenoliths which show higher, more variable Ti contents and lower Cr#. Hence, most olivine inclusions in Akwatia diamonds escaped the refertilisation processes that have affected most mantle xenoliths. Lherzolitic inclusions are probably the result of refertilisation after undergoing high-degree melting first. Trivalent cations appear to behave differently in harzburgitic diamond-hosted olivine inclusions than lherzolitic inclusions and olivine from mantle xenoliths. Some divalent chromium is predicted to be present in most olivine inclusions, which may explain high concentrations up to 0.16 wt% Cr2O3 observed in some diamond inclusions. Strong heterogeneity of Cr, V and Al in several inclusions may also result in apparent high Cr contents, and is probably due to late-stage processes during exhumation. However, in general, diamond-hosted olivine inclusions have lower Cr and V than expected compared to mantle xenoliths. Reduced Na activity in depleted harzburgites limits the uptake of Cr, V and Sc via Na–M3+ exchange. In contrast, Al partitioning in harzburgites is not significantly reduced compared to lherzolites, presumably due to uptake of Al in olivine by Al–Al exchange.

The recent discovery in high-pressure experiments of compounds stable to 24–26 GPa with Fe₄O₅, Fe₅O₆, Fe₇O₉, and Fe₉O11 stoichiometry has raised questions about their existence within the Earth’s mantle. Incorporating both ferric and ferrous iron in their structures, these oxides if present within the Earth could also provide insight into diamond-forming processes at depth in the planet. Here we report the discovery of metallic particles, dominantly of FeNi (Fe0.71Ni0.24Cu0.05), in close spatial relation with nearly pure magnetite grains from a so-called superdeep diamond from the Earth’s mantle. The microstructural relation of magnetite within a ferropericlase (Mg0.60Fe0.40)O matrix suggests exsolution of the former. Taking into account the bulk chemistry reconstructed from the FeNi(Cu) alloy, we propose that it formed by decomposition of a complex metal M oxide (M₄O₅) with a stoichiometry of (Fe3+ 2.15Fe2+ 1.59Ni2+ 0.17Cu⁺ 0.04)Σ = 3.95O₅. We further suggest a possible link between this phase and variably oxidized ferropericlase that is commonly trapped in superdeep diamond. The observation of FeNi(Cu) metal in relation to magnetite exsolved from ferropericlase is interpreted as arising from a multistage process that starts from diamond encapsulation of ferropericlase followed by decompression and cooling under oxidized conditions, leading to the formation of complex oxides such as Fe₄O₅ that subsequently decompose at shallower P-T conditions.

Nitrogen is the most abundant element in the Earth's atmosphere, yet its geochemical behavior and distribution among the various reservoirs (atmosphere, crust, mantle, and core) remain poorly understood. Although estimates of N and C fluxes in the mantle vary, there is a consensus regarding the disparity between input and output, leading to an increase in N and C contents in the mantle. The low solubility of N in mantle minerals raises questions about possible N or C storage in the mantle. Evidence suggests that Fe–N–C phases, such as Fe 3 C, Fe 7 C 3 , ε-Fe 3 N, metals, and non-stoichiometric carbonitrides, may be accessory phases at mantle pressure and temperature conditions, and thus potential hosts of C and N in the deep mantle. To investigate the phase relations and melting behavior in the (Fe,Ni)–N–C system, 19 experiments were conducted with varying starting compositions at 10 GPa and 1000–1400 °C. The results indicate that carbides, nitrides, carbonitrides, nitrocarbides, Fe(Ni)-metal, Fe-oxides, and diamond are stable at deep upper mantle pressure conditions. However, the compositions of naturally occurring nitrocarbides with high C and N contents, as found in diamond inclusions, could not be reproduced in the experiments. The significant incorporation of Ni in the experimental phases, which is also not observed in natural carbonitrides and nitrocarbides, suggests their formation in Ni-poor regimes. The solidus temperatures of the N- and C-rich systems are well below the adiabatic temperatures of the surrounding mantle. Therefore, it is hypothesized that cold regions in subduction zones, such as within or at the edge of a C- and N-rich subducted plate, are the likely formation environment for solid Fe–C–N phases.

The Sm–Nd isotope systematics and geochemistry of eclogitic, websteritic and peridotitic garnet and clinopyroxene inclusions together with characteristics of their corresponding diamond hosts are presented for the Letlhakane mine, Botswana. These data are supplemented with new inclusion data from the nearby (20–30 km) Orapa and Damtshaa mines to evaluate the nature and scale of diamond-forming processes beneath the NW part of the Kalahari Craton and to provide insight into the evolution of the deep carbon cycle. The Sm–Nd isotope compositions of the diamond inclusions indicate five well-defined, discrete eclogitic and websteritic diamond-forming events in the Orapa kimberlite cluster at 220 ± 80 Ma, 746 ± 100 Ma, 1110 ± 64 Ma, 1698 ± 280 Ma and 2341 ± 21 Ma. In addition, two poorly constrained events suggest ancient eclogitic (> 2700 Ma) and recent eclogitic and websteritic diamond formation (< 140 Ma). Together with sub-calcic garnets from two harzburgitic diamonds that have Archaean Nd mantle model ages (TCHUR) between 2.86 and 3.38 Ga, the diamonds studied here span almost the entire temporal evolution of the SCLM of the Kalahari Craton. The new data demonstrate, for the first time, that diamond formation occurs simultaneously and episodically in different parageneses, reflecting metasomatism of the compositionally heterogeneous SCLM beneath the area (~ 200 km2). Diamond formation can be directly related to major tectono-magmatic events that impacted the Kalahari Craton such as crustal accretion, continental breakup and large igneous provinces. Compositions of dated inclusions, in combination with marked variations in the carbon and nitrogen isotope compositions of the host diamonds, record mixing arrays between a minimum of three components (A: peridotitic mantle; B: eclogites dominated by mafic material; C: eclogites that include recycled sedimentary material). Diamond formation appears dominated by local fluid–rock interactions involving different protoliths in the SCLM. Redistribution of carbon during fluid–rock interactions generally masks any potential temporal changes of the deep carbon cycle.

We studied a suite of Cullinan diamonds (<0.3 ct) with mineral inclusions, which comprised 266 Type I and 75 blank Type II (<20 ppm N) diamonds, as classified by infrared spectroscopy. More than 90% (n = 68) of Type II diamonds do not luminesce. In contrast, 51.9% (n = 177) of Type I diamonds luminesce, with blue colors of different intensity. Carbon isotopic compositions of Type I and II diamonds are similar, with δ13CVPDB ranging from −2.1 to −7.7‰ for Type I diamonds (n = 25), and from −1.3 to −7.8‰ for Type II diamonds (n = 20). The Type II diamonds are sourced from three parageneses, lithospheric lherzolitic (45%), lithospheric eclogitic (33%), and sublithospheric mafic (22%). The lherzolitic suite contains Cr-pyrope, forsterite, enstatite, clinopyroxene and Cr-spinel formed at 1090–1530 °C and P = 4.6–7.0 GPa. Lithospheric eclogitic diamonds containing garnet, omphacite, kyanite and coesite comprise 33% of Type II diamonds. The sublithospheric mafic paragenesis is mainly represented by Cr-free majorite, various CaSiO3 phases and omphacite equilibrated at 11.6–26 GPa, in the transition zone and the lower mantle. The lherzolitic paragenesis predominates in Type II diamonds, whereas 79% Type I diamonds are sourced from eclogites. The higher incidence of sublithospheric inclusions was found in Type II diamonds, 22% against 6% in Type I diamonds. The similarity of the mineral parageneses and C isotopic compositions in the small Cullinan Type II and Type I diamonds indicate the absence of distinct mantle processes and carbon sources for formation of studied Type II diamonds. The parent rocks and the carbon sources generally vary for Type II diamonds within a kimberlite and between kimberlites.

The stability of the majorite component in garnet has been experimentally investigated at high pressure and high temperature, focusing on the effect of bulk composition and temperature. High-pressure experiments were performed in a multi-anvil apparatus, at pressures ranging from 6 to 14.5 GPa, and temperatures between 1400 and 1700 °C. Experiments were performed in a range of bulk compositions in the system SiO 2 –Al 2 O 3 –Cr 2 O 3 –CaO–MgO with varying Cr/(Cr + Al) ratios. The majorite content of garnet gradually increases with pressure, and the composition of the garnet, specifically the Cr/(Cr + Al) ratio, exerts a significant effect on the majorite substitution. We found no significant effect of temperature. We use the experimental results in combination with the literature data to derive two empirical geobarometers, which can be used to determine the equilibration pressure of natural majoritic garnets of peridotitic and eclogitic bulk compositions. The barometer for peridotitic compositions is P = - 77.1 + 27.6 × Si + 1.67 × Cr And the barometer for eclogitic compositions is P = - 29.6 + 11.8 × Si + 7.81 × Na + 4.49 × Ca .

Goldschmidtite is a new perovskite-group mineral (IMA No. 2018-034) with the ideal formula (K,REE,Sr)(Nb,Cr)O3. A single grain of goldschmidtite with a maximum dimension of ∼100 µm was found as an inclusion in a diamond from the Koffiefontein pipe in South Africa. In addition to the dark green and opaque goldschmidtite, the diamond contained a Cr-rich augite (websteritic paragenesis) and an intergrowth of chromite, Mg-silicate, and unidentified K-Sr-REE-Nb-oxide. Geothermobarometry of the augite indicates that the depth of formation was ∼170 km. The chemical composition of gold-schmidtite determined by electron microprobe analysis (n = 11, WDS, wt%) is: Nb2O5 44.82, TiO2 0.44, ThO2 0.10, Al2O3 0.35, Cr2O3 7.07, La2O3 11.85, Ce2O3 6.18, Fe2O3 1.96, MgO 0.70, CaO 0.04, SrO 6.67, BaO 6.82, K2O 11.53, total 98.53. The empirical formula (expressed to two decimal places) is (K0.50La0.15Sr0.13Ba0.09Ce0.08)Σ0.95(Nb0.70Cr0.19Fe0.05Al0.01Mg0.04Ti0.01)Σ1.00O3. Goldschmidtite is cubic, space group Pm3m, with unit-cell parameters: a = 3.9876(1) Å, V = 63.404(6) Å3, Z = 1, resulting in a calculated density of 5.32(3) g/cm3. Goldschmidtite is the K-analog of isolueshite, (Na,La)NbO3. Raman spectra of goldschmidtite exhibit many second-order broad bands at 100 to 700 cm-1 as well as a pronounced peak at 815 cm-1, which is possibly a result of local ordering of Nb and Cr at the B site. The name goldschmidtite is in honor of the eminent geochemist Victor Moritz Goldschmidt (1888-1947), who formalized perovskite crystal chemistry and identified KNbO3 as a perovskite-structured compound.