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Diamonds are the deepest accessible "fragments" of Earth, providing records of deep geological processes. Absolute ages for diamond formation are crucial to place these records in the correct time context. Diamond ages are typically determined by dating inclusions, assuming that they were formed simultaneously with their hosts. One of the most widely used mineral inclusions for dating diamond is garnet, which is amenable to Sm-Nd geochronology and is common in lithospheric diamonds. By investigating worldwide garnet-bearing diamonds, we provide crystallographic evidence that garnet inclusions that were previously considered to be syngenetic may instead be protogenetic, i.e., they were formed before the host diamond, raising doubts about the real significance of many reported diamond "ages." Diffusion modeling at relevant pressures and temperatures, however, demonstrates that isotopic resetting would generally occur over geologically short time scales. Therefore, despite protogenicity, the majority of garnet-based ages should effectively correspond to the time of diamond formation. On the other hand, our results indicate that use of large garnet inclusions (e.g., >100 μm) and diamond hosts formed at temperatures lower than ~1000 °C is not recommended for diamond age determinations. [ABSTRACT FROM AUTHOR]

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

We describe a new methodology to collect energy domain Mössbauer spectra of inclusions in natural diamonds using a Synchrotron Mössbauer Source (SMS). Measurements were carried out at the Nuclear Resonance beamline ID18 at the European Synchrotron Radiation Facility (Grenoble, France). We applied this non-destructive approach to collect SMS spectra of a ferropericlase inclusion still contained within its diamond host from Juina (Brazil). The high spatial resolution of the measurement (~ 15 μm) enabled multiple regions of the 190 × 105 μm 2 inclusion to be sampled and showed that while Fe 3 + /Fe tot values in ferropericlase were below the detection limit (0.02) overall, there was a magnetic component whose abundance varied systematically across the inclusion. Hyperfine parameters of the magnetic component are consistent with magnesioferrite, and the absence of superparamagnetism allows the minimum particle size to be estimated as ~ 30 nm. Bulk Fe 3 + /Fe tot values are similar to those reported for other ferropericlase inclusions from Juina, and their variation across the inclusion can provide constraints on its history. [ABSTRACT FROM AUTHOR]

Three single crystals of clinopyroxene trapped within three different gem-quality diamonds from the Udachnaya kimberlite (Siberia, Russia) were analysed in situ by single-crystal synchrotron X-ray diffraction in order to obtain information on their chemical composition and infer source assemblage type. A non-destructive approach was used with high-energy (≈ 60 keV; λ ≈ 0.206 Å) at I15, the extreme-conditions beamline at Diamond Light Source. A dedicated protocol was used to center the mineral inclusions located deep inside the diamonds in the X-ray beam. Our results reveal that two of the inclusions can be associated with peridotitic paragenesis whereas the third is eclogitic. This study also demonstrates that this non-destructive experimental approach is extremely efficient in evaluating the origin of minerals trapped in their diamond hosts. [ABSTRACT FROM AUTHOR]

In this work we report for the first time the crystallographic orientations of olivine inclusions trapped in diamonds from the Kaapvaal craton (South Africa) determined by single-crystal X-ray diffraction, and analyze them together with all available data in the literature. The overall data set indicates no preferred orientation of the olivine inclusions with respect to their diamond hosts. However, diamonds containing multiple olivine inclusions sometimes show clusters of olivines with the same orientation in the same diamond host. We conclude that such clusters can only be interpreted as the remnants of single olivine crystals pre-dating the growth of the host diamonds. [ABSTRACT FROM AUTHOR]

We report P – V and T – V Equations of State (EoS) for synthetic single crystal pyrope (Py, Mg 3 Al 2 Si 3 O 12 ) and the P – V EoS for synthetic single crystals of almandine (Alm, Fe 3 Al 2 Si 3 O 12 ) as well as an intermediate composition (Py 60 Alm 40 ) as measured by in-situ high-pressure and high-temperature X-ray diffraction experiments. The unit-cell volumes of the three samples were measured at room temperature and different pressures and up to about 8 GPa in a diamond-anvil cell. The high-temperature experiment was carried out using a micro-furnace. The pressure-volume data were fitted to a third order Birch–Murnaghan EoS giving the following coefficients: V 0 = 1506.15(16) Å 3 , K T 0 = 163.7(1.7) GPa and K ′ = 6.4(4) for pyrope, V 0 = 1533.52(10) Å 3 , K T 0 = 172.6(1.5) GPa and K ′ = 5.8(5) for almandine and V 0 = 1516.32(13) Å 3 , K T 0 = 167.2(1.7) GPa and K ′ = 5.6(5) for the intermediate Py 60 Alm 40 composition. The unit-cell volume along the pyrope–almandine join changes linearly within the error of measurement indicating ideality in the volume of mixing behaviour for the solid solution. The first pressure derivative, K ′, for all three garnets is similar within experimental uncertainty with an average value of K ′ = 6.0(4). The thermal expansion parameters for end-member pyrope, as described using to the Kroll-type EoS, with the Einstein temperature, θ E , fixed to 320 K, are α (303 K, 1 bar) = 2.543(5) ∗ 10 − 5 K − 1 and V 0 = 1504.64(4) Å 3 . The determined thermoelastic parameters were combined in a thermal-pressure type EoS (thermal- P type EoS) to calculate the entrapment pressures, P e , for natural garnet inclusions in diamonds at mantle temperatures. A calculated pressure of 5.8 GPa at T = 1500 K using our newly determined thermoelastic parameters appears to be more consistent with diamond-forming conditions compared to the higher pressures that range up to 6.8 GPa at T = 1500 K, which are obtained using thermoelastic data in the literature. [ABSTRACT FROM AUTHOR]

The identification ofsyngeneticinclusions in diamond (i.e. inclusions of minerals that crystallized at the same time and by the same genesis as their host) has long been of paramount importance in diamond studies. However, the widespread assumption that many or most inclusions in diamonds are syngenetic is based on qualitative morphological criteria and few direct measurements. In order to provide statistically significant information on inclusion–host genetic relations for at least one kimberlite, we have determined the crystallographic orientations of 43 olivine inclusions with diamond-imposed morphology, a feature generally interpreted to indicate syngenesis, in 20 diamonds from the Udachnaya kimberlite (Siberia). Our unprecedented large data set indicates no overall preferred orientation of these olivines in diamond. However, multiple inclusions within a single diamond frequently exhibit similar orientations, implying that they were derived from original single monocrystals. Therefore, regardless of the possible chemical re-equilibration during diamond-forming processes, at least some of the olivines may have existed prior to the diamond (i.e. they areprotogenetic). Our results imply that a diamond-imposed morphology alone cannot be considered as unequivocal proof of syngenicity of mineral inclusions in diamonds. [ABSTRACT FROM PUBLISHER]

Three natural olivines with Fo80Fa20, Fo71Fa29, and Fo62Fa38 compositions were investigated in situ at high pressure by single-crystal X-ray diffraction using a diamond-anvil cell up to ~8 GPa at room temperature. The bulk modulus, KT0, and its first pressure derivative, K', do not show any significant variation among the compositions investigated and, using the data on a further sample with Fo92Fa8 composition recently investigated in the same laboratory and using the same experimental technique, we obtain, for the first time, a single equation of state for the entire Fo92Fa8-Fo62Fa38 compositional range. The equation has the following coefficients: KT0 = 124.7(9) GPa and K' = 5.3(3) and can be used for thermodynamic calculations involving the most common mantle olivine compositions. [ABSTRACT FROM AUTHOR]

Four synthetic crystals belonging to the jadeite (Jd, NaAlSi2O6)-hedenbergite (Hd, CaFeSi2O6) solid solution were investigated by X-ray diffraction in situ at high pressure using a diamond anvil cell to Pmax = 10.6 GPa. The samples exhibited space group symmetry C2/c throughout the investigated pressure range and did not show any phase transformations. V0, KT0, and K′ were simultaneously refined by fitting a third-order Birch-Murnaghan equation of state to pressure-volume data for all samples. The following relationship between bulk modulus and molar fraction of jadeite is observed: KT0 = 108.7(2) (GPa) + 0.191(9) × [% molar Jd] + 0.0006(1) × [% molar Jd]2 The bulk modulus of hedenbergite is 19% lower than jadeite with a strong axial anisotropy that increases with increasing the Hd content. In particular, the compressibility along the b axis (the most compressible in pyroxenes) increases by about 35% going from Jd to Hd while along the c axis the increase in compressibility is about 24%. The a axis does not show any variation in the deformation rate along the join. The analysis of the crystal structure behavior with pressure for all samples clearly indicates that the main cause of the strong anisotropy on the b-c plane is related to the narrowing of the M1 octahedral chain and to anion-anion interactions increasing the packing efficiency of the anion skeletons of the crystals going from Jd to Hd. [ABSTRACT FROM AUTHOR]

Sulfides are the most abundant inclusions in diamonds and a key tool for dating diamond formation via Re-Os isotopic analyses. The manner in which fluids invade the continental lithospheric mantle and the time scale at which they equilibrate with preexisting (protogenetic) sulfides are poorly understood yet essential factors to understanding diamond formation and the validity of isotopic ages. We investigated a suite of sulfide-bearing diamonds from two Canadian cratons to test the robustness of Re-Os in sulfide for dating diamond formation. Single-crystal X-ray diffraction (XRD) allowed determination of the original monosulfide solid-solution (Mss) composition stable in the mantle, indicating subsolidus conditions of encapsulation, and providing crystallographic evidence supporting a protogenetic origin of the inclusions. The results, coupled with a diffusion model, indicate Re-Os isotope equilibration is sufficiently fast in sulfide inclusions with typical grain size, at mantle temperatures, for the system to be reset by the diamond-forming event. This confirms that even if protogenetic, the Re-Os isochrons defined by these minerals likely reflect the ages of diamond formation, and this result highlights the power of this system to date the timing of fluid migration in mantle lithosphere. [ABSTRACT FROM AUTHOR]

Diamonds are unrivalled in their ability to record the mantle carbon cycle and mantle f O 2 over a vast portion of Earth's history. Diamonds' inertness and antiquity means their carbon isotopic characteristics directly reflect their growth environment within the mantle as far back as ∼3.5 Ga. This paper reports the results of a thorough secondary ion mass spectrometry (SIMS) carbon isotope and nitrogen concentration study, carried out on fragments of 144 diamond samples from various locations, from ∼3.5 to 1.4 Ga for P [peridotitic]-type diamonds and 3.0 to 1.0 Ga for E [eclogitic]-type diamonds. The majority of the studied samples were from diamonds used to establish formation ages and thus provide a direct connection between the carbon isotope values, nitrogen contents and the formation ages. In total, 908 carbon isotope and nitrogen concentration measurements were obtained. The total δ13C data range from −17.1 to −1.9 ‰ (P = −8.4 to −1.9 ‰; E = −17.1 to −2.1‰) and N contents range from 0 to 3073 at. ppm (P = 0 to 3073 at. ppm; E = 1 to 2661 at. ppm). In general, there is no systematic variation with time in the mantle carbon isotope record since > 3 Ga. The mode in δ13C of peridotitic diamonds has been at −5 (±2) ‰ since the earliest diamond growth ∼3.5 Ga, and this mode is also observed in the eclogitic diamond record since ∼3 Ga. The skewness of eclogitic diamonds' δ13C distributions to more negative values, which the data establishes began around 3 Ga, is also consistent through time, with no global trends apparent. No isotopic and concentration trends were recorded within individual samples, indicating that, firstly, closed system fractionation trends are rare. This implies that diamonds typically grow in systems with high excess of carbon in the fluid (i.e. relative to the mass of the growing diamond). Any minerals included into diamond during the growth process are more likely to be isotopically reset at the time of diamond formation, meaning inclusion ages would be representative of the diamond growth event irrespective of whether they are syngenetic or protogenetic. Secondly, the lack of significant variation seen in the peridotitic diamonds studied is in keeping with modeling of Rayleigh isotopic fractionation in multicomponent systems (RIFMS) during isochemical diamond precipitation in harzburgitic mantle. The RIFMS model not only showed that in water-maximum fluids at constant depths along a geotherm, fractionation can only account for variations of <1‰, but also that the principal δ13C mode of −5 ± 1‰ in the global harzburgitic diamond record occurs if the variation in f O 2 is only 0.4 log units. Due to the wide age distribution of P-type diamonds, this leads to the conclusion that the speciation and oxygen fugacity of diamond forming fluids has been relatively consistent. The deep mantle has therefore generated fluids with near constant carbon speciation for 3.5 Ga. [ABSTRACT FROM AUTHOR]

Type IIb diamonds are those that contain more boron than nitrogen. The presence of this uncompensated boron gives rise to absorption in the infrared part of the electromagnetic spectrum, extending into the visible region and often resulting in blue colouration. Here we report on the expansion of the DiaMap freeware (for the automated spectral deconvolution of Type I [nitrogen containing] diamonds) to work on Type IIb diamonds, returning concentrations from three boron-related absorption bands, and determining which band provides the most reliable value. The program uses the calibration coefficients of Collins (2010), which show good relative agreement between the three bands, but might require some further study to confirm their absolute accuracy to the uncompensated boron concentration. The methodology of DiaMap_IIb is applicable to all Type IIb diamonds, both natural and synthetic. Analysis of high-resolution Fourier-transform infrared (FTIR) maps of two high-pressure high-temperature (HPHT) synthetic diamonds using DiaMap_IIb, confirm the growth sector dependence of the boron incorporation. Partitioning of boron strongly favours the octahedral {111} sectors. Unlabelled Image • The causes of the three main Boron-related IR absorption bands are reported. • Detailed methodology for processing IR spectra from Type IIb diamonds is provided. • DiaMap_IIb is an automated script for processing batches of spectra from IR mapping. • Boron partitioning strongly favours incorporation into octahedral growth sectors. [ABSTRACT FROM AUTHOR]

In this study, we report the first direct evidence for water-bearing fluids in the uppermost lower mantle from natural ferropericlase crystal contained within a diamond from São Luíz, Brazil. The ferropericlase exhibits exsolution of magnesioferrite, which places the origin of this assemblage in the uppermost part of the lower mantle. The presence of brucite–Mg(OH) 2 precipitates in the ferropericlase crystal reflects the later-stage quenching of H 2 O-bearing fluid likely in the transition zone, which has been trapped during the inclusion process in the lower mantle. Dehydration melting may be one of the key processes involved in transporting water across the boundary between the upper and lower mantle. [ABSTRACT FROM AUTHOR]

“Super-deep” diamonds are thought to crystallize between 300 and 800 km depth because some of the inclusions trapped within them are considered to be the products of retrograde transformation from lower mantle or transition zone precursors. In particular, single inclusion CaSiO 3 -walstromite is believed to derive from CaSiO 3 -perovskite, although its real depth of origin has never been proven. Our aim is therefore to determine for the first time the pressure of formation of the diamond-CaSiO 3 -walstromite pair by “single-inclusion elastic barometry” and to determine whether CaSiO 3 -walstromite derives from CaSiO 3 -perovskite or not. We investigated several single phases and assemblages of Ca-silicate inclusions still trapped in a diamond coming from Juina (Brazil) by in-situ analyses (single-crystal X-ray diffraction and micro-Raman spectroscopy) and we obtained a minimum entrapment pressure of ~ 5.7 GPa (∼ 180 km) at 1500 K. However, the observed coexistence of CaSiO 3 -walstromite, larnite ( β -Ca 2 SiO 4 ) and CaSi 2 O 5 -titanite in one multiphase inclusion within the same diamond indicates that the sample investigated is sub-lithospheric with entrapment pressure between ~ 9.5 and ~ 11.5 GPa at 1500 K, based on experimentally-determined phase equilibria. In addition, thermodynamic calculations suggested that, within a diamond, single inclusions of CaSiO 3 -walstromite cannot derive from CaSiO 3 -perovskite, unless the diamond around the inclusion expands by ~ 30% in volume. [ABSTRACT FROM AUTHOR]

When and how Earth's ancient crust – the cratons – became underpinned by cool, thick lithospheric mantle roots capable of hosting diamonds are among the most controversial aspects of Archean geology. Alluvial diamonds in cratonic sedimentary cover rocks, whose minimum age is determined by detrital-zircon geochronology, provide a unique perspective on this topic. A new discovery of a diamond-bearing quartz-pebble conglomerate from the northern Slave craton, Canada contains detrital zircon with a restricted U-Pb age distribution that has a dominant peak at ∼2.94 Ga and depositional age of ∼2.83 Ga. Pressure-temperature constraints derived from an olivine-diamond host pair lie on a conductive Mesoarchean geotherm of ∼36–38 mW/m2, comparable to the coolest modern lithospheric geotherms. This result is at odds with a hotter geothermal gradient related to nearby Mesoarchean komatiites. We propose a model whereby early building blocks for cratons were small but with deep cool roots that formed by slab-stacking, and were subsequently juxtaposed with regions of thinner, hotter lithosphere. This heterogeneous initial architecture later amalgamated and thickened through lateral accretion forming the more uniformly thick cratonic lithosphere observed today. Thermal modelling indicates that stacking/thickening of cool initial lithosphere into a lithospheric keel thick enough to stabilise diamonds is the most likely way of generating the observed geotherm by Mesoarchean times. • Detrital zircon in host sedimentary rock has a Mesoarchean U-Pb age of >2.83 Ga. • Oxidizing diamond-forming fluids had crustal component (non-mantle δ 13 C- δ 15 N). • PT constraints show cool conductive Mesoarchean mantle geotherm of ∼36–38 mW/m2. • Early cratonic building blocks were small with deep cool roots. • These blocks likely formed through slab-stacking. [ABSTRACT FROM AUTHOR]

The study of diamond and its solid inclusions is of paramount importance to acquire direct information on the deepest regions of the Earth. However, although diamond is one of the most studied materials in geology, the diamond-inclusion relationships are not yet understood: do they form simultaneously (syngenesis) or are inclusions pre-existing objects on which diamond nucleated (protogenesis)? Here we report, for the first time, adhesion energies between diamond (D) and forsterite (Fo) to provide a crucial contribution to the syngenesis/protogenesis debate. The following interfaces were investigated at quantum-mechanical level: (i) (001) D /(001) Fo , (ii) (001) D /(021) Fo , and (iii) (111) D /(001) Fo . Our data, along with the ones recently obtained on the (110) D /(101) Fo interface, revealed an unexpected thermodynamic behaviour, all interfaces showing almost equal and low adhesion energies: accordingly, diamond and olivine have an extremely low chemical affinity and cannot develop preferential orientations, even during an eventual epitaxial growth. Combining these results with those of our previous work concerning the morphology constraints of diamond on its inclusions, we can state that the two main arguments used so far in favour of diamond/inclusions syngenesis cannot be longer considered valid, at least for olivine. [ABSTRACT FROM AUTHOR]