Deep carbon through time: Earth’s diamond record and its implications for carbon cycling and fluid speciation in the mantle

Diamonds are unrivalled in their ability to record the mantle carbon cycle and mantle fO2 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 fO2 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

Methane-related diamond crystallization in the Earth's mantle: Stable isotope evidences from a single diamond-bearing xenolith

Mineralogical studies of deep-seated xenoliths and mineral inclusions in diamonds indicate that there is significant variability in oxygen fugacity within the Earth's upper mantle. This variability is consistent both with the occurrence of reduced (methane-bearing) or oxidized (CO2/carbonate-bearing) fluids. Invariably, direct sampling of reduced deep fluids is not possible as they are unquenchable and re-equilibrate with either the surrounding mantle or are affected by degassing. Key information about the nature of such fluids might be found in diamond if it were possible to study a population related to a single source. Usually, diamonds within a kimberlite pipe have different parageneses and can be shown to have formed at different times and depths. We studied 59 diamonds extracted from a single diamondiferous peridotite xenolith (with a volume of only 27 cm3), from the Cullinan mine (formerly called the Premier mine) in South Africa. Diamond sizes range from 0.0005 to 0.169 carats (0.1 to 33.8 mg). A correlation between the nitrogen contents of the diamonds (range 40 to 1430 ppm) and their nitrogen aggregation state (varying from 10 to 85% of IaB defects) is compatible with a single growth event. δ13C-values range from − 4.2‰ to − 0.1‰, with slight internal variability measured in the largest diamonds. Nitrogen isotope measurements show δ15N ranging from − 1.2‰ to + 7.2‰. On the centimeter scale of this upper mantle rock, the variations for nitrogen content, nitrogen aggregation state, carbon and nitrogen isotopic compositions, respectively, cover 64%, 75%, 15% and 23% of the ranges known for peridotitic diamonds. In spite of such large ranges, N-content, δ13C and δ15N within this diamond population are distinctly coupled. These relationships do not support a mixing of carbon sources, but are best explained by a Rayleigh distillation within the sub-continental mantle at depths > 150 km and T > 1200 °C, which precipitates diamonds from methane-bearing fluid(s). The involvement of this reduced metasomatic agent also suggests that the heterogeneous redox state of Archean cratons may mostly result from the heterogeneous nature of percolating fluids. The striking variability of the four determined parameters at cm scale may also account for the difficulty in interpreting these parameters in larger productions, such as those from a mine, because in these cases, the diamonds are mixed and sub-populations cannot be disentangled

Sulfur- and oxygen-isotope constraints on the sedimentary history of apparent conglomerates from the Nuvvuagittuq Greenstone Belt (Nunavik, Québec)

International audienceMafic igneous rocks of the Nuvvuagittuq Greenstone Belt (NGB) crystallized before 3.8 Ga and possibly as early as 4.3 Ga, potentially making the belt the oldest known supracrustal sequence on Earth. However, detrital zircons from a rare quartz-biotite schist in the NGB yield significantly younger ages of ≈3.77 Ga or less. These appear to be inconsistent with the ages of the mafic igneous rocks, as the quartz-biotite schist has been interpreted as a metaconglomerate, formed by the dismantling of preexisting lithologies. In order to assess this genetic interpretation, we performed a sulfur and oxygen isotope study of the quartz-biotite schist. Sulfide grains found in quartz clasts and the matrix show significant mass-independent fractionation of sulfur isotopes (+0.2‰≤Δ33S‰≤+1.0‰; mean Δ33S=+0.5±0.1‰). Secondary sulfides from crosscutting veins do not show mass-independent fractionation of sulfur isotopes (-0.1‰≤Δ33S≤+0.3‰; mean Δ33S=+0.1±0.1‰). Oxygen isotope compositions of quartz from clasts, matrix and a fine-grained lens are highly enriched in 18O (16.9‰≤δ18O≤26.7‰). Non-zero Δ33S values indicate a surficial origin for sulfur, probably the Eoarchean atmosphere, while high δ18O values suggest a low-temperature (65±18 °C) origin for the quartz, likely as chemical precipitation of a chert precursor from Si-saturated seawater. Therefore, the coupled S- and O-isotope measurements show that primary isotopic signatures characteristic of surficial environments survived the protracted metamorphic history of the NGB, and suggest that the quartz-biotite schist contains material that originated as chemical metasediments. The near mono-mineralic compositions of the clasts (quartz) and their shared 18O-enrichment suggest that they had a common protolith, which was deposited prior to the formation of the schist, and subsequently reworked. Whether the quartz-biotite schist represents a metaconglomerate or a structural melange, it preserves remnants of some of the oldest chemical sediments on Earth

Protogenetic sulfide inclusions in diamonds evidenced from δ33S, δ34S, δ15N and δ13C analyses

International audienc

Hydrothermally-altered mafic crust as source for early Earth TTG: Pb/Hf/O isotope and trace element evidence in zircon from TTG of the Eoarchean Saglek Block, N. Labrador

International audienc

Super-reducing conditions in ancient and modern volcanic systems: sources and behaviour of carbon-rich fluids in the lithospheric mantle

International audienceOxygen fugacity (ƒO2) is a key parameter of Earth's mantle, because it controls the speciation of the fluids migrating at depth; a major question is whether the sublithospheric mantle is metal-saturated, keeping ƒO2 near the Iron-Wustite (IW) buffer reaction. Cretaceous basaltic pyroclastic rocks on Mt. Carmel, Israel erupted in an intraplate environment with a thin, hot lithosphere. They contain abundant aggregates of hopper-shaped crystals of Ti-rich corundum, which have trapped melts with phenocryst assemblages (Ti2O3, SiC, TiC, silicides, native V) requiring extremely low ƒO2. These assemblages are interpreted to reflect interaction between basaltic melts and mantle-derived fluids dominated by CH4 + H2. Similar highly reduced assemblages are found associated with volcanism in a range of tectonic situations including subduction zones, major continental collisions, intraplate settings, craton margins and the cratons sampled by kimberlites. This distribution, and the worldwide similarity of δ13C in mantle-derived SiC and associated diamonds, suggest a widespread process, involving similar sources and independent of tectonic setting. We suggest that the common factor is the ascent of abiotic (CH4 + H2) fluids from the sublithospheric mantle; this would imply that much of the mantle is metal-saturated, consistent with observations of metallic inclusions in sublithospheric diamonds (e.g. Smith et al. 2016). Such fluids, perhaps carried in rapidly ascending deep-seated magmas, could penetrate high up into a depleted cratonic root, establishing the observed trend of decreasing ƒO2 with depth (e.g. Yaxley et al. in Lithos 140:142-151, 2012). However, repeated metasomatism (associated with the intrusion of silicate melts) will raise the FeO content near the base of the craton over time, developing a carapace of oxidizing material that would prevent the rise of CH4-rich fluids into higher levels of the subcontinental lithospheric mantle (SCLM). Oxidation of these fluids would release CO2 and H2O to drive metasomatism and low-degree melting both in the carapace and higher in the SCLM. This model can explain the genesis of cratonic diamonds from both reduced and oxidized fluids, the existence of SiC as inclusions in diamonds, and the abundance of SiC in some kimberlites. It should encourage further study of the fine fractions of heavy-mineral concentrates from all types of explosive volcanism

How Multiple Sulfur Isotopes (δ33S, δ34S, δ36S) Help Unravel the Context of Thermochemical Sulfate Reaction during Metamorphic Events: Application to Subducted Evaporites from the French Alps

International audienc

Two billion years of episodic and simultaneous websteritic and eclogitic diamond formation beneath the Orapa kimberlite cluster, Botswana

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