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

In situ multiple sulfur isotope analysis by SIMS of pyrite, chalcopyrite, pyrrhotite, and pentlandite to refine magmatic ore genetic models

With growing interest in the application of in situ multiple sulfur isotope analysis to a variety of mineral systems, we report here the development of a suite of sulfur isotope standards for distribution relevant to magmatic, magmatic-hydrothermal, and hydrothermal ore systems. These materials include Sierra pyrite (FeS2), Nifty-b chalcopyrite (CuFeS2), Alexo pyrrhotite (Fe(1 −x)S), and VMSO pentlandite ((Fe,Ni)9S8) that have been chemically characterized by electron microprobe analysis, isotopically characterized for δ33S, δ34S, and δ36S by fluorination gas-source mass spectrometry, and tested for homogeneity at the micro-scale by secondary ion mass spectrometry. Beam-sample interaction as a function of crystallographic orientation is determined to have no effect on δ34S and Δ33S isotopic measurements of pentlandite. These new findings provided the basis for a case study on the genesis of the Long-Victor nickel-sulfide deposit located in the world class Kambalda nickel camp in the southern Kalgoorlie Terrane of Western Australia. Results demonstrate that precise multiple sulfur isotope analyses from magmatic pentlandite, pyrrhotite and chalcopyrite can better constrain genetic models related to ore-forming processes. Data indicate that pentlandite, pyrrhotite and chalcopyrite are in isotopic equilibrium and display similar Δ33S values + 0.2‰.This isotopic equilibrium unequivocally fingerprints the isotopic signature of the magmatic assemblage. The three sulfide phases show slightly variable δ34S values (δ34Schalcopyrite = 2.9 ± 0.3‰, δ34Spentlandite = 3.1 ± 0.2‰, and δ34Spyrrhotite = 3.9 ± 0.5‰), which are indicative of natural fractionation. Careful in situ multiple sulfur isotope analysis of multiple sulfide phases is able to capture the subtle isotopic variability of the magmatic sulfide assemblage, which may help resolve the nature of the ore-forming process. Hence, this SIMS-based approach discriminates the magmatic sulfur isotope signature from that recorded in metamorphic- and alteration-related sulfides, which may not be resolved during bulk rock fluorination analysis. The results indicate that, unlike the giant dunite-hosted komatiite systems that thermo-mechanically assimilated volcanogenic massive sulfides proximal to vents and display negative Δ33S values, the Kambalda ores formed in relatively distal environments assimilating abyssal sulfidic shales

An atmospheric source of S in Mesoarchaean structurally-controlled gold mineralisation of the Barberton Greenstone Belt

The Barberton Greenstone Belt of southern Africa hosts several Mesoarchaean gold deposits. The ores were mostly formed in greenschist facies conditions, and occur as hydrothermal alteration zones around extensional faults that truncate and post-date the main compressional structures of the greenstone belt. Ore deposition was accompanied by the intrusion of porphyries, which has led to the hypothesis that gold may have been sourced from magmas. Because the transport of Au in the hydrothermal fluids is widely believed to have involved S complexes, tracing the origin of S may place strong constraints on the origin of Au. We measured multiple S isotopes in sulfide ore from Sheba and Fairview mines of the Barberton Greenstone Belt to distinguish “deep” S sources (e.g. magmas) from “surface” S sources (i.e. rocks of the volcano-sedimentary succession that contain S processed in the atmosphere preserved as sulfide and sulfate minerals). Ion probe (SIMS) analyses of pyrite from ore zones indicate mass-independent fractionation of S isotopes (Δ33S = −0.6‰ to +1.0‰) and the distribution of the analyses in the Δ33S–δ34S space matches the distribution peak of previously published analyses of pyrite from the entire volcano-sedimentary succession. Notwithstanding that the H2O–CO2 components of the fluids may have been introduced from a deep source external to the greenstone belt rocks, the fact that S bears an atmospheric signature suggests the hypothesis that the source of Au should also be identified in the supracrustal succession of the greenstone belt. Our findings differ from conclusions of previous studies of other Archaean shear-hosted Au deposits based on mineralogical and isotopic evidence, which suggested a magmatic or mantle source for Au, and imply that there is no single model that can be applied to this type of mineralisation in the Archaean

Homogenisation of sulphide inclusions within diamonds: A new approach to diamond inclusion geochemistry

Base metal sulphide (BMS) inclusions in diamonds provide a unique insight into the chalcophile and highly siderophile element composition of the mantle. Entombed within their diamond hosts, these provide a more robust (closed system) sample, from which to determine the trace element, Re-Os and S-isotopic compositions of the mantle than mantle xenoliths or orogenic peridotites, as they are shielded from alteration during ascent to the Earth’s crust and subsequent surface weathering. However, at temperatures below 1100 °C some BMS inclusions undergo subsolidus re-equilibration from an original monosulphide solid solution (Mss) and this causes fractionation of the major and trace elements within the inclusions. Thus to study the subjects noted above, current techniques require the entire BMS inclusion to be extracted for analyses. Unfortunately, ‘flaking’ of inclusions during break-out is a frequent occurrence and hence the risk of accidentally under-sampling a portion of the BMS inclusion is inherent in current practices. This loss may have significant implications for Re-Os isotope analyses where incomplete sampling of a Re-rich phase, such as chalcopyrite that typically occurs at the outer margins of BMS inclusions, may induce significant bias in the Re-Os and 187Os/188Os measurements and resulting model and isochron ages. We have developed a method for the homogenisation of BMS inclusions in diamond prior to their break-out from the host stone. Diamonds are heated to 1100 °C and then quenched to chemically homogenise any sulphide inclusions for both major and trace elements. Using X-ray Computed Microtomography (µCT) we determine the shape and spatial setting of multiple inclusions within a host stone and crucially show that the volume of a BMS inclusion is the same both before and after homogenisation. We show that the homogenisation process significantly reduces the inherent variability of in situ analysis when compared with unhomogenised BMS, thereby widening the scope for multiple methods for quantitative analysis, even on ‘flakes’ of single BMS inclusions. Finally we show that the trace elements present in peridotite (P-type) and eclogitic (E-type) BMS are distinct, with P-type diamonds having systematically higher total platinum-group element (particularly Os, Ir, Ru) and Te and As concentrations. These distinctions suggest that the PGE and semi-metal budgets of mantle-derived partial melts will be significantly dependent upon the type(s) and proportions of sulphides present in the mantle source

Origine et formation des diamants dans le manteau supérieur : apport d'une systématique multi-isotopique (carbone, azote et soufre)

The purpose of this thesis was to better understand the origin and speciation of carbon in the metasomatic fluids that give rise to diamonds. It included the analysis of diamonds of the same xenolite, polycrystalline diamonds and diamonds with sulphide inclusions. This work was carried out in close collaboration with, among others, Dr. Jeff Harris (University of Glasgow) for the selection and characterization of the samples and Dr. Marc Chaussidon and Dr. Claire Rollion-Bard (CRPG-Nancy) for the implementation of the first measurements of the 33S / 32S and 34S / 32S isotopic compositions.This work has enabled several advances. First, the existence of reduced fluids in the mantle (i.e. containing methane) could be demonstrated. Finally, the opposite, if not contradictory, conclusions drawn from previous studies have been clarified by systematic analysis of the isotopic compositions of C, N in diamonds and S in sulphides from the same sample.This work confirmed the surface origin of sulfur (∆33S ≠ 0 per thousand) of sulphide inclusions with mantle signatures of diamonds (δ13C and δ15N ~ -5 per thousand). The data support a model of metasomatic diamond formation, by precipitation by mantle fluids including a pre-existing sulfide.he main implications of this work revolve around our understanding of the ages of diamond formation, the analysis of inclusions not necessarily making it possible to deduce the age of formation. On the other hand, this study illustrates significant differences between diamonds with sulfide inclusion and diamond with silicate inclusion, suggesting that the “ages” of formation of diamonds with silicate inclusion (or sulfide) cannot be generalized to all of the diamonds.Le but de cette thèse était de mieux comprendre l’origine et la spéciation du carbone des fluides métasomatiques qui donnent naissance aux diamants. Elle incluait l’analyse de diamants d’un même xénolite, de diamants polycristallins et de diamants à inclusions de sulfures. Ces travaux ont été menés en étroite collaboration avec, entre autres, le Dr. Jeff Harris (University of Glasgow) pour le choix et la caractérisation des échantillons et les Dr. Marc Chaussidon et Dr Claire Rollion-Bard (CRPG-Nancy) pour la mise en œuvre des premières mesures des compositions isotopiques 33S/32S et 34S/32S.Ce travail a permis plusieurs avancées. Tout d’abord, l’existence de fluides réduits dans le manteau (i.e. contenant du méthane) a pu être démontrée. Enfin, les conclusions opposées sinon contradictoires déduites des études précédentes ont été clarifiées par l’analyse systématique des compositions isotopiques du C, N des diamants et S des sulfures d’un même échantillon.Ce travail a permis de confirmer l’origine superficielle du soufre (∆33S ≠ 0 pour mille) des inclusions de sulfures avec des signatures mantéliques des diamants (δ13C et δ15N ~ -5 pour mille). Les données soutiennent un modèle de formation métasomatique des diamants, par précipitation par des fluides mantéliques englobant un sulfure pré-existant.es principales implications de ce travail tournent autour de notre compréhension des âges de formation des diamants, l’analyse des inclusions ne permettant pas nécessairement de déduire l’âge de formation. D’autre part, cette étude illustre des différences significatives entre diamants à inclusion de sulfure et diamant à inclusion silicatée, suggérant que les “âges” de formation des diamants à inclusion silicatée (ou de sulfure) ne peuvent être généralisés à l’ensemble des diamants

Origine et formation des diamants dans le manteau supérieur terrestre (apport d'une systématique multi-isotopique (carbone, azote et soufre))

PARIS7-Bibliothèque centrale (751132105) / SudocSudocFranceF

Effect of metamorphic overprint on early Earth isotopic ages: the case study of Saglek block (Labrador, Canada)

International audienc

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