Marco L. Fiorentini

Atmospheric Sulfur in Archean Komatiite-Hosted Nickel Deposits

Early Ore Formation Ore deposits contain most of the worlds metal resources, from commonly used metals such as iron, to precious and expensive metals such as platinum. Understanding how these ancient deposits form may lead to more efficient metal extraction and give clues about early Earth. Bekker et al. (p. 1086) studied sulfur and iron isotopes in 2.7-billion-year old Fe-Ni sulfide deposits from Canada and Australia and found that most of the metal-scavenging sulfur was originally atmospheric in origin. Photochemical reactions in the ancient oxygen-free atmosphere produced sulfide that eventually circulated to the sea floor and mixed with newly erupted komatite magmas. Thus, global surface processes in the oceans, atmosphere, and on continents are geochemically linked to ore-forming processes within Earth. The source of sulfur in economic iron-nickel sulfide deposits is primarily derived from the atmosphere. Some of Earth’s largest iron-nickel (Fe-Ni) sulfide ore deposits formed during the Archean and early Proterozoic. Establishing the origin of the metals and sulfur in these deposits is critical for understanding their genesis. Here, we present multiple sulfur isotope data implying that the sulfur in Archean komatiite-hosted Fe-Ni sulfide deposits was previously processed through the atmosphere and then accumulated on the ocean floor. High-temperature, mantle-derived komatiite magmas were then able to incorporate the sulfur from seafloor hydrothermal sulfide accumulations and sulfidic shales to form Neoarchean komatiite-hosted Fe-Ni sulfide deposits at a time when the oceans were sulfur-poor.

Progressive mixing of meteoritic veneer into the early Earth’s deep mantle

Komatiites are ancient volcanic rocks, mostly over 2.7 billion years old (from the Archaean era), that formed through high degrees of partial melting of the mantle and therefore provide reliable information on bulk mantle compositions. In particular, the platinum group element (PGE) contents of komatiites provide a unique source of information on core formation, mantle differentiation and possibly core–mantle interaction. Most of the available PGE data on komatiites are from late Archaean (∼2.7–2.9 Gyr old) or early Proterozoic (2.0–2.5 Gyr old) samples. Here we show that most early Archaean (3.5–3.2 Gyr old) komatiites from the Barberton greenstone belt of South Africa and the Pilbara craton of Western Australia are depleted in PGE relative to late Archaean and younger komatiites. Early Archaean komatiites record a signal of PGE depletion in the lower mantle, resulting from core formation. This signal diminishes with time owing to progressive mixing-in to the deep mantle of PGE-enriched cosmic material that the Earth accreted as the ‘late veneer’ during the Early Archaean (4.5–3.8 Gyr ago) meteorite bombardment.

Archean komatiite volcanism controlled by the evolution of early continents

Significance Komatiites are rare, ultra-high-temperature (∼1,600 °C) lavas that were erupted in large volumes 3.5–1.5 bya but only very rarely since. They are the signature rock type of a hotter early Earth. However, the hottest, most extensive komatiites have a very restricted distribution in particular linear belts within preserved Archean crust. This study used a combination of different radiogenic isotopes to map the boundaries of Archean microcontinents in space and time, identifying the microplates that form the building blocks of Precambrian cratons. Isotopic mapping demonstrates that the major komatiite belts are located along these crustal boundaries. Subsequently, the evolution of the early continents controlled the location and extent of major volcanic events, crustal heat flow, and major ore deposit provinces. The generation and evolution of Earth’s continental crust has played a fundamental role in the development of the planet. Its formation modified the composition of the mantle, contributed to the establishment of the atmosphere, and led to the creation of ecological niches important for early life. Here we show that in the Archean, the formation and stabilization of continents also controlled the location, geochemistry, and volcanology of the hottest preserved lavas on Earth: komatiites. These magmas typically represent 50–30% partial melting of the mantle and subsequently record important information on the thermal and chemical evolution of the Archean–Proterozoic Earth. As a result, it is vital to constrain and understand the processes that govern their localization and emplacement. Here, we combined Lu-Hf isotopes and U-Pb geochronology to map the four-dimensional evolution of the Yilgarn Craton, Western Australia, and reveal the progressive development of an Archean microcontinent. Our results show that in the early Earth, relatively small crustal blocks, analogous to modern microplates, progressively amalgamated to form larger continental masses, and eventually the first cratons. This cratonization process drove the hottest and most voluminous komatiite eruptions to the edge of established continental blocks. The dynamic evolution of the early continents thus directly influenced the addition of deep mantle material to the Archean crust, oceans, and atmosphere, while also providing a fundamental control on the distribution of major magmatic ore deposits.

Fluid flux melting generated postcollisional high Sr/Y copper ore–forming water-rich magmas in Tibet

Miocene postcollisional porphyry Cu deposits in southern Tibet are genetically associated with dacitic-rhyolitic intrusions with unusually high Sr/Y ratios (>40), which have been attributed to dehydration melting of garnet amphibolite in a thickened lower crust. To test this hypothesis and examine the hydration state of copper ore-forming high Sr/Y magmas, we utilize a geohygrometer for granitoid rocks, entailing zircon-saturation thermometry and H 2 O-dependent phase equilibria. The results show that these Tibetan high Sr/Y magmas had dissolved H 2 O contents >10 wt%, which considerably exceeds the water supply by dehydration melting of basaltic amphibolites (maximum of 6.7 ± 1.4 wt%). Our results indicate that high Sr/Y dacitic-rhyolitic magmas cannot be produced by dehydration melting of basaltic amphibolites. While H 2 O-added melting of basaltic amphibolites can produce high Sr/Y dacitic-rhyolitic melts, it does not yield high enough Mg# (>50) to match the Tibetan ore-forming porphyries. We propose an alternative model for the genesis of copper ore-forming high Sr/Y magmas in Tibet, and suggest that the high Sr/Y dacitic-rhyolitic porphyries in southern Tibet are residually H 2 O-enriched, high-pressure differentiation products of hydrous mafic partial melts of Tibetan mantle. This hypothesis is based on the previous investigation of Miocene mafic microgranular enclaves (mantle-derived melts), which define a fractionation trend with, and have Sr-Nd-Hf isotopic compositions similar to, the host Tibetan ore-forming porphyries.

Crustal evolution, intra-cratonic architecture and the metallogeny of an Archaean craton

Abstract The generation of the Earths continental crust modified the composition of the mantle and provided a stable, buoyant reservoir capable of capturing mantle material and ultimately preserving ore deposits. Within the continental crust, lithospheric architecture and associated cratonic margins are a first-order control on camp-scale mineralization. Here we show that the evolving crustal architecture of the Archaean Yilgarn Craton, Western Australia, played a key role in controlling the localization of camp-scale gold, iron and nickel mineralized systems. The age and source characteristics of Archaean lithosphere are heterogeneous in both space and time and are recorded by the varying Nd isotopic signature of crustal rocks. Spatial and temporal variations in isotopic character document the evolution of an intra-cratonic architecture through time, and in doing so map transient lithospheric discontinuities where gold, nickel and iron mineral systems were concentrated. Komatiite-hosted nickel deposits cluster into camps localized within young, juvenile crust at the isotopic margin with older lithosphere; orogenic gold systems are typically localized along major structures within juvenile crust; and banded iron formation (BIF)-hosted iron deposits are localized at the edge of, and within, older lithospheric blocks. Furthermore, this work shows that crustal evolution plays an important role in the development and localization of favourable sources of nickel, gold and iron by controlling the occurrence of thick BIFs, ultramafic lavas and fertile (juvenile) crust, respectively. Fundamentally, this study demonstrates that the lithospheric architecture of a craton can be effectively imaged by isotopic techniques and used to identify regions prospective for camp-scale mineralization.

Three-dimensional morphology of magmatic sulfides sheds light on ore formation and sulfide melt migration

The morphology of magmatic sulfides in igneous cumulates is controlled by the wetting properties of sulfide liquids against silicates. The formation of nickel sulfide ores, the behavior of sulfide liquids during mantle melting, and potentially the segregation of the Earth9s core, are all controlled by the ability of sulfide liquids to migrate through the pore space of partially molten silicates. Three-dimensional X-ray tomographic images of sulfide aggregates in komatiitic olivine cumulates indicate that sulfide liquids have a limited tendency to wet olivine crystals, forming interconnected networks only in the absence of silicate melt. Consequently, the ability of sulfide liquids to migrate through the pore space of olivine cumulates is limited. We conclude that disseminated sulfide ores in komatiites formed by accumulation of transported sulfide blebs a few millimeters in size, and not by settling of sulfide-olivine aggregates, and that sulfides accumulated in the proportions in which they are now found, rather than by percolation through cumulate pore space. It is unlikely that sulfide droplets can be entrained and carried from the mantle at low degrees of partial melting. Our results also support the hypothesis that segregation of the Earth9s core took place from a magma ocean, rather than by percolation of sulfidic melt through partially molten mantle.

Use and calibration of portable X-Ray fluorescence analysers: application to lithogeochemical exploration for komatiite-hosted nickel sulphide deposits

Portable X-Ray Fluorescence (pXRF) analysers allow on-site geochemical analysis of rock powders and drill core. The main advantages of pXRF analysis over conventional laboratory analysis are the speed of data collection and the low cost of the analyses, permitting the collection of extensive, spatially representative datasets. However, these factors only become useful if the quality of the data meets the requirements needed for the purposes of the study. Here, we evaluate the possible use of portable XRF to determine element concentrations and ratios used in exploration for komatiite-hosted nickel sulphides. A portable XRF analyser was used to measure a series of chalcophile and lithophile element concentrations (Si, S, K, Ca, Ti, Cr, Fe, Ni, Cu, Zn, As, Sr, and Zr) of 75 samples from three komatiite units associated with nickel sulphide ores in the Yilgarn Craton, Western Australia. Crucial steps in the study were the development of a strict calibration process as well as numerous data quality checks. The 670 analyses collected in this study were compared with conventional laboratory XRF data on discriminant diagrams commonly utilized in exploration for komatiite-hosted nickel sulphides (Cr vs Ni and Ni/Ti vs Ni/Cr). After comparing the results obtained with pXRF during this study with the laboratory values, we can conclude that portable XRF analyses can be used for rapid assessment of the nickel sulphide prospectivity of komatiites provided that strict control protocols are followed. Supplementary Material: is available at http://www.geolsoc.org.uk/SUP18706

Spatio-temporal constraints on lithospheric development in the southwest–central Yilgarn Craton, Western Australia

The Archean western Yilgarn Craton contains an extensive record of supracrustal formation from ca 3730 to ca 2675 Ma, as well as evidence of an ensialic crustal component as old as ca 4400 Ma. These features make the western Yilgarn Craton one of the oldest crustal provinces on Earth and ideal for the study of Archean crustal evolution. Spatial analysis of new and collated U–Pb age data define three broad pulses of granite emplacement at ca 3000–2820, ca 2805–2720 and ca 2720–2600 Ma, with a period of regional quiescence at 2820–2805 Ma. Within these pulses, major peaks in granite production are defined at ca 2920, ca 2890, ca 2845, ca 2790, ca 2750, ca 2690, ca 2665, ca 2655, ca 2630, and ca 2615 Ma; with lesser inherited material as old as 3670 Ma. In the western Yilgarn Craton, all terranes show evidence of granite activity at ca 3000–2820 Ma. The South West Terrane and Southern Cross Domain share granite pulses at ca 2950–2920, 2880–2820 and 2800–2720 Ma, although during these intervals granite magmatism tends to dominate in one terrane, i.e. ca 2805–2780 Ma granite activity predominantly occurs in the South West Terrane, while 2780–2720 Ma activity is focused in the Southern Cross Domain. Including the period of quiescence, granite production is relatively minor between ca 2820 and ca 2720 Ma relative to the 3000–2820 Ma and 2720–2600 Ma intervals, suggesting limited crustal development at this time. This period corresponds with widespread greenstone formation throughout the western Yilgarn Craton. The major pulse of granite emplacement and crustal evolution occurs at ca 2700–2600 Ma, with the main phases of activity at ca 2680–2650 Ma in the Southern Cross Domain and ca 2640–2620 Ma in the South West Terrane. These pulses coincide with a craton-wide transition in granite geochemistry from high-Ca to low-Ca at ca 2650 Ma and suggest significant variations in the method and timing of melt generation. Results from this study provide new constraints on the spatio-temporal evolution of the lithosphere in the western Yilgarn Craton. The spatial distribution of these age data suggest that existing terrane boundaries should be revised with the South West Terrane separated into at least two distinct domains, and the boundary between the Youanmi and South West Terranes moved westward to correspond with the eastern extent of charnockite granites.

Extremely Ni-rich Fe–Ni sulfide assemblages in komatiitic dunite at Betheno, Western Australia: results from synchrotron X-ray fluorescence mapping

Fresh unserpentinised komatiitic dunite at Betheno (Western Australia) contains a distinctive sulfide assemblage of pentlandite, pyrite and millerite. The Ni tenor (i.e. Ni concentration in the original sulfide liquid) of this assemblage is in excess of 30 wt%, and the bulk sulfide composition falls within the compositional range of monosulfide solution (MSS) above 800°C. Such assemblages have conventionally been interpreted as the result of hydrothermal upgrading of normal lower Ni-rich magmatic assemblages, but this explanation is not applicable at Betheno. Subtle zonation of Ni concentration in the host olivine, revealed by high-resolution X-ray fluorescence mapping using the Maia detector on the Australian Synchrotron, suggests that coupled subsolidus re-equilibration of Ni and Fe between olivine and sulfide is not a plausible explanation, and the olivine appears to have gained Ni from sulfides rather than the other way around. This leaves a primary magmatic origin as the favoured interpretation, and supports the existence of a stable pyrite–millerite tie-line in the Fe–Ni–S system at low temperatures. Further evidence for this comes from the existence of similar assemblages in fresh dunites from the nearby Perseverance nickel deposit. Hydrothermal alteration is evidently not necessary to form unusually Ni-rich sulfide assemblages. The exceptionally high Ni tenors are attributed to open-system equilibration of sulfide liquid with typical Ni-undepleted olivine, under conditions where sulfide compositions are essentially buffered by the olivine composition, and to the known positive correlation between the Fe/Ni distribution coefficient between olivine and sulfide and the Ni tenor. Other Ni-rich, millerite-bearing assemblages, such as those from the Black Swan nickel deposit, may also have primary origins.

Did diamond-bearing orangeites originate from MARID-veined peridotites in the lithospheric mantle?

Kimberlites and orangeites (previously named Group-II kimberlites) are small-volume igneous rocks occurring in diatremes, sills and dykes. They are the main hosts for diamonds and are of scientific importance because they contain fragments of entrained mantle and crustal rocks, thus providing key information about the subcontinental lithosphere. Orangeites are ultrapotassic, H2O and CO2-rich rocks hosting minerals such as phlogopite, olivine, calcite and apatite. The major, trace element and isotopic compositions of orangeites resemble those of intensely metasomatized mantle of the type represented by MARID (mica-amphibole-rutile-ilmenite-diopside) xenoliths. Here we report new data for two MARID xenoliths from the Bultfontein kimberlite (Kimberley, South Africa) and we show that MARID-veined mantle has mineralogical (carbonate-apatite) and geochemical (Sr-Nd-Hf-O isotopes) characteristics compatible with orangeite melt generation from a MARID-rich source. This interpretation is supported by U-Pb zircon ages in MARID xenoliths from the Kimberley kimberlites, which confirm MARID rock formation before orangeite magmatism in the area.