International audienceScapolite is an important reservoir for volatiles in the deep crust and provides unique insights into the S isotope signatures at the mantle/crust interface. Here we document the first scapolite reference material (herein referred to as CB1) for in situ S isotope analysis. The chemical and isotopic composition of this euhedral, S-rich scapolite megacryst was characterized via LA-ICP-MS, EPMA, SIMS, and bulk fluorination gas source isotope ratio mass spectrometry. The CB1 scapolite is isotopically homogeneous and our results show that crystal orientation does not affect in situ S isotope SIMS analysis. This makes CB1 an ideal primary calibration standard for in situ analysis of S isotope ratios (36S/32S, 34S/32S and 33S/32S) in scapolite. With this reference material in hand, we then applied in situ SIMS analysis of S isotopes for the first time on scapolite in granulite samples from the lower crust/upper mantle. The analysed sample suite comprises rocks from classic granulite xenolith locations in southeastern Australia, as well as a sample from the high-grade suture zone of the Dahomeyides in south-eastern Ghana. The results show that scapolites in the lower crust have δ34S values between ~− 0.5 and + 4 (‰ VCDT). These values fall within the range of S isotope signatures present in mantle rocks and provide no evidence for the recycling of seawater-derived S into the lower crust. We propose that scapolite formed during granulite facies metamorphism of igneous cumulates, where S was sourced from precursor igneous sulfides. Sulfur isotope heterogeneities between individual scapolite grains in some of the studied samples may reflect non-uniform S-isotope compositions of igneous S-phases, which precipitated from mantle-derived melt
Harzburgites and dunites forming the base of the Late Cretaceous–Paleocene Papuan Ultramafic Belt (PUB) and Marum ophiolites of Papua New Guinea (PNG) are amongst the most refractory mantle peridotites on Earth. We present a new integrated dataset of major element, bulk plus mineral trace element and Re–Os isotopic analyses aimed at better understanding the genesis of these peridotites. The PUB harzburgites contain olivine (Fo92–93), low-Al enstatite (less than or equal to 0.5 wt. % Al2O3 and CaO), and Cr-rich spinel (Cr# = 0.90–0.95). The Marum harzburgites are less refractory with olivine (Fo91.9–92.7), enstatite (~0.5–1.0 wt. % Al2O3 and CaO), minor clinopyroxene (diopside), and spinel (Cr# = 0.71–0.77). These major element characteristics reflect equivalent or greater levels of melt depletion than that experienced by Archean cratonic peridotites. Whereas bulk-rock heavy rare earth element (HREE) abundances mirror the refractory character indicated by the mineral chemistry and major elements, large-ion lithophile elements (LILEs) indicate a more complex melting and metasomatic history. In-situ olivine and orthopyroxene REE measurements show that harzburgites and dunites have experienced distinct melt-rock interaction processes, with dunite channels/lenses, specifically, showing higher abundances of HREE in olivine. Distinctive severe inter-element fraction of platinum group elements and Re result in complex patterns that we refer to as “M-shaped”. These fractionated highly siderophile element (HSE) patterns likely reflect the dissolution of HSE-rich phases in highly depleted peridotites by interaction with subduction-related melts/fluids, possibly high-temperature boninites. Osmium isotope compositions of the PNG peridotites are variable (187Os/188Os = 0.1204 to 0.1611), but fall within the range of peridotites derived from Phanerozoic oceanic mantle, providing no support for ancient melt depletion, despite their refractory character. This provides further evidence that highly depleted peridotites can be produced in the modern Earth, in subduction zone environments. The complex geochemistry indicates a multi-stage process for the formation of the PNG mantle peridotites in a modern geodynamic environment. The first stage involves partial melting at low-pressure (<2 GPa) and high-temperature (~1250–1350 0C) to form low-K, low-Ti tholeiitic magmas that formed the overlying cumulate peridotite–gabbro and basalt (PUB only) sequences of the ophiolites. This is inferred to have occurred in a fore-arc setting at the initiation of subduction. Later stages involved fluxing of the residual harzburgites with hydrous fluids and melts to form replacive dunites and enstatite dykes, and interaction of the residual peridotites in the overlying mantle wedge with high-temperature hydrous melts from the subducting slab to generate the extremely refractory harzburgites. This latter stage can be linked to the eruption of low-Ca boninites at Cape Vogel, and other arc-related volcanics, in a nascent oceanic island arc. Both ophiolites were emplaced shortly after when the embryonic oceanic island arc collided with the Australian continent.
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