Selenium isotope systematics of mid-ocean-ridge basalts and implications for the long-term volatile and chalcophile record of the crust–mantle system

Selenium is a chalcophile, moderately volatile and redox-sensitive element. The Se isotopic and elemental systematics of mantle-derived rocks and melts may therefore provide new approaches to study the terrestrial volatile origin and evolution as well as secular changes of redox conditions across the surface and mantle reservoirs. Selenium is significantly depleted in mantle samples (at ng/g levels), posing analytical challenges for Se isotopic studies of the igneous system. This study presents an analytical protocol suitable for precise and accurate determination of Se isotope and Se–Te abundances of igneous rocks. The Se–Te elemental systematics provide a petrogenetic context for interpreting Se isotope systematics. The new method was used to analyze a suite of basaltic glasses from the Pacific–Antarctic ridge (PAR) and the Mid-Atlantic ridge (MAR). The magmatic differentiation involving concurrent sulfide segregation results in significant chalcophile element fractionation but no measurable Se isotopic variation. Because of the demonstrated lack of Se isotopic fractionation between sulfides and silicate melt, the Se isotope systematics of MORB reflects a source signature. The southern MAR displays a significant source heterogeneity due to the localized interaction between the ridge and Shona and Discovery mantle plumes that incorporate recycled components

Moderate levels of oxygenation during the late stage of Earth's Great Oxidation Event

FOO and RS acknowledge financial support from the University of Tübingen and the German Research Foundation (DFG Grant SCHO1071/11-1). FOO and MBA are thankful for support from the Natural Environment Research Council (NERC grant NE/V004824/1). The stable isotope facilities at IDYST were funded by the University of Lausanne. SK, YA and MIV-R acknowledge European Research Council (ERC) Starting Grant 636808 (O2RIGIN). AH and FOO acknowledge support from National Research Foundation of South Africa (NRF Grant 75892). SK also acknowledges the Ramon y Cajal contract (RYC2020-030014-I). Participation by AB was supported by Discovery and Accelerator Grants from the Natural Sciences and Engineering Research Council of Canada (NSERC) and ACS PF grant (624840ND2). EES acknowledges funding from a NERC Frontiers grant (NE/V010824/1). SWP acknowledges support from a Royal Society Wolfson Research Merit Award. MIV-R additionally acknowledges funding support from the German Research Foundation (DFG Grant VA 1568/1-1).The later stages of Earth's transition to a permanently oxygenated atmosphere during the Great Oxidation Event (GOE; ∼2.43–2.06 Ga) is commonly linked with the suggestion of an “oxygen overshoot” during the ∼2.22–2.06 Ga Lomagundi Event (LE), which represents Earth's most pronounced and longest-lived positive carbon isotope excursion. However, the magnitude and extent of atmosphere-ocean oxygenation and implications for the biosphere during this critical period in Earth's history remain poorly constrained. Here, we present nitrogen (N), selenium (Se), and carbon (C) isotope data, as well as bio-essential element concentrations, for Paleoproterozoic marine shales deposited during the LE. The data provide evidence for a highly productive and well-oxygenated photic zone, with both inner and outer-shelf marine environments characterized by nitrate- and Se oxyanion-replete conditions. However, the redoxcline subsequently encroached back onto the inner shelf during global-scale deoxygenation of the atmosphere-ocean system at the end of the LE, leading to locally enhanced water column denitrification and quantitative reduction of selenium oxyanions. We propose that nitrate-replete conditions associated with fully oxygenated continental shelf settings were a common feature during the LE, but nitrification was not sufficiently widespread for the aerobic nitrogen cycle to impact the isotopic composition of the global ocean N inventory. Placed in the context of Earth's broader oxygenation history, our findings indicate that O2 levels in the atmosphere-ocean system were likely much lower than modern concentrations. Early Paleoproterozoic biogeochemical cycles were thus far less advanced than after Neoproterozoic oxygenation.Publisher PDFPeer reviewe

Selenium and tellurium in Reykjanes Ridge and Icelandic basalts: Evidence for degassing-induced Se isotope fractionation

Selenium behaves as a chalcophile and moderately volatile element during planetary accretion and magmatic processes on Earth. Together with the geochemically similar S and Te, Se is more volatile than most other moderately volatile elements and thus potentially becomes a new tracer to constrain the mechanism of volatile depletion in the Earth's mantle and other planetary bodies. As previously observed for several volatile elements, stable isotopes of Se are expected to fractionate upon eruptive outgassing of magmas. To understand the degassing behavior of Se and associated isotope fractionation, we report on Se and Te contents and Se isotope compositions (δSe) of submarine glasses across a range of distant ridge depth intervals along the Reykjanes Ridge and subglacial/subaerial basalts on Iceland (51–65°N; N = 22). Selenium (150–399 ng/g) and Te (2.61–14.5 ng/g) contents of the submarine glasses display progressive enrichment along the Reykjanes Ridge towards Iceland. This can be explained either by enhanced mantle melting towards Iceland or by enrichment of Se–Te contents in the mantle source due to the Icelandic plume–Reykjanes Ridge interaction. Both scenarios are equally plausible. The δSe values of submarine Reykjanes Ridge glasses range between −0.20 ± 0.08‰ and −0.08 ± 0.08‰ (on average −0.15 ± 0.07‰; 2SD, N = 15), which are unaffected by the Icelandic plume contribution and remain strictly within the previously reported average for depleted MORBs. These new data combined with literature δSe for depleted MORBs define a highly homogeneous depleted mantle composition δSe = −0.15 ± 0.11‰ (2SD, N = 44). On the other hand, we observed degassing of Se and Te to a variable extent (~40–95%) in submarine Reykjanes glasses at depths shallower than ~250 m and in subaerial/subglacial basalts on Iceland. Degassing-induced Se isotope fractionation shifted δSe of subaerial lavas towards heavier values (by up to ~0.44‰) well outside the range of submarine MORBs. However, when Se outgassing is associated with subglacial eruption, the outer glass rim of basalt preserves the primary/undegassed Se isotopic signature; whereas the pillow interior experiencing further Se loss (~50%) is enriched in heavier isotopes (−0.01 ± 0.12‰) relative to the outer glass rim (−0.22 ± 0.08‰). These observations are complemented by measurements of BHVO-2G from high-temperature heating experiments of the natural Hawaiian basalt BHVO-2, which show evaporation of 40% Se and 85% Te and resulting shift in δSe by ~+0.74‰. Degassing-induced Se isotope fractionation during volcanic eruption may be well explained by a simple Rayleigh distillation model with an empirical fractionation factor α of ~0.9998 (between volcanic gas and silicate melt). The results presented here show that Se isotope and Se–Te systematics can potentially contribute further constraints on degassing of chalcophile and volatile elements during terrestrial volcanism and large-scale planetary processes.We are especially grateful to Jean-Guy Schilling for his initial support and encouragement of the project, and to Katherine A. Kelley for providing us with all the samples. We acknowledge fruitful discussions with Ronny Schoenberg, Jabrane Labidi, and Timon Kurzawa, and lab support from Elmar Reitter and Maria Isabel Varas-Reus. We also thank Frances Jenner, Alex McCoy-West, and an anonymous reviewer for their through reviews and constructive suggestions, and Julie Prytulak for the efficient editorial handling. S. K. acknowledges financial support by the ERC Starting Grant O2RIGIN (636808)

Recycled selenium in hot spot-influenced lavas records ocean-atmosphere oxygenation

International audienceOxygenation of Earth's oceans and atmosphere through time has consequences for subducted surface signatures that are now stored in the mantle. Here, we report significant mass-dependent selenium isotope variations in modern hot spot-influenced oceanic lavas. These variations are correlated with tracers of mantle source enrichment, which can only be explained by incorporation of abyssal pelagic sediments subducted from a redox-stratified mid-Proterozoic ocean. Selenium geochemical signatures of these sediments have mostly been preserved during long-term recycling and may therefore complement the global surface sediment record as ancient oxygen archives. Combined deep mantle and surface perspectives, together with emerging models for atmospheric oxygen based on selenium systematics, further imply a significantly oxygenated ocean-atmosphere system throughout the mid-Proterozoic