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1. Redox and mineral controls on Fe and Ti isotopic fractionations during calc-alkaline magmatic differentiation

   https://doi.org/10.1016/j.gca.2023.06.016  

   Johnson, Aleisha C.; Zhang, Zhe J.; Dauphas, Nicolas; Rudnick, Roberta L.; Foden, John D.; Toc, Magali (August 2023, Geochimica et Cosmochimica Acta)

   Titanium and Fe isotopic compositions of lavas from a calc-alkaline differentiation suite and corresponding mineral separates from the Rindjani Volcano, Indonesia show that Fe and Ti isotopic fractionations between minerals and melts are lower than those recorded in other suites at all stages of differentiation. The limited isotopic fractionation for Ti is likely due to low-Ti magnetite and clinopyroxene being the dominant carriers of Ti in Rindjani lavas, as these minerals are thought to have limited equilibrium Ti isotopic fractionation relative to silicate magmas. Other magmatic differentiation suites controlled by removal of Ti-rich magnetite and characterized by a lesser role of clinopyroxene have larger Ti isotopic fractionations. This effect is an indirect consequence of the elevated Fe3+/Fe2+ ratio of calc-alkaline magmas such as Rindjani, which promotes Fe3+ incorporation into magnetite at the expense of Fe2+-Ti4+ pairs, such that increased oxygen fugacity will subdue Ti isotopic fractionation in global magmatic series. Similarly, we find negligible Fe isotopic fractionation in Rindjani bulk rocks and mineral separates, unlike previous studies. This is also likely due to the oxidized nature of the Rindjani differentiation suite, which leads to similar Fe3+/Fe2+ ratios in melt and minerals and decreases overall mineral-melt Fe fractionation factors. Paired Ti and Fe isotopic analyses may therefore represent a powerful tool to assess oxygen fugacity during differentiation, independent from Fe 3+ determinations of erupted samples. 

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2. Investigating Thaw and Plant Productivity Constraints on Old Soil Carbon Respiration From Permafrost

   https://doi.org/10.1029/2020JG006000  

   Mauritz, Marguerite; Pegoraro, Elaine; Ogle, Kiona; Ebert, Christopher; Schuur, Edward A. G. (June 2021, Journal of Geophysical Research: Biogeosciences)

   Abstract Isotopic radiocarbon (Δ¹⁴C) signatures of ecosystem respiration (Reco) can identify old soil carbon (C) loss and serve as an early indicator of permafrost destabilization in a warming climate. Warming also stimulates plant productivity causing plant respiration to dominate Reco Δ¹⁴C signatures and potentially obscuring old soil C loss. Here, we investigate how a wide spatio‐temporal gradient of permafrost thaw and plant productivity affects Reco Δ¹⁴C patterns and isotopic partitioning. Spatial gradients came from a warming experiment with doubling thaw depth and variable biomass, and a vegetation removal manipulation to eliminate plant contributions. We sampled in August and September to capture transitions from high to low plant productivity, decreased surface soil temperature, and relatively small seasonal thaw extensions. We found that surface processes dominate spatial variation in old soil C loss and a process‐based partitioning approach was crucial for constraining old soil C loss. Resampling the same plots in different times of the year revealed that old soil C losses tripled with cooling surface temperature, and the largest old soil C losses were detected when the organic‐to‐mineral soil horizons thawed (∼50–60 cm). We suggest that the measured increase in old soil respiration over the season and when the organic‐to‐mineral horizon thawed, may be explained by mobilization of nitrogen that stimulates microbial decomposition at depth. Our results suggest that soil C in the organic to mineral horizon may be an important source of soil C loss as the entire Arctic region warms and could lead to nonlinearities in projected permafrost climate feedbacks. 

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3. Zirconium stable isotope fractionation during intra-crustal magmatic differentiation in an active continental arc

   https://doi.org/10.1016/j.gca.2023.11.023  

   Zieman, Lisa J.; Ibañez-Mejia, Mauricio; Tissot, François L.H.; Tompkins, Hannah G.D.; Pardo, Natalia; Bloch, Elias M. (January 2024, Geochimica et Cosmochimica Acta)

   Zirconium (Zr) stable isotope variations occur among co-existing Zr-rich accessory phases as well as at the bulk-rock scale, but the petrologic mechanism(s) responsible for Zr isotope fractionation during magmatic differentiation remain unclear. Juvenile magma generation and intra-crustal differentiation in convergent continental margins may play a crucial role in developing Zr isotope variations, and the Northern Volcanic Zone of the Andes is an ideal setting to test this hypothesis. To investigate the influence of these processes on Zr stable isotope compositions, we report δ94/90ZrNIST of whole rock samples from: 1) juvenile arc basalts from the Quaternary Granatifera Tuff, Colombia; 2) lower crust-derived garnet pyroxenites (i.e., arclogites), hornblendites, and gabbroic cumulates found in the same unit; and 3) felsic volcanic products from the Doña Juana Volcanic Complex, a dacitic composite volcano in close proximity to and partially covering the Granatifera Tuff. The basalts have δ94/90ZrNIST values ranging from −0.025 ± 0.018 ‰ to +0.003 ± 0.015 ‰ (n = 8), within the range of mid-ocean ridge basalts. The dacites have δ94/90ZrNIST values ranging from +0.008 ± 0.013 ‰ to +0.043 ± 0.015 ‰ (n = 14), slightly positive relative to the Granatifera and mid-ocean ridge basalts. In contrast, the (ultra)mafic cumulates have highly variable, predominantly positive δ94/90ZrNIST values, ranging from −0.134 ± 0.012 ‰ to +0.428 ± 0.012 ‰ (n = 15). Individual grains and mineral fractions of major rock-forming phases, including garnet (n = 21), amphibole (n = 9), and clinopyroxene (n = 18), were analyzed from 8 (ultra)mafic cumulates. The mineral fractions record highly variable Zr isotopic compositions, with inter-mineral fractionation (Δ94/90Zrgarnet-amphibole) up to 2.067 ‰. Recent ab initio calculations of Zr–O bond force constants in rock-forming phases predict limited inter-mineral Zr isotope fractionation in high-temperature environments, suggesting that the large fractionations we observe are not the product of vibrational equilibrium processes. Instead, we propose a scenario in which large Zr isotopic fractionations develop kinetically, induced by sub-solidus Zr diffusion between coexisting phases via changes in Zr distribution coefficients that arise from changes in temperature. Altogether, Zr isotope variability in this calc-alkaline continental arc setting exhibits no correlation with indices of magmatic differentiation (e.g., Mg#, SiO2), and is not a simple function of fractional crystallization. Furthermore, the garnet clinopyroxenite cumulates studied here represent density-unstable lower arc crust material; consequently, material with isotopically variable δ94/90Zr can be recycled into the mantle as a consequence of lower crustal foundering. 

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4. Mineral dust and pedogenesis in the alpine critical zone

   https://doi.org/10.5194/soil-10-167-2024  

   Munroe, Jeffrey S; Santis, Abigail A; Soderstrom, Elsa J; Tappa, Michael J; Bauer, Ann M (January 2024, SOIL)

   The influence of mineral dust deposition on soil formation in the mountain critical zone was evaluated at six sites in southwestern North America. Passive samplers collected dust for 2 years, and representative soil and rock were gathered in the vicinity of each dust sampler. All materials (dust, soil, and rock) were analyzed to determine their mineralogy (with X-ray diffraction), geochemistry (with inductively coupled plasma mass spectrometry (ICP-MS)), and radiogenic isotope fingerprint (87Sr/86Sr and εNd). In addition, the grain size distribution of dust and soil samples was determined with laser scattering, and standard soil fertility analysis was conducted on the soil samples. Results reveal that minerals present in the dust but absent in the local bedrock are detectable in the soil. Similarly, the geochemistry and isotopic fingerprint of soil samples are more similar to dust than to local bedrock. End-member mixing models evaluating soil as a mixture of dust and rock suggest that the fine fractions of the sampled soils are dominated by dust deposition, with dust contents approaching 100 %. Dust content is somewhat higher in soils compared to bedrock types more resistant to weathering. These results emphasize the dominant control that mineral dust deposition can exert on pedogenesis in the mountain critical zone. 

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5. Sublithospheric Diamonds; Plate Tectonics from Earth's Deepest Mantle Samples

   https://doi.org/10.1146/annurev-earth-032320-105438  

   Shirey, Steven B; Pearson, D Graham; Stachel, Thomas; Walter, Michael J (July 2024, Annual Review of Earth and Planetary Sciences)

   Sublithospheric diamonds and the inclusions they may carry crystallize in the asthenosphere, transition zone, or uppermost lower mantle (from 300 to ∼800 km), and are the deepest minerals so far recognized to form by plate tectonics. These diamonds are distinctive in their deformation features, low nitrogen content, and inclusions of these major mantle minerals: majoritic garnet, clinopyroxene, ringwoodite, CaSi perovskite, ferropericlase, and bridgmanite or their retrograde equivalents. The stable isotopic compositions of elements within these diamonds (δ11B, δ13C, δ15N) and their inclusions (δ18O, δ56Fe) are typically well outside normal mantle ranges, showing that these elements were either organic (C) or modified by seawater alteration (B, O, Fe) at relatively low temperatures. Metamorphic minerals in cold slabs are effective hosts that transport C as CO3 and H as H2O, OH, or CH4 below the island arc and mantle wedge. Warming of the slab generates carbonatitic melts, supercritical aqueous fluids, or metallic liquids, forming three types of sublithospheric diamonds. Diamond crystallization occurs by movement and reduction of mobile fluids as they pass through host mantle via fractures—a process that creates chemical heterogeneity and may promote deep focus earthquakes. Geobarometry of majoritic garnet inclusions and diamond ages suggest upward transport, perhaps to the base of mantle lithosphere. From there, diamonds are carried to Earth's surface by eruptions of kimberlite magma. Mineral assemblages in sublithospheric diamonds directly trace Earth's deep volatile cycle, demonstrating how the hydrosphere of a rocky planet can connect to its solid interior.▪Sublithospheric diamonds from the deep upper mantle, transition zone, and lower mantle host Earth's deepest obtainable mineral samples.▪Low-temperature seawater alteration of the ocean floor captures organic and inorganic carbon at the surface eventually to become some of the most precious gem diamonds.▪Subduction transports fluids in metamorphic minerals to great depth. Fluids released by slab heating migrate, react with host mantle to induce diamond crystallization, and may trigger earthquakes.▪Sublithospheric diamonds are powerful tracers of subduction—a plate tectonic process that deeply recycles part of Earth's planetary volatile budget. 

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