Sulfur loss from subducted altered oceanic crust and implications for mantle oxidation

© The Author(s), [year]. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Walters, J. B., Cruz-Uribe, A. M., & Marschall, H. R. Sulfur loss from subducted altered oceanic crust and implications for mantle oxidation. Geochemical Perspectives Letters, 13, (2020): 36-41, doi:10.7185/geochemlet.2011.Oxygen fugacity (fO2) is a controlling factor of the physics of Earth’s mantle; however, the mechanisms driving spatial and secular changes in fO2 associated with convergent margins are highly debated. We present new thermodynamic models and petrographic observations to predict that oxidised sulfur species are produced during the subduction of altered oceanic crust. Sulfur loss from the subducting slab is a function of the protolith Fe3+/ΣFe ratio and subduction zone thermal structure, with elevated sulfur fluxes predicted for oxidised slabs in cold subduction zones. We also predict bi-modal release of sulfur-bearing fluids, with a low volume shallow flux of reduced sulfur followed by an enhanced deep flux of sulfate and sulfite species, consistent with oxidised arc magmas and associated copper porphyry deposits. The variable SOx release predicted by our models both across and among active margins may introduce fO2 heterogeneity to the upper mantle.We thank James Connolly for modelling support and Peter van Keken for providing updated P–T paths for the Syracuse et al. (2010) models. The manuscript benefited from the editorial handling by Helen Williams and from constructive reviews of Maryjo Brounce, Katy Evans, and an anonymous reviewer. JBW acknowledges Fulbright and Chase Distinguished Research fellowships. This work was supported by NSF grant EAR1725301 awarded to AMC

Isotopic compositions of sulfides in exhumed high-pressure terranes: Implications for sulfur cycling in subduction zones

Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 20(7), (2019): 3347-3374, doi:10.1029/2019GC008374.Subduction is a key component of Earth's long‐term sulfur cycle; however, the mechanisms that drive sulfur from subducting slabs remain elusive. Isotopes are a sensitive indicator of the speciation of sulfur in fluids, sulfide dissolution‐precipitation reactions, and inferring fluid sources. To investigate these processes, we report δ34S values determined by secondary ion mass spectroscopy in sulfides from a global suite of exhumed high‐pressure rocks. Sulfides are classified into two petrogenetic groups: (1) metamorphic, which represent closed‐system (re)crystallization from protolith‐inherited sulfur, and (2) metasomatic, which formed during open system processes, such as an influx of oxidized sulfur. The δ34S values for metamorphic sulfides tend to reflect their precursor compositions: −4.3 ‰ to +13.5 ‰ for metabasic rocks, and −32.4 ‰ to −11.0 ‰ for metasediments. Metasomatic sulfides exhibit a range of δ34S from −21.7 ‰ to +13.9 ‰. We suggest that sluggish sulfur self‐diffusion prevents isotopic fractionation during sulfide breakdown and that slab fluids inherit the isotopic composition of their source. We estimate a composition of −11 ‰ to +8 ‰ for slab fluids, a significantly smaller range than observed for metasomatic sulfides. Large fractionations during metasomatic sulfide precipitation from sulfate‐bearing fluids, and an evolving fluid composition during reactive transport may account for the entire ~36 ‰ range of metasomatic sulfide compositions. Thus, we suggest that sulfates are likely the dominant sulfur species in slab‐derived fluids.All isotopic data and analysis locations are detailed in the supporting information accompanying this article. The authors would like to thank B. Monteleone and M. Yates for assistance with SIMS and EPMA analyses, respectively. J. Selverstone is thanked for providing samples and D. Whitney for providing additional field context. The authors would also like to thank J. Alt, C. LaFlamme, and an anonymous reviewer for their thoughtful and thorough reviews, as well as careful editorial handling by J. Blichert‐Toft. This project was funded by National Science Foundation Grant EAR 1725301 awarded to A. M. C. and a Geological Society of America grant to J. B. W.2019-12-1

A communal catalogue reveals Earth's multiscale microbial diversity

Our growing awareness of the microbial world's importance and diversity contrasts starkly with our limited understanding of its fundamental structure. Despite recent advances in DNA sequencing, a lack of standardized protocols and common analytical frameworks impedes comparisons among studies, hindering the development of global inferences about microbial life on Earth. Here we present a meta-analysis of microbial community samples collected by hundreds of researchers for the Earth Microbiome Project. Coordinated protocols and new analytical methods, particularly the use of exact sequences instead of clustered operational taxonomic units, enable bacterial and archaeal ribosomal RNA gene sequences to be followed across multiple studies and allow us to explore patterns of diversity at an unprecedented scale. The result is both a reference database giving global context to DNA sequence data and a framework for incorporating data from future studies, fostering increasingly complete characterization of Earth's microbial diversity.Peer reviewe

A communal catalogue reveals Earth’s multiscale microbial diversity

Our growing awareness of the microbial world’s importance and diversity contrasts starkly with our limited understanding of its fundamental structure. Despite recent advances in DNA sequencing, a lack of standardized protocols and common analytical frameworks impedes comparisons among studies, hindering the development of global inferences about microbial life on Earth. Here we present a meta-analysis of microbial community samples collected by hundreds of researchers for the Earth Microbiome Project. Coordinated protocols and new analytical methods, particularly the use of exact sequences instead of clustered operational taxonomic units, enable bacterial and archaeal ribosomal RNA gene sequences to be followed across multiple studies and allow us to explore patterns of diversity at an unprecedented scale. The result is both a reference database giving global context to DNA sequence data and a framework for incorporating data from future studies, fostering increasingly complete characterization of Earth’s microbial diversity

31st Annual Meeting and Associated Programs of the Society for Immunotherapy of Cancer (SITC 2016) : part two

Background The immunological escape of tumors represents one of the main ob- stacles to the treatment of malignancies. The blockade of PD-1 or CTLA-4 receptors represented a milestone in the history of immunotherapy. However, immune checkpoint inhibitors seem to be effective in specific cohorts of patients. It has been proposed that their efficacy relies on the presence of an immunological response. Thus, we hypothesized that disruption of the PD-L1/PD-1 axis would synergize with our oncolytic vaccine platform PeptiCRAd. Methods We used murine B16OVA in vivo tumor models and flow cytometry analysis to investigate the immunological background. Results First, we found that high-burden B16OVA tumors were refractory to combination immunotherapy. However, with a more aggressive schedule, tumors with a lower burden were more susceptible to the combination of PeptiCRAd and PD-L1 blockade. The therapy signifi- cantly increased the median survival of mice (Fig. 7). Interestingly, the reduced growth of contralaterally injected B16F10 cells sug- gested the presence of a long lasting immunological memory also against non-targeted antigens. Concerning the functional state of tumor infiltrating lymphocytes (TILs), we found that all the immune therapies would enhance the percentage of activated (PD-1pos TIM- 3neg) T lymphocytes and reduce the amount of exhausted (PD-1pos TIM-3pos) cells compared to placebo. As expected, we found that PeptiCRAd monotherapy could increase the number of antigen spe- cific CD8+ T cells compared to other treatments. However, only the combination with PD-L1 blockade could significantly increase the ra- tio between activated and exhausted pentamer positive cells (p= 0.0058), suggesting that by disrupting the PD-1/PD-L1 axis we could decrease the amount of dysfunctional antigen specific T cells. We ob- served that the anatomical location deeply influenced the state of CD4+ and CD8+ T lymphocytes. In fact, TIM-3 expression was in- creased by 2 fold on TILs compared to splenic and lymphoid T cells. In the CD8+ compartment, the expression of PD-1 on the surface seemed to be restricted to the tumor micro-environment, while CD4 + T cells had a high expression of PD-1 also in lymphoid organs. Interestingly, we found that the levels of PD-1 were significantly higher on CD8+ T cells than on CD4+ T cells into the tumor micro- environment (p < 0.0001). Conclusions In conclusion, we demonstrated that the efficacy of immune check- point inhibitors might be strongly enhanced by their combination with cancer vaccines. PeptiCRAd was able to increase the number of antigen-specific T cells and PD-L1 blockade prevented their exhaus- tion, resulting in long-lasting immunological memory and increased median survival

MinPlot: A mineral formula recalculation and plotting program for electron probe microanalysis

MinPlot is a MATLAB®-based mineral formula recalculation and compositional plotting program for electron microprobe analyses (EPMA). The program offers recalculation and structural formula assignment for 15 different mineral groups: Garnet, pyroxene, olivine, amphibole, feldspar, mica, staurolite, cordierite, chlorite, chloritoid, talc, epidote, titanite, spinel, and sulfides. MinPlot is a fast and easy to use command line program and requires no prior computer programming knowledge. Percent mass fractions of oxides are loaded from datafiles and the user answers simple prompts to select mineral type, normalization scheme, and plotting options. Recalculated mineral formulas are automatically saved as output files and plots may be further manually customized by the user prior to saving. MinPlot can perform thousands of calculations in seconds and the modular nature of the program makes it simple to add new calculation routines in future releases. Combined, these features make MinPlot a powerful and useful program for the processing of EPMA data

Sulfur and Trace Metal Cycling at Convergent Margins

Subduction zones are the site of long-term chemical exchange between Earth’s surface and interior geochemical reservoirs. Subducting slabs are progressively depleted in volatiles and other mobile elements through dehydration and melting reactions. These elements are then introduced to the mantle wedge and volcanic arc. One consequence of this cycle is that volcanic arcs produce the most oxidized magmas on Earth. Sulfur, which exhibits a range in valence states from S2- to S6+, is one of the few elements in the subducting slab capable of oxidizing the arc and mantle wedge. Sulfides in the slab may also act as an important host of chalcophile and siderophile minor and trace elements (CSEs), such as Co, Ni, Cu, and As. The extraction of sulfur from the slab may also liberate and transfer these elements to the arc, where they may contribute to the formation of ore deposits. Such chemical and advective processes, which occur at depths in excess of 50 km, are not directly observable. Rocks and minerals in exhumed high-pressure terranes provide a chemical archive of sulfur and CSE extraction during subduction. In this dissertation, I examine the sulfur isotopic composition of sulfides in high-pressure and slab fluids, predict the concentration and speciation of sulfur in slab fluids, and characterize the CSE budget of the subducted mafic crust. Sulfur isotopes are a sensitive indicator of redox conditions and sulfur mobility. In situ sulfur isotope measurements were conducted using secondary ion mass spectrometry (SIMS) on sulfides in high-pressure metamorphic rocks. Sulfides are classified into two categories: 1. Metamorphic sulfides, which preserve a record of prograde subduction metamorphism, and 2. Metasomatic sulfides precipitated from slab-derived fluids. The isotopic composition of metamorphic sulfides reflects their protolith compositions: −4.3 to +13.5 ‰ for metabasic rocks, and −32.4 to −11.0 ‰ for metasediments. From these data, I estimate that prograde sulfide breakdown will release slab fluids with an isotopic composition of −11 to +8 ‰. Metasomatic sulfides exhibit a range in δ34S values from −21.7 to +13.9 ‰, significantly larger than the range of predicted slab fluid compositions. The observed range of metasomatic sulfide compositions likely indicates large isotopic fractions between and oxidized slab fluid and the precipitating sulfide grains. In support of the sulfur isotope observations, I used equilibrium thermodynamic forward modeling software to predict the speciation and concentration of sulfur in slab fluids. Sulfur loss from the slab is sensitive to protolith Fe3+/SFe ratio and subduction zone thermal structure. Subduction of altered oceanic crust in cold subduction zones was found to produce significant fluxes of sulfate and sulfite species. In contrast, subduction along a warm subduction geothermal gradient produces a bi-modal release of sulfur-bearing fluids, with a low-volume shallow flux of reduced sulfur, followed by a high-volume deep flux of sulfate and sulfite species. Sulfur oxidation in these systems is balanced by ferric iron reduction. Matrix sulfides in high-pressure metamorphic rocks are rarely associated with peak metamorphic conditions, suggesting that sulfur is almost completely extracted from the slab across the blueschist to eclogite transition. The thermodynamic models predict that sulfur oxidation is balanced by iron reduction in the eclogitic slab residuum. This prediction is supported by the observation that oceanic eclogites display lower bulk rock Fe3+/SFe when compared to blueschist and altered oceanic crust. Prograde sulfur-loss is anticipated to redistribute and/or release sulfide-hosted minor and trace CSEs. In situsulfide and silicate compositions were determined by laser ablation inductively coupled mass spectrometry (LA-ICP-MS) for the elements Cr, Co, Ni, Cu, Zn, Ga, Ge, As, Mo, Ag, Cd, In, Sn, Sb, Te, Tl, and Bi. Sulfides host nearly the entire Cu, As, Ag, Cd, and Te budget of subducted rocks. These elements are incompatible in garnet, omphacite, phengite, and rutile, and are almost completely lost from the slab during prograde sulfide breakdown. Cobalt, Ni, Zn, Ga, Ge, Mo, Sn, and Tl are hosted in silicate and oxide phases. While Co, Ni, Zn, Ga, and Pb may be partially lost during lawsonite, epidote, and amphibole dehydration reactions, Ge, Tl, Sn, and Mo are largely retained in garnet, phengite, and rutile. Mobilization of the latter elements may require high fO2 conditions or melting. Consistent with estimated CSE budgets, minor and trace element zoning in metasomatic sulfide and silicate minerals suggest that Co, Ni, and As are mobile in slab fluids. Sulfur lost from the slab is expected to oxidize the subarc mantle and arc magmas, whereas mobile CSE elements may contribute to the formation of arc-related ore deposits

Growth of kyanite and Fe‐Mg chloritoid in Fe2O3‐rich high‐pressure–low‐temperature metapelites and metapsammites: A case study from the Massa Unit (Alpi Apuane, Italy)

AbstractChloritoid and kyanite coexist in metapelites from the high‐pressure/low‐temperature Massa Unit in the Alpi Apuane metamorphic complex (Northern Apennines, Italy). The composition of chloritoid is extremely variable throughout the Massa Unit. Fe‐chloritoid occurs in association with hematite‐free, graphite‐bearing schists, whereas strongly zoned Fe‐Mg chloritoid is found with hematite and kyanite. We investigated the effect of different bulk Fe2O3 contents in controlling chloritoid composition through phase equilibria modelling of four selected samples, representative of the different chloritoid‐bearing parageneses found in the Massa Unit. The ferric iron content, measured through wet chemical titration, ranges from 0 (graphite‐chloritoid schist) to 73% of the total iron (hematite‐chloritoid schist). We show that Mg‐rich chloritoid compositions and stability of kyanite at greenschist to blueschist facies conditions can be reproduced in the MnO–Na2O–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O (MnNKFMASHTO) chemical system only considering the presence of significant amounts of ferric iron as part of the bulk composition. The stabilization of kyanite at lower grade is directly linked to the presence of Fe2O3, which renders the reactive bulk rock composition effectively enriched in Al2O3 with respect to Fe and Mg. We also document that high Fe2O3 contents exacerbate the effect of chloritoid fractionation, producing strongly zoned Fe‐Mg‐chloritoid grains. Finally, the P–T modelling of the Massa Units performed in this study allows, for the first time, the recognition of a two‐stage evolution at peak conditions, with an earlier pressure peak (1.2–1.3 GPa at 350–400°C), and a later thermal peak (0.7–1.1 GPa at 440–480°C), compatible with subduction, underthrusting and exhumation of the Adria continental margin during growth of the Northern Apennine orogenic wedge.https://data.mendeley.com/datasets/wm3nwkrd4m/

Deer density effects on vegetation in aspen forest understories over site productivity and stand age gradients

Studies examining the interacting effects of ungulate herbivore pressure and site productivity on vegetation are mostly on grassland–grazing systems and have shown conflicting patterns. Here we examine the effects of deer density (\u3e30 years differences in density between two landowners), site productivity (site index, SI) and stand age on subcanopy vegetation characteristics in 60 closed canopy, clear-cut originPopulus tremuloides dominated stands, Michigan, USA. Stand age effects were included because age varied among stands and can affect subcanopy vegetation patterns. Compared with fewer deer, stands with more deer had greater total forest floor vegetation mass, and its major components bracken fern (Pteridium aquilinum), sedge (mostly Carex pensylvanica) and trees/shrubs \u3c0.25 m tall, but lower forb mass and lower forest floor vegetation species richness and diversity. Deer density and SI had strong interacting effects on total forest floor mass, forb mass, and species richness. Forb mass increased with SI, but only in stands with fewer deer, whilst total vegetation mass was greater in stands with more deer at lower SI and declined with SI more sharply than for stands with fewer deer. Species richness increased with SI but more so at lower than higher deer density. Deer density and age had interacting effects on mass of trees/shrubs \u3c0.25 m tall and sedge. Compared with fewer deer, stands with more deer had greater sedge and tree/shrub mass, and sedge mass decreased and tree/shrub mass increased more sharply with age. In lower deer stands there was a dense subcanopy tree and shrub strata within and beyond the reach of deer 0.9–10 m tall whereas in higher deer stands this vegetation layer was nearly absent. We conclude that higher deer browse pressure in early successional Populus stands (1) strongly limits the recruitment of woody stems to larger (\u3e0.9 m tall) size classes, which could affect long-term successional trajectories, and (2) diminishes forb density and species richness, especially at higher site productivity, but increases total forest floor vegetation mass (mostly bracken fern and sedge), especially at lower site productivity. Given associations of bracken fern and sedge with poorer and/or more open sites and assuming high palatability of forbs, this pattern may result from the combination of selective herbivory and higher light availability caused by limited recruitment of trees and shrubs to taller strata

Growth of kyanite and Fe-Mg chloritoid in Fe2O3-rich high-pressure–low-temperature metapelites and metapsammites: A case study from the Massa Unit (Alpi Apuane, Italy)

Chloritoid and kyanite coexist in metapelites from the high-pressure/low-temperature Massa Unit in the Alpi Apuane metamorphic complex (Northern Apennines, Italy). The composition of chloritoid is extremely variable throughout the Massa Unit. Fe-chloritoid occurs in association with hematite-free, graphite-bearing schists, whereas strongly zoned Fe-Mg chloritoid is found with hematite and kyanite. We investigated the effect of different bulk Fe2O3 contents in controlling chloritoid composition through phase equilibria modelling of four selected samples, representative of the different chloritoid-bearing parageneses found in the Massa Unit. The ferric iron content, measured through wet chemical titration, ranges from 0 (graphite-chloritoid schist) to 73% of the total iron (hematite-chloritoid schist). We show that Mg-rich chloritoid compositions and stability of kyanite at greenschist to blueschist facies conditions can be reproduced in the MnO–Na2O–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O (MnNKFMASHTO) chemical system only considering the presence of significant amounts of ferric iron as part of the bulk composition. The stabilization of kyanite at lower grade is directly linked to the presence of Fe2O3, which renders the reactive bulk rock composition effectively enriched in Al2O3 with respect to Fe and Mg. We also document that high Fe2O3 contents exacerbate the effect of chloritoid fractionation, producing strongly zoned Fe-Mg-chloritoid grains. Finally, the P–T modelling of the Massa Units performed in this study allows, for the first time, the recognition of a two-stage evolution at peak conditions, with an earlier pressure peak (1.2–1.3 GPa at 350–400°C), and a later thermal peak (0.7–1.1 GPa at 440–480°C), compatible with subduction, underthrusting and exhumation of the Adria continental margin during growth of the Northern Apennine orogenic wedge