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  • 1
    Publication Date: 2020-03-01
    Description: We present in situ secondary ion mass spectrometry (SIMS) and electron microprobe analyses of coexisting garnet, omphacite, phengite, amphibole, and apatite, combined with pyrohydrolysis bulk-rock analyses to constrain the distribution, abundance, and behavior of halogens (F and Cl) in six MORB-like eclogites from the Raspas Complex (Southern Ecuador). In all cases concerning lattice-hosted halogens, F compatibility decreases from apatite (1.47–3.25 wt%), to amphibole (563–4727 μg/g), phengite (610–1822 μg/g), omphacite (6.5–54.1 μg/g), and garnet (1.7–8.9 μg/g). The relative compatibility of Cl in the assemblage is greatest for apatite (192–515 μg/g), followed by amphibole (0.64–82.7 μg/g), phengite (1.2–2.1 μg/g), omphacite (〈0.05–1.0 μg/g), and garnet (〈0.05 μg/g). Congruence between SIMS-reconstructed F bulk abundances and yield-corrected bulk pyrohydrolysis analyses indicates that F is primarily hosted within the crystal lattice of eclogitic minerals. However, SIMS-reconstructed Cl abundances are a factor of five lower, on average, than pyrohydrolysis-derived bulk concentrations. This discrepancy results from the contribution of fluid inclusions, which may host at least 80% of the bulk rock Cl. The combination of SIMS and pyrohydrolysis is highly complementary. Whereas SIMS is well suited to determine bulk F abundances, pyrohydrolysis better quantifies bulk Cl concentrations, which include the contribution of fluid inclusion-hosted Cl. Raspas eclogites contain 145–258 μg/g F and at least 7–11 μg/g Cl. We estimate that ~95% of F is retained in the slab through eclogitization and returned to the upper mantle during subduction, whereas at least 95% of subducted Cl is removed from the rock by the time the slab equilibrates at eclogite facies conditions. Our calculations provide further evidence for the fractionation of F from Cl during high-pressure metamorphism in subduction zones. Although the HIMU (high U/Pb) mantle source (dehydrated oceanic crust) is often associated with enrichments in Cl/K and F/Nd, Raspas eclogites show relatively low halogen ratios identical within uncertainty to depleted MORB mantle (DMM). Thus, the observed halogen enrichments in HIMU ocean island basalts require either further fractionation during mantle processing or recycling of a halogen-enriched carrier lithology such as serpentinite into the mantle.
    Print ISSN: 0003-004X
    Electronic ISSN: 1945-3027
    Topics: Geosciences
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  • 2
    Publication Date: 2021-06-11
    Electronic ISSN: 2375-2548
    Topics: Natural Sciences in General
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  • 3
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Contributions to Mineralogy and Petrology 172 (2017): 51, doi:10.1007/s00410-017-1368-7.
    Description: The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth's upper mantle, and their distribution in peridotite minerals, remains to be constrained. Here we developed a method to measure low concentrations of halogens (≥ 0.4 μg/g F and ≥ 0.3 μg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole 〉 clinopyroxene 〉 olivine ~ orthopyroxene, while F compatibility ranks as follows: amphibole 〉 clinopyroxene 〉 orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (〈 1 μg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4–31 μg/g F and 0.14–0.38 μg/g Cl. The bulk F content of oceanic-like peridotites (2.1–9.4 μg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that nearly all MORB may be somewhat contaminated by seawater-rich material and that the Cl content of DMM could be overestimated. With this study, we demonstrate that the halogen contents of natural peridotite minerals are a unique tool to understand the cycling of halogens, from ridge settings to subduction zones.
    Description: This research was supported by grant NSF EAR-P&G 1524311 and DOEI award 18563 to VLR. Urann was supported by the Stanley W. Watson Student Fellowship Fund based at WHOI.
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 4
    Publication Date: 2022-10-26
    Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Ma, Q., Dick, H. J. B., Urann, B., & Zhou, H. Silica-rich vein formation in an evolving stress field, Atlantis Bank Oceanic Core Complex. Geochemistry Geophysics Geosystems, 21(7), (2020): e2019GC008795, doi:10.1029/2019GC008795.
    Description: Drilling 809‐m Hole U1473A in the gabbro batholith at the Atlantis Bank Oceanic Core Complex (OCC) found two felsic vein generations: late magmatic fractionates, rich in deuteric water, hosted by oxide gabbros, and anatectic veins associated with dike intrusion and introduction of seawater‐derived volatiles. Microtextures show a change from compressional to tensional stress during vein formation. Temperatures and oxidation state were obtained from amphibole‐plagioclase and oxide pairs in the adjacent gabbros. Type I veins generally have reverse shear‐sense, with restricted ΔFMQ, high Mt/Ilm ratios, and low‐amphibole Cl/F indicating deuteric fluids. They formed during percolation and fractionation of Fe‐Ti‐rich melts into the primary olivine gabbro. Type II veins are usually hosted by olivine gabbro, occur at dike contacts and the margins of normal‐sense shear zones. They are undeformed or weakly deformed, with highly variable ΔFMQ, low Mt/Ilm ratios, and high‐amphibole Cl/F, indicating seawater‐derived fluids. The detachment fault on which the gabbro massif was emplaced rooted near the base of the dike‐gabbro transition beneath the rift valley. The ingress of seawater volatiles began at 〉800°C and penetrated at least ~590 m into the lower crust during extensional faulting in the rift valley and adjacent rift mountains. The sequence of the felsic vein formation likely reflects asymmetric diapiric flow, with a reversal of the stress regime, and a transition from juvenile to seawater‐derived volatiles. This, in turn, is consistent with fault capture leading to the large asymmetries in spreading rates during OCC formations and heat flow beneath the rift mountains.
    Description: This study was supported by the Chinese National Key Basic Research Program (Grant 2012CB417300). H. Dick and B. Urann were supported by U.S. National Science Foundation (Grant OCE‐MG&G 8371300). Emmanuel Codillo provided numerous useful comments and moral support. We thank N. Chatterjee for assistance in analyzing major element mineral composition in the MIT Electron Microprobe Laboratory. The great contributions of 360 Scientific Party for their initial shipboard description and interpretations of the Hole U1473A cores made this work possible. Special thanks go to C. J. MacLeod, Expedition cochief scientist, and Peter Blum, staff scientist, Stephen Midgley, IODP operations superintendent, and Siem Offshore James Samuel McLelland, offshore installation manager, ship's master Terry Skinner, and the crew and drillers on the JOIDES Resolution.
    Keywords: Felsic veins ; Magma chambers ; Ocean ridge ; Geothermometry ; Flourine‐chlorine ; Dynamics
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 5
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-10-26
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2021.
    Description: This thesis explores the volatile content of the mantle, subducted oceanic crust, and arc magmas as well as the structure of slow spreading ocean crust and the heterogeneity of Earth’s upper mantle. In Chapter 2, I directly explore the halogen (F and Cl) content of mantle minerals in situ, then use these measurements to assess the halogen content of the upper mantle. In Chapter 3, I investigate the volatile content of Raspas eclogites (SW Ecuador), a proxy for deeply subducted oceanic crust, to evaluate volatile transfer from crustal generation at divergent plate boundaries (e.g., mid-ocean ridges) to recycling of ocean crust at subduction zones. In Chapter 4, I use the H2O content of nominally anhydrous minerals in plutonic arc cumulates to elucidate the H2O content of the melts from which the rocks crystallized. In this way, I assert that primitive arc magmas may contain 4–10 wt.% H2O and through fractional crystallization up to ~20 wt.% H2O, making them far more hydrous than traditional methods (i.e., olivine-hosted melt inclusions) surmise. In Chapter 5, I show that mantle peridotite exposed along the 16ºN region of the Mid-Atlantic Ridge originated in an arc setting and has been remixed into subridge mantle, indicating that the sub-ridge mantle is more heterogeneous and depleted than inferences made from mid-ocean ridge basalts suggest. Chapter 6 surveys the life cycle of oceanic core complexes through zircon geochronology and posits an updated framework for understanding the termination of oceanic core complexes, and more broadly oceanic detachment faults. Together, this contribution highlights the chemical heterogeneity of the mantle, and quantifies the full extent of volatiles hosted by mantle and crustal reservoirs.
    Description: The Stanley Watson Fellowship (WHOI) provided financial support during my first year of graduate school. The Academic Programs Office Ocean Venture Fund (WHOI) provided seed funding which initiated Chapters 3 and 4, and ultimately led to two funded NSF proposals. These resources are vital to JP students, and I am incredibly grateful for them. Primary support was provided by the National Science Foundation grants to Veronique Le Roux (EAR P&G #1524311, #1839128, #1855302) and Henry Dick (MG&G #1637130, #1657983).
    Keywords: Geochemistry of the crust and mantle ; Volatile elements ; Tectonics
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 6
    Publication Date: 2022-05-27
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Le Roux, V., Urann, B. M., Brunelli, D., Bonatti, E., Cipriani, A., Demouchy, S., & Monteleone, B. D. Postmelting hydrogen enrichment in the oceanic lithosphere. Science Advances, 7(24), (2021): eabf6071, https://doi.org/10.1126/sciadv.abf6071.
    Description: The large range of H2O contents recorded in minerals from exhumed mantle rocks has been challenging to interpret, as it often records a combination of melting, metasomatism, and diffusional processes in spatially isolated samples. Here, we determine the temporal variations of H2O contents in pyroxenes from a 24-Ma time series of abyssal peridotites exposed along the Vema fracture zone (Atlantic Ocean). The H2O contents of pyroxenes correlate with both crustal ages and pyroxene chemistry and increase toward younger and more refractory peridotites. These variations are inconsistent with residual values after melting and opposite to trends often observed in mantle xenoliths. Postmelting hydrogen enrichment occurred by ionic diffusion during cryptic metasomatism of peridotite residues by low-degree, volatile-rich melts and was particularly effective in the most depleted peridotites. The presence of hydrous melts under ridges leads to widespread hydrogen incorporation in the oceanic lithosphere, likely lowering mantle viscosity compared to dry models.
    Description: Funding for this study was supported by NSF EAR-P&G 1524311 and 1839128 to V.L.R. and the Andrew W. Mellon Foundation Award for Innovative Research to V.L.R. A.C. and D.B. were funded by the Italian Programma di Rilevante Interesse Nazionale PRIN 20178LPCPW and PRIN2017KY5ZX8, respectively. Revisions were performed within the duration of a “Visiting Scholar at SCIENCE 2020” award to V.L.R. (University of Copenhagen, Denmark), with support from the Department of Geosciences and Natural Resource Management, Section for Geology.
    Repository Name: Woods Hole Open Access Server
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  • 7
    Publication Date: 2022-05-26
    Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Urann, B. M., Dick, H. J. B., Parnell-Turner, R., & Casey, J. F. Recycled arc mantle recovered from the Mid-Atlantic Ridge. Nature Communications, 11(1), (2020): 3887, doi:10.1038/s41467-020-17604-8.
    Description: Plate tectonics and mantle dynamics necessitate mantle recycling throughout Earth’s history, yet direct geochemical evidence for mantle reprocessing remains elusive. Here we present evidence of recycled supra-subduction zone mantle wedge peridotite dredged from the Mid-Atlantic Ridge near 16°30′N. Peridotite trace-element characteristics are inconsistent with fractional anhydrous melting typically associated with a mid-ocean ridge setting. Instead, the samples are best explained by hydrous flux melting which changed the melting reactions such that clinopyroxene was not exhausted at high degrees of melting and was retained in the residuum. Based on along-axis ridge depth variations, this buoyant refractory arc mantle is likely compensated at depth by denser, likely garnet-rich, lithologies within the mantle column. Our results suggest that highly refractory arc mantle relicts are entrained in the upper mantle and may constitute 〉60% of the upper mantle by volume. These highly refractory mantle domains, which contribute little to mantle melting, are under-represented in compilations of mantle composition that rely on inverted basalt compositions alone.
    Description: We thank the science party for their dutiful collection and description of dredge samples, and in particular chief scientist Dr. Deborah K. Smith. Analysis work for this research was supported by an internal grant from the MIT EAPS Student Research Fund to BMU. Urann was supported by the Stanley W. Watson Student Fellowship Fund based at WHOI. Dick and Urann were supported by NSF OCE-1637130 and OCE-1155650. Dr. Yongjun Gao is thanked for conducting LA-ICP-MS trace elements analyses.
    Repository Name: Woods Hole Open Access Server
    Type: Article
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