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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., 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., 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).

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.

© 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., 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., 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.