Schwarzenbach Esther M.

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Esther M.

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  • Preprint
    Chromium isotope fractionation during subduction-related metamorphism, black shale weathering, and hydrothermal alteration
    ( 2016-01) Wang, Xiangli ; Planavsky, Noah J. ; Reinhard, Christopher T. ; Zou, Huijuan ; Ague, Jay J. ; Wu, Yuanbao ; Gill, Benjamin C. ; Schwarzenbach, Esther M. ; Peucker-Ehrenbrink, Bernhard
    Chromium (Cr) isotopes are an emerging proxy for redox processes at Earth’s surface. However, many geological reservoirs and isotope fractionation processes are still not well understood. The purpose of this contribution is to move forward our understanding of (1) Earth’s high temperature Cr isotope inventory and (2) Cr isotope fractionations during subduction-related metamorphism, black shale weathering and hydrothermal alteration. The examined basalts and their metamorphosed equivalents yielded δ53Cr values falling within a narrow range of -0.12±0.13‰ (2SD, n=30), consistent with the previously reported range for the bulk silicate Earth (BSE). Compilations of currently available data for fresh silicate rocks (43 samples), metamorphosed silicate rocks (50 samples), and mantle chromites (39 samples) give δ53Cr values of -0.13±0.13‰, -0.11±0.13‰, and -0.07±0.13‰, respectively. Although the number of high-temperature samples analyzed has tripled, the originally proposed BSE range appears robust. This suggests very limited Cr isotope fractionation under high temperature conditions. Additionally, in a highly altered metacarbonate transect that is representative of fluid-rich regional metamorphism, we did not find resolvable variations in δ53Cr, despite significant loss of Cr. This work suggests that primary Cr isotope signatures may be preserved even in instances of intense metamorphic alteration at relatively high fluid-rock ratios. Oxidative weathering of black shale at low pH creates isotopically heavy mobile Cr(VI). However, a significant proportion of the Cr(VI) is apparently immobilized near the weathering surface, leading to local enrichment of isotopically heavy Cr (δ53Cr values up to ~0.5‰). The observed large Cr isotope variation in the black shale weathering profile provides indirect evidence for active manganese oxide formation, which is primarily controlled by microbial activity. Lastly, we found widely variable δ53Cr (-0.2‰ to 0.6‰) values in highly serpentinized peridotites from ocean drilling program drill cores and outcropping ophiolite sequences. The isotopically heavy serpentinites are most easily explained through a multi-stage alteration processes: Cr loss from the host rock under oxidizing conditions, followed by Cr enrichment under sulfate reducing conditions. In contrast, Cr isotope variability is limited in mildly altered mafic oceanic crust.
  • Article
    Sulphur and carbon cycling in the subduction zone mélange
    (Nature Publishing Group, 2018-10-19) Schwarzenbach, Esther M. ; Caddick, Mark J. ; Petroff, Matthew ; Gill, Benjamin C. ; Cooperdock, Emily H. G. ; Barnes, Jaime D.
    Subduction zones impose an important control on the geochemical cycling between the surficial and internal reservoirs of the Earth. Sulphur and carbon are transferred into Earth’s mantle by subduction of pelagic sediments and altered oceanic lithosphere. Release of oxidizing sulphate- and carbonate-bearing fluids modifies the redox state of the mantle and the chemical budget of subduction zones. Yet, the mechanisms of sulphur and carbon cycling within subduction zones are still unclear, in part because data are typically derived from arc volcanoes where fluid compositions are modified during transport through the mantle wedge. We determined the bulk rock elemental, and sulphur and carbon isotope compositions of exhumed ultramafic and metabasic rocks from Syros, Greece. Comparison of isotopic data with major and trace element compositions indicates seawater alteration and chemical exchange with sediment-derived fluids within the subduction zone channel. We show that small bodies of detached slab material are subject to metasomatic processes during exhumation, in contrast to large sequences of obducted ophiolitic sections that retain their seafloor alteration signatures. In particular, fluids circulating along the plate interface can cause sulphur mobilization during several stages of exhumation within high-pressure rocks. This takes place more pervasively in serpentinites compared to mafic rocks.
  • Article
    Fluid‐mediated mass transfer between mafic and ultramafic rocks in subduction zones
    (American Geophysical Union, 2022-07-11) Codillo, Emmanuel A. ; Klein, Frieder ; Dragovic, Besim ; Marschall, Horst R. ; Baxter, Ethan ; Scambelluri, Marco ; Schwarzenbach, Esther M.
    Metasomatic reaction zones between mafic and ultramafic rocks exhumed from subduction zones provide a window into mass-transfer processes at high pressure. However, accurate interpretation of the rock record requires distinguishing high-pressure metasomatic processes from inherited oceanic signatures prior to subduction. We integrated constraints from bulk-rock geochemical compositions and petrophysical properties, mineral chemistry, and thermodynamic modeling to understand the formation of reaction zones between juxtaposed metagabbro and serpentinite as exemplified by the Voltri Massif (Ligurian Alps, Italy). Distinct zones of variably metasomatized metagabbro are dominated by chlorite, amphibole, clinopyroxene, epidote, rutile, ilmenite, and titanite between serpentinite and eclogitic metagabbro. Whereas the precursor serpentinite and oxide gabbro formed and were likely already in contact in an oceanic setting, the reaction zones formed by diffusional Mg-metasomatism between the two rocks from prograde to peak, to retrograde conditions in a subduction zone. Metasomatism of mafic rocks by Mg-rich fluids that previously equilibrated with serpentinite could be widespread along the subduction interface, within the subducted slab, and the mantle wedge. Furthermore, the models predict that talc formation by Si-metasomatism of serpentinite in subduction zones is limited by pressure-dependent increase in the silica activity buffered by the serpentine-talc equilibrium. Elevated activities of aqueous Ca and Al species would also favor the formation of chlorite and garnet. Accordingly, unusual conditions or processes would be required to stabilize abundant talc at high P-T conditions. Alternatively, a different set of mineral assemblages, such as serpentine- or chlorite-rich rocks, may be controlling the coupling-decoupling transition of the plate interface.
  • Article
    Effect of water activity on rates of serpentinization of olivine
    (Nature Publishing Group, 2017-07-14) Lamadrid, Hector ; Rimstidt, J. Donald ; Schwarzenbach, Esther M. ; Klein, Frieder ; Ulrich, Sarah ; Dolocan, Andrei ; Bodnar, Robert J.
    The hydrothermal alteration of mantle rocks (referred to as serpentinization) occurs in submarine environments extending from mid-ocean ridges to subduction zones. Serpentinization affects the physical and chemical properties of oceanic lithosphere, represents one of the major mechanisms driving mass exchange between the mantle and the Earth’s surface, and is central to current origin of life hypotheses as well as the search for microbial life on the icy moons of Jupiter and Saturn. In spite of increasing interest in the serpentinization process by researchers in diverse fields, the rates of serpentinization and the controlling factors are poorly understood. Here we use a novel in situ experimental method involving olivine micro-reactors and show that the rate of serpentinization is strongly controlled by the salinity (water activity) of the reacting fluid and demonstrate that the rate of serpentinization of olivine slows down as salinity increases and H2O activity decreases.