Carbonate transfer during the onset of slab devolatilization: new insights from Fe and Zn stable isotopes

Carbonate transfer during the onset of slab devolatilization: new insights from Fe and Zn stable... ABSTRACT Long-term carbon cycling is a subject of recent controversy as new mass balance calculations suggest that most carbon is transferred from the slab to the mantle wedge by fluids during subduction, limiting the efficiency of carbon recycling to the deep mantle. Here, we examine the large scale mobility of carbon during subduction using new isotopic tracers sensitive to H-C-O-S-Cl fluids, namely iron and zinc stable isotopes, in samples interpreted to represent residual slab (Queyras, Western Alps) and sub-arc mantle (Kohistan, Himalaya). We show that during subduction there are several stages of carbonate precipitation and dissolution at metasomatic interfaces between metasedimentary and ultramafic rocks in the slab. During the early stages of subduction, before the slab reaches the 300-400 °C isotherms, the infiltration of sediment-derived fluids into ultramafic lithologies enhances carbonate precipitation in antigorite-bearing serpentinites. Carbonate storage in serpentinites therefore acts as a temporary reservoir of carbon in subduction zones. This episode is accompanied by a decrease in serpentinite iron isotope composition (δ56Fe), due to interaction with low-δ56Fe sediment-derived fluids, and an increase in the concentrations of fluid-mobile elements (e.g. B, Li, As). At higher temperatures (> 400 °C), carbonate is leached from the serpentinites by fluids. This is accompanied by a decrease in serpentinite zinc isotope composition (δ66Zn) which we interpret as the release of a carbonate-bearing fluid with an isotopically heavy δ66Zn signature. Thermodynamic modelling reveals that the sudden change in fluid carbon mobility is due to a decrease in the aCO2 of the fluids released during slab prograde metamorphism, which shifts from sediment- to serpentinite-dominated dehydration. This demonstrates that slab fluids bearing oxidized carbon (e.g. CO2), associated with isotopically light Fe, heavy Zn and fluid-mobile elements, can be released before the slab reaches eclogite facies P-T conditions. These observations provide strong evidence for the mobility of carbon in fluids during the early stages of subduction. Moreover, the fluids released will act as a potential metasomatic agent for the fore-arc mantle (or slab/mantle interface). The observation of carbonate-bearing metamorphic veins in the Himalayan sub-arc mantle with complementary light δ56Fe and heavy δ66Zn signatures provides further support for the large scale transfer of both sulphate- and carbonatebearing fluids during the early stages of subduction. This suggests that the fore-arc may have an important role in delivering water, sulfur and carbon to the source of arc-magmas. © The Author(s) 2018. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com This article is published and distributed under the terms of the Oxford University Press, Standard Journals Publication Model (https://academic.oup.com/journals/pages/about_us/legal/notices) http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Journal of Petrology Oxford University Press

Carbonate transfer during the onset of slab devolatilization: new insights from Fe and Zn stable isotopes

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Publisher
Oxford University Press
Copyright
© The Author(s) 2018. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com
ISSN
0022-3530
eISSN
1460-2415
D.O.I.
10.1093/petrology/egy057
Publisher site
See Article on Publisher Site

Abstract

ABSTRACT Long-term carbon cycling is a subject of recent controversy as new mass balance calculations suggest that most carbon is transferred from the slab to the mantle wedge by fluids during subduction, limiting the efficiency of carbon recycling to the deep mantle. Here, we examine the large scale mobility of carbon during subduction using new isotopic tracers sensitive to H-C-O-S-Cl fluids, namely iron and zinc stable isotopes, in samples interpreted to represent residual slab (Queyras, Western Alps) and sub-arc mantle (Kohistan, Himalaya). We show that during subduction there are several stages of carbonate precipitation and dissolution at metasomatic interfaces between metasedimentary and ultramafic rocks in the slab. During the early stages of subduction, before the slab reaches the 300-400 °C isotherms, the infiltration of sediment-derived fluids into ultramafic lithologies enhances carbonate precipitation in antigorite-bearing serpentinites. Carbonate storage in serpentinites therefore acts as a temporary reservoir of carbon in subduction zones. This episode is accompanied by a decrease in serpentinite iron isotope composition (δ56Fe), due to interaction with low-δ56Fe sediment-derived fluids, and an increase in the concentrations of fluid-mobile elements (e.g. B, Li, As). At higher temperatures (> 400 °C), carbonate is leached from the serpentinites by fluids. This is accompanied by a decrease in serpentinite zinc isotope composition (δ66Zn) which we interpret as the release of a carbonate-bearing fluid with an isotopically heavy δ66Zn signature. Thermodynamic modelling reveals that the sudden change in fluid carbon mobility is due to a decrease in the aCO2 of the fluids released during slab prograde metamorphism, which shifts from sediment- to serpentinite-dominated dehydration. This demonstrates that slab fluids bearing oxidized carbon (e.g. CO2), associated with isotopically light Fe, heavy Zn and fluid-mobile elements, can be released before the slab reaches eclogite facies P-T conditions. These observations provide strong evidence for the mobility of carbon in fluids during the early stages of subduction. Moreover, the fluids released will act as a potential metasomatic agent for the fore-arc mantle (or slab/mantle interface). The observation of carbonate-bearing metamorphic veins in the Himalayan sub-arc mantle with complementary light δ56Fe and heavy δ66Zn signatures provides further support for the large scale transfer of both sulphate- and carbonatebearing fluids during the early stages of subduction. This suggests that the fore-arc may have an important role in delivering water, sulfur and carbon to the source of arc-magmas. © The Author(s) 2018. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com This article is published and distributed under the terms of the Oxford University Press, Standard Journals Publication Model (https://academic.oup.com/journals/pages/about_us/legal/notices)

Journal

Journal of PetrologyOxford University Press

Published: Jun 6, 2018

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