Pervasive subduction zone devolatilization recycles CO₂ into the forearc

The fate of subducted CO₂ remains the subject of widespread disagreement, with different models predicting either wholesale (up to 99%) decarbonation of the subducting slab or extremely limited carbon loss and, consequently, massive deep subduction of CO₂. The fluid history of subducted rocks lies at the heart of this debate: rocks that experience significant infiltration by a water-bearing fluid may release orders of magnitude more CO₂ than rocks that are metamorphosed in a closed chemical system. Numerical models make a wide range of predictions regarding water mobility, and further progress has been limited by a lack of direct observations. Here we present a comprehensive field-based study of decarbonation efficiency in a subducting slab (Cyclades, Greece), and show that ~40% to ~65% of the CO₂ in subducting crust is released via metamorphic decarbonation reactions at forearc depths. This result precludes extensive deep subduction of most CO₂ and suggests that the mantle has become more depleted in carbon over geologic time

Pervasive subduction zone devolatilization recycles CO₂ into the forearc

The fate of subducted CO₂ remains the subject of widespread disagreement, with different models predicting either wholesale (up to 99%) decarbonation of the subducting slab or extremely limited carbon loss and, consequently, massive deep subduction of CO₂. The fluid history of subducted rocks lies at the heart of this debate: rocks that experience significant infiltration by a water-bearing fluid may release orders of magnitude more CO₂ than rocks that are metamorphosed in a closed chemical system. Numerical models make a wide range of predictions regarding water mobility, and further progress has been limited by a lack of direct observations. Here we present a comprehensive field-based study of decarbonation efficiency in a subducting slab (Cyclades, Greece), and show that ~40% to ~65% of the CO₂ in subducting crust is released via metamorphic decarbonation reactions at forearc depths. This result precludes extensive deep subduction of most CO₂ and suggests that the mantle has become more depleted in carbon over geologic time

Models of permeability contrasts in subduction zone melange: Implications for gradients

Abstract Geological and geochemical evidence from previous studies suggest limited fluid flow through the interiors of many blocks of subducted oceanic crust within meta-ultramafic or metasedimentary mélange matrix on the islands of Syros and Tinos, Cyclades, Greece. This finding is provocative because metamorphic devolatilization of igneous and sedimentary rocks during subduction should have liberated substantial volumes of fluid. In an effort to address this problem, two-dimensional numerical models incorporating permeability anisotropy and devolatilization are used to investigate spatial patterns of steady-state fluid flow through subduction zone mélange under high-pressure/low-temperature (HP/LT) conditions. The modeling shows that as the permeability of the mélange blocks decreases relative to the mélange matrix, more flow is diverted around the blocks into the matrix. The ratio of the maximum flux (in matrix) relative to the minimum flux (in blocks) increases with the permeability contrast between the matrix and the less permeable blocks. Order-of-magnitude variations in permeability produce order-of-magnitude spatial variations in fluid fluxes between block interiors and surrounding matrix; flux variations of a factor of 10 or more can be present over very short length scales (as little as meter scale). The largest fluxes are produced in the matrix adjacent to block margins lying subparallel to regional foliation and flow direction. Fluid-rock reaction on block margins would be greatest in these areas, leading to asymmetrical distributions of reaction progress around blocks (illustrated herein by field mapping of a mélange block on Syros). However, syn-metamorphic deformation can rotate blocks and strip off reaction zones at their margins, so it is likely that reaction zone asymmetries are commonly disrupted in nature. The inferred absence of strong fluid-rock reaction within mélange blocks on Syros and Tinos could reflect low permeabilities in block interiors which acted to divert flow into mélange matrix. Consequently, fluxes of subduction zone fluids through the mélange matrix could have easily been very large, while low permeabilities shielded block interiors from the regional flow to varying degrees

Field‐based evidence for intra‐slab high‐permeability channel formation at eclogite‐facies conditions during subduction

International audienceFluid release from subducting oceanic lithosphere is a key process for subduction zone geodynamics, from controlling arc volcanism to seismicity and tectonic exhumation. However, many fundamental details of fluid composition, flow pathways, and reactivity with slab-forming rocks remain to be thoroughly understood. In this study we investigate a multi-kilometer-long, high-pressure metasomatic system preserved in the lawsonite-eclogite metamorphic unit of Alpine Corsica, France. The fluid-mediated process was localized along a major intra-slab interface, which is the contact between basement and cover unit. Two distinct metasomatic stages are identified and discussed. We show that these two stages resulted from the infiltration of deep fluids that were derived from the same source and had the same slab-parallel, updip flow direction. By mass balance analysis, we quantify metasomatic mass changes along this fluid pathway and the time-integrated fluid fluxes responsible for them. In addition, we also assess carbon fluxes associated with these metasomatic events. The magnitude of the estimated fluid fluxes (104-105) indicates that major intra-slab interfaces such as lithological boundaries acted as fluid channels facilitating episodic pulses of fluid flow. We also show that when fluids are channelized, high time-integrated fluid fluxes lead to carbon fluxes several orders of magnitude higher than carbon fluxes generated by local dehydration reactions. Given the size and geologic features of the investigated metasomatic system, we propose that it represents the first reported natural analogue of the so-called high permeability channels predicted by numerical simulations

Uncovering and quantifying the subduction zone sulfur cycle from the slab perspective

Sulfur belongs among H2O, CO2, and Cl as one of the key volatiles in Earth’s chemical cycles. High oxygen fugacity, sulfur concentration, and δ34S values in volcanic arc rocks have been attributed to significant sulfate addition by slab fluids. However, sulfur speciation, flux, and isotope composition in slab-dehydrated fluids remain unclear. Here, we use high-pressure rocks and enclosed veins to provide direct constraints on subduction zone sulfur recycling for a typical oceanic lithosphere. Textural and thermodynamic evidence indicates the predominance of reduced sulfur species in slab fluids; those derived from metasediments, altered oceanic crust, and serpentinite have δ34S values of approximately −8‰, −1‰, and +8‰, respectively. Mass-balance calculations demonstrate that 6.4% (up to 20% maximum) of total subducted sulfur is released between 30–230 km depth, and the predominant sulfur loss takes place at 70–100 km with a net δ34S composition of −2.5 ± 3‰. We conclude that modest slab-to-wedge sulfur transport occurs, but that slab-derived fluids provide negligible sulfate to oxidize the sub-arc mantle and cannot deliver 34S-enriched sulfur to produce the positive δ34S signature in arc settings. Most sulfur has negative δ34S and is subducted into the deep mantle, which could cause a long-term increase in the δ34S of Earth surface reservoirs

Chromium isotope fractionation during subduction-related metamorphism, black shale weathering, and hydrothermal alteration

© The Author(s), 2016. This is the author's version of the work and is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Chemical Geology 423 (2016): 19-33, doi:10.1016/j.chemgeo.2016.01.003.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.Funding for this research was provided by Agouron Institute to XLW, National Science Foundation (NSF) EAR-0105927 and EAR-1250269 to JJA, and NSF EAR-1324566 to ES. NJP and CTR acknowledge funding from the Alternative Earths NAI.2017-01-1

Osmium isotopes fingerprint mantle controls on the genesis of an epithermal gold province

The formation of crustal blocks enriched with gold (Au) deposits above subduction zones is intimately bound to the genesis and evolution of magmatic-hydrothermal systems. A longstanding question, however, is whether the metal fertility of these systems stems from distinct sources that are anomalously enriched in Au or from subsequent processes occurring during crustal magma emplacement and hydrothermal activity. The Deseado Massif auriferous province in southern Patagonia (Argentina) is a unique place to test these contrasting hypotheses because Au-bearing mantle xenoliths indicate the presence of an underlying Au-rich lithospheric mantle reservoir. However, direct geochemical links between the Au-rich mantle source and the formation of the Deseado Massif auriferous province in the overlying crust remain to be established. To address this prominent gap in knowledge, we used sulfide Re-Os geochronology to identify the source of Au at Cerro Vanguardia, the largest low-sulfidation epithermal Au-Ag deposit in the Deseado Massif. Pyrite from high-grade Au quartz veins yielded an isochron age of 147.4 ± 2.9 Ma (mean square of weighted deviates = 1.04, n = 8) and an initial 187Os/188Os ratio of 0.26 ± 0.01, fingerprinting a dominant mantle control for the source of Os and, by inference, the source of Au. Our data provide a unique geochemical linkage between an Au-rich subcontinental lithospheric mantle source and the genesis of epithermal Au deposits, supporting the hypothesis that pre-enriched mantle domains may be a critical factor underpinning the global-scale localization of Au provinces.Fil: Tassara, Santiago. University of Yale; Estados UnidosFil: Rooney, Alan D.. University of Yale; Estados UnidosFil: Ague, Jay. J.. University of Yale; Estados UnidosFil: Guido, Diego Martin. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. Instituto de Recursos Minerales. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Instituto de Recursos Minerales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; ArgentinaFil: Reich, Martin. Universidad de Chile; ChileFil: Barra, Fernando. Universidad de Chile; ChileFil: Navarrete Granzotto, César Rodrigo. Universidad Nacional de la Patagonia "San Juan Bosco"; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Slab-derived devolatilization fluids oxidized by subducted metasedimentary rocks

Metamorphic devolatilization of subducted slabs generates aqueous fluids that ascend into the mantle wedge, driving the partial melting that produces arc magmas. These magmas have oxygen fugacities some 10–1,000 times higher than magmas generated at mid-ocean ridges. Whether this oxidized magmatic character is imparted by slab fluids or is acquired during ascent and interaction with the surrounding mantle or crust is debated. Here we study the petrology of metasedimentary rocks from two Tertiary Aegean subduction complexes in combination with reactive transport modelling to investigate the oxidative potential of the sedimentary rocks that cover slabs. We find that the metasedimentary rocks preserve evidence for fluid-mediated redox reactions and could be highly oxidized. Furthermore, the modelling demonstrates that layers of these oxidized rocks less than about 200 m thick have the capacity to oxidize the ascending slab dehydration flux via redox reactions that remove H2, CH4 and/or H2S from the fluids. These fluids can then oxidize the overlying mantle wedge at rates comparable to arc magma generation rates, primarily via reactions involving sulfur species. Oxidized metasedimentary rocks need not generate large amounts of fluid themselves but could instead oxidize slab dehydration fluids ascending through them. Proposed Phanerozoic increases in arc magma oxygen fugacity may reflect the recycling of oxidative weathering products following Neoproterozoic–Palaeozoic marine and atmospheric oxygenation