Mantle oxidation influenced by reduction-oxidation budget of Mariana-type subduction zones

Oceanic plates descending into subduction zones transport a significant amount of oxidized material to both the subduction zone and the Earth's deeper layers (Wood et al. 1990). However, the specific mechanism of mass transfer and the corresponding flux released at different depths remains unclear. Through the use of numerical modeling and a coupled geochemical database, we examined redox dynamics in subduction zones, particularly focusing on Mariana-type subduction zones, representative of the modern plate tectonic regime (Yao et al., 2021).Our findings highlight two primary mechanisms in the mantle oxidation processes related to subduction. Firstly, desulfurization enables subduction fluids to carry substantial oxidation fluxes into the sub-arc mantle. Mass balance calculations emphasize the sufficiency of these fluxes in oxidizing both the arc magma and mantle wedge, with the hydrated mantle being the primary fluid contributor, followed by the altered oceanic crust. Secondly, partial melting of slab-top rocks, where Fe3+-rich melts from sediments and altered oceanic crust play a predominant role in the oxidation of the back-arc mantle. Importantly, during Mariana-type subduction, the majority of oxidation fluxes penetrate the deeper mantle with subducting slabs. According to our models, we illustrate that during the modern era of plate tectonics, the oxidation fluxes generated by Mariana-type subduction zones had a significant global impact on Earth's mantle redox evolution and the oxygenation of our planet.ReferencesWood, B. J., Bryndzia, T., Johnson, K. E. Mantle oxidation state and its relationship to tectonic environment and fluid speciation. Science 248, 337-345 (1990).Yao, J., Cawood, P. A., Zhao, G., Han, Y., Xia, X., Liu, Q., Wang, P. Mariana-type ophiolites constrain the establishment of modern plate tectonic regime during Gondwana assembly. Nat. Commun. 12(1), 4189 (2021).

Geochemistry of subducted metabasites exhumed from the Mariana forearc: Implications for Pacific seamount subduction

Oxidation of the sub-arc mantle driven by slab-derived fluids has been hypothesized to contribute to the formation of gold deposits in magmatic arc environments that host the majority of metal resources on Earth. However, the mechanism by which the infiltration of slab-derived fluids into the mantle wedge changes its oxidation state and affects Au enrichment remains poorly understood. Here, we present the results of a numerical model that demonstrates that slab-derived fluids introduce large amounts of sulfate (S6+) into the overlying mantle wedge that increase its oxygen fugacity by up to 3 to 4 log units relative to the pristine mantle. Our model predicts that as much as 1 wt.% of the total dissolved sulfur in slab-derived fluids reacting with mantle rocks is present as the trisulfur radical ion, S3-. This sulfur ligand stabilizes the aqueous Au(HS)S3- complex, which can transport Au concentrations of several grams per cubic meter of fluid. Such concentrations are more than three orders of magnitude higher than the average abundance of Au in the mantle. Our data thus demonstrate that an aqueous fluid phase can extract 10 to 100 times more Au than in a fluid-absent rock-melt system during mantle partial melting at redox conditions close to the sulfide-sulfate boundary. We conclude that oxidation by slab-derived fluids is the primary cause of Au mobility and enrichment in the mantle wedge and that aqueous fluid-assisted mantle melting is a prerequisite for formation of Au-rich magmatic hydrothermal and orogenic gold systems in subduction zone settings.

The Kamchatka volcanic arc (Russia) is one of best-studied, but most complex tectonic margins on Earth, with an extensive geologic history extending back to the Late Cretaceous. Unlike many other subduction zones, primitive basalts with Mg# > 65 are abundant in Kamchatka, thereby allowing characterization of the mantle source through compositional analyses of near-liquidus minerals in the rocks. In this paper, we present a comprehensive dataset on the composition of Cr-spinel inclusions in olivine for all main Late Quaternary volcanic zones in Kamchatka, comprising 1604 analyses of spinel inclusions and their host-olivine in 104 samples from 30 volcanic complexes (single volcanoes and volcanic fields). The studied rocks are basalts, basaltic andesites and high-Mg andesites, which cover the whole compositional range of the primitive Late Quaternary volcanic rocks in Kamchatka. The spinel composition shows large variability. Spinel inclusions with the lowest Cr# and Fe3+/Fe2+ ratios were found in basalts from Sredinny Range and Northern Kamchatka, whereas the most Cr-rich and oxidized spinel inclusions occur in basalts and high-Mg andesites from the Central Kamchatka Depression. Intermediate Cr-spinel compositions characterize the Eastern Volcanic Belt of Kamchatka. The compositions of olivine-spinel pairs were used to quantify the oxidation state of parental Kamchatka magmas and the degree of partial mantle melting. The redox conditions recorded in spinel compositions range from ΔQFM = +0.7 to +3.7. ΔQFM for spinel from the Sredinny Range and Northern Kamchatka correlates with a number of whole-rock proxies for the involvement of slab-derived components (e.g., La/Nb and Ba/La), which suggests a coupling between mantle oxidation state and slab-derived fluid/melt metasomatism. These correlations were not observed in frontal Kamchatka volcanoes with the highest estimated ΔQFM, which possibly indicates buffering of the mantle oxidation state by sulfur. The estimated degrees of partial mantle melting range from 8 to >20% for Kamchatka volcanoes. Spinel from the Central Kamchatka Depression has the highest Cr# and could crystallize from magmas generated from the most depleted sources. In contrast to the Eastern Volcanic Belt, spinel Cr# and the inferred degrees of melting in the Central Kamchatka Depression do not correlate with spinel TiO2 content. The apparent decoupling between the proxies of mantle depletion in the CKD spinel is interpreted to reflect refertilization of the CKD mantle by oxidized Ti-rich slab- or mantle lithosphere-derived melts near the northern edge of the subducting Pacific Plate. This study demonstrates that the composition of Cr-spinel in volcanic rocks in combination with bulk-rock compositions can be a powerful tool to map regional variations of the mantle source depletion, oxidation state, and involvement of various slab-derived components in island-arc magmatism.

The redox budget of subduction zones

Subduction zones are key regions of chemical and mass transfer between the Earth’s surface and mantle. During subduction, oxidized material is carried into the mantle and large amounts of water are released due to the breakdown of hydrous minerals such as lawsonite. Dehydration accompanied by the release of oxidizing species may play a key role in controlling redox changes in the subducting slab and overlying mantle wedge. Here we present measurements of oxygen fugacity, using garnet–epidote oxybarometry, together with analyses of the stable iron isotope composition of zoned garnets from Sifnos, Greece. We find that the garnet interiors grew under relatively oxidized conditions whereas garnet rims record more reduced conditions. Garnet δ56Fe increases from core to rim as the system becomes more reduced. Thermodynamic analysis shows that this change from relatively oxidized to more reduced conditions occurred during lawsonite dehydration. We conclude that the garnets maintain a record of progressive dehydration and that the residual mineral assemblages within the slab became more reduced during progressive subduction-zone dehydration. This is consistent with the hypothesis that lawsonite dehydration accompanied by the release of oxidizing species, such as sulfate, plays an important and measurable role in the global redox budget and contributes to sub-arc mantle oxidation in subduction zones. Lawsonite dehydration and release of oxidizing fluids could play an important role in sub-arc mantle oxidation in subduction zones, suggest measurements of changing oxygen fugacity in zoned garnets from Sifnos, Greece.

The sulfur concentration at anhydrite saturation in silicate melts: Implications for sulfur cycle and oxidation state in subduction zones

The earth's mantle is degassed along mid-ocean ridges, while rehydration and possibly recarbonaton occurs at subduction zones. These processes and the speciation of C-H-O fluids in the mantle are related to the oxidation state of mantle peridotite. Peridotite xenoliths from continental localities exhibit an oxygen fugacity (fo(2)) range from -1.5 to +1.5 log units relative to the FMQ (fayalite-magnetite-quartz) buffer. The lowest values are from zones of continental extension. Highly oxidized xenoliths (fo(2) greater than FMQ) come from regions of recent or acive subduction (for example, Ichinomegata, Japan), are commonly amphibole-bearing, and show trace element and isotopic evidence of fluid-rock interaction. Peridotites from ocean ridges are reduced and have an averae fo(2) of about -0.9 log units relative to FMQ, virtually coincident with values obtained from mid-ocean ridge basalt (MORB) glasses. These data are further evidence of the genetic link between MORB liquids and residual peridotite and indicate that the asthenosphere, although reducing, has CO(2) and H(2)O as its major fluid species. Incorporation of oxidized material from subduction zones into the continental lithosphere produces xenoliths that have both asthenospheric and subduction signatures. Fluids in the lithosphere are also dominated by CO(2) and H(2)O, and native C is generally unstable. Although the occurrence of native C (diamond) in deep-seated garnetiferous xenoliths and kimberlites does not require reducing conditions, calculations indicate that high Fe(3+) contents are stabilized in the garnet structure and that fo(2) deareases with increasing depth.

The redox geodynamics linking basalts and their mantle sources through space and time

The generation and migration of slab-derived fluids modulate subduction zone seismicity, arc magmatism, and deep volatile cycling. However, the redox species and oxygen fugacity (fO2) (hereafter expressed as log units relative to the fayalite–magnetite–quartz buffer, △FMQ) of slab-derived fluids are highly debated. Here we conducted phase equilibria modeling on altered oceanic crust (AOC) and serpentinites along typical subduction geotherms in the C-S-bearing system over a pressure range of 0.5–6 GPa. With the averaged compositions of AOC and serpentinite, our calculated results show that oxidized carbon-sulfur species dominate slab-derived fluids during slab subduction. As a result, slab-derived fluids are highly oxidized and at or above the typical △FMQ values of arc magmas at forearc to subarc depths. The predicted oxidized carbon and sulfur species are compatible with natural observations in fluid inclusions from many oceanic HP metamorphic rocks. More importantly, it is revealed that, the redox state of slab-derived fluids is primarily controlled by the redox budget (RB) of the slab prior to subduction. Subduction-zone thermal structure, however, only exerts a minor influence on the slab-derived fluid fO2, which is supported by the similar fO2 ranges in arc lavas from cold and hot subduction zones. Our models further show that, if an open system is assumed, most of carbon (>70%) and sulfur (>50%) in cold subducted AOC and serpentinite would be lost at subarc depths. Small amounts of carbon and sulfur could be transported into the deeper mantle via closed-system subduction and open-system cold subduction, supplying the source materials for volatile-rich intraplate magmas and superdeep diamonds.

The redox state of subduction zones: insights from arc-peridotites

Author index volume 35

Light Fe isotopes in arc magmas from cold subduction zones: Implications for serpentinite-derived fluids oxidized the sub-arc mantle

The inner and outer layers of the Earth can be connected by plate tectonics with exchange of material and energy, thus shaping the habitable Earth today. However, the existence of Archean plate tectonics has been controversial. One of the reasons is the lack of rock records that can best represent the presence of the convergent plate boundaries during that time, such as continental lithosphere with ultrahigh-pressure metamorphism (> 2.7 GPa or 80–100 km). Here we investigated the peridotites from the North China Craton, and conducted a systematic investigation involving field survey, mineralogy, petrology, geochronology and geochemistry on these peridotites. Temperature and pressure conditions for protoliths of these peridotites, as well as oxygen fugacity (fO2), were also calculated, to constrain petrogenesis, tectonic setting, and characteristics of mantle fO2.In situ U-Pb dating on zircons from the peridotites yields metamorphic/altered age of 2535–2517 Ma and were intruded by the unmetamorphosed granite dykes at ~2500 Ma. Garnet pseudomorphs and pyroxene with exsolved textures were identified in these peridotites, suggesting that the original garnet and pyroxene were brought from high pressures and the breakdown was induced by decompression. Reintegrating the compositions of the original garnet and pyroxene and compositions of the original garnet and pyroxene indicate that these peridotites were brought up or once seated at mantle depths of 110–130 km. The calculated dT/dP thermal gradients is around 375 oC/GPa, close to those of modern collisional orogens.   The occurrence of phlogopite and amphibole in the studied peridotites and the enrichment of light rare earth elements in their bulk-rock and mineral trace elements, as well as the higher contents of magnesium and aluminum in the rim, and chromium and iron in the core of spinels in some samples, which further demonstrates that the studied peridotites experienced mantle metasomatism during plate subduction. Using Olivine-orthopyroxene-spinel oxybarometry, this dissertation obtained the fO2 of these Archean metasomatized peridotites to range from ΔFMQ +1.0 to ΔFMQ +1.7, which are more oxidized than the Archean ambient mantle, but are similar to the modern sub-arc mantle.The ultrahigh-pressure peridotites prove that some forms of plate tectonics have been operating at least since the Neoarchean, and also indicate that the continental deep subduction could have existed at least prior to 2.5 billion years ago. During this process, the Neoarchean mantle oxidation was increased, in which subducted crustal materials would have significantly metasomatized the mantle and increased its oxygen fugacity. This process may have contributed to the Archean atmospheric redox evolution and triggered the GOE in the early Proterozoic.

The Archean mantle redox state played an important role in degassing of the Earth's interior and thus influenced atmospheric oxygen levels of the early Earth. But it is unclear if any parts of the uppermost mantle were significantly oxidized by a certain point in the Archean. Here, we investigate oxygen fugacity (fO2) of Archean (> 2535–2517 Ma) peridotites in the North China Craton. Petrology and geochemistry reveal that they experienced strong Neoarchean subduction-related metasomatism. These Neoarchean subduction-metasomatized peridotites record fO2 of ΔFMQ +1.3 ± 0.4 (SD) [relative to the fayalite-magnetite-quartz (FMQ) buffer], which are more oxidized than the Archean ambient mantle, but similar to the modern sub-arc mantle. We propose that this Neoarchean rise of mantle oxidation in the North China Craton was induced by plate subduction, during which the Neoarchean sub-arc mantle in the North China Craton could have been metasomatized and oxidized, and its oxygen fugacity was increased. This process may have had connections with the Great Oxidation Event in the Early Proterozoic.