Abiotic passive nitrogen and methane enrichment during exhumation of subducted rocks: primary multiphase fluid inclusions in high‐pressure rocks from the Cabo Ortegal Complex, NW Spain

Primary multiphase fluid inclusions (MFI) were studied in one eclogite and two granulites from the Cabo Ortegal Complex (COC, NW-Spain) by means of Raman imaging, SEM-EDS and FIB-SEM. Complementary, secondary MFI in pyroxenites from COC were also investigated. MFI hosted in eclogite and granulites occur along growth zones or in 3D clusters in garnet porphyroblasts suggesting a primary origin at high-pressure (HP) metamorphic conditions. The mineral assemblage of MFI is mainly composed of Fe-Mg-Ca-carbonates and phyllosilicates ± graphite ± quartz ± corundum ± pyrite ± apatite ± rutile and a fluid phase composed of nitrogen ± methane ± carbon-dioxide. The mineral proportions vary among the lithologies. Dominant carbonates and hydrous silicates are interpreted as step-daughter minerals (crystals formed in the MFI after entrapment as a result of fluid-host interaction), whereas apatite, quartz and rutile are considered in part as accidentally trapped minerals since they also occur as crystal inclusions together with MFI in each rock type. Quartz and corundum occur together in MFI in ultramafic granulite and are regarded as step-daughter minerals in this lithology. These observations suggest that the MFI are products of post-entrapment reactions of a homogeneous COHN fluid system with the host mineral. Thermodynamic calculations in the CaFMAS-COHN system confirmed that bulk composition of the MFI in eclogite is similar to the host garnet+COHN composition except for a potential lost of H2O. Carbonation and hydration reaction between the host (i.e., garnet or pyroxene) and the fluid inclusion results in the consumption of all CO2 and part of the H2O from the fluid phase producing Ca-Fe-Mg-carbonates and hydrous step-daughter minerals, mostly pyrophyllite and chlorite. Nitrogen content of the originally trapped COHN fluid in eclogite was estimated to have a maximum value of 10 mol% at peak HP conditions and 30–40 mol% at retrograde conditions that is within the range of the observed MFI in the residual fluid (13–68 mol%). Pseudosection modelling confirmed the stability of the phase assemblage in the MFI in a specific low pressure, low temperature stability field (between 300–400 °C at pressures < 1 GPa), caused by H2O and CO2-consuming reactions possibly in a single step. Our findings indicate that such processes in the exhuming HP units may play a role in global nitrogen and carbon cycling as well as potentially contributing to nitrogen and methane supply to subsurface-surface environments during devolatilization in the forearc regions of convergent plate margins

Olivine-rich veins in high-pressure serpentinites: A far-field paleo-stress snapshot during subduction

Field observations within the Atg-serpentinite domain of the subducted ultramafic massif from Cerro del Almirez (SE Spain) reveal the existence of two generations of abundant olivine-rich veins formed as open, mixed mode and shear fractures during prograde metamorphism. Type I veins were synchronous with the development of the serpentinite main foliation (S1) and shearing, whereas Type II veins post-date the S1 surfaces. These structural relationships indicate that, while the Atgserpentinites underwent ductile plastic deformation at temperatures of 450◦-600 ◦C and pressures of 0.7–1.7 GPa, they also experienced punctuated brittle behaviour events. The brittle fractures were most likely due to fluid overpressures formed by release of H2O during the brucite breakdown reaction for the case of Type I veins (2 vol % H2O) and due to a combination of minor dehydration reactions related to continuous compositional and structural changes in antigorite (0.3 vol % H2O) for Type II veins. Type II olivine-rich veins were formed by brittle failure in a well-defined paleo-stress field and were not significantly deformed after their formation. Comparison of the principal paleo-stress orientation inferred from Type II veins with those formed at peak metamorphic conditions in the ultramafic rocks at Cerro del Almirez shows a relative switch in the orientation of the maximum and minimum principal paleo-stress axes. These relative changes can be attributed to the cyclic evolution of shear stress, fluid pressure and fault-fracture permeability allowing for stress reversal.MICIN/AEI PID2019-105192GB-I00Junta de Andalucia RNM-208 RNM-141 RNM-145 RNM-131 RNM-374FEDER program "una manera de hacer Europa"Spanish Government RYC2018-024363-IUniversidad de Granada/ CBU

Chromium Isotope Behavior During Serpentinite Dehydration in Oceanic Subduction Zones

Fluids released through the dehydration of serpentinite can be rich in Cl −, which enables the significant mobility of Cr in subduction zones. However, the Cr isotope behavior accompanying the mobility of Cr during serpentinite dehydration is still poorly constrained. Here, we report high-precision Cr isotope data for a unique suite of serpentinites that represent metamorphic products at different depths in oceanic subduction zones. Low-grade serpentinites affected by significant Cr loss during serpentinization exhibit remarkably higher δ 53Cr, while samples with Cr contents >∼1,800 ppm typically preserve mantle-like δ 53Cr. Antigorite serpentinites have an average δ 53Cr value of −0.17‰ ± 0.19‰ (n = 12, 2SD), which is statistically lower than those of low-grade serpentinite (−0.05‰ ± 0.30‰, n = 80, 2SD) and higher-grade chlorite harzburgite (−0.10‰ ± 0.27‰, n = 22, 2SD). This suggests that resolvable Cr isotope fractionation occurs during serpentinite dehydration, which is explained by the variability of Cr isotope behavior in the presence of Cl-bearing fluids at different dehydration stages. No obvious Cr isotope fractionation was found during chlorite harzburgite dehydration, probably related to the limited Cr mobility in a Cl-poor fluid. Other processes, such as melt extraction, external fluid influx and retrograde metamorphism, have negligible effects on the Cr isotope systematics of meta-serpentinites. Fluids released by serpentinite dehydration may have a great effect on the Cr isotope heterogeneity of mantle wedge peridotites and arc magmas.National Key Ramp;D Program of ChinaStrategic Priority Research Program (B) of CAS 2018YFA0702600National Natural Science Foundation of China (NSFC) XDB41000000Fundamental Research Funds for the Central Universities 42073029 41973004CNSAMICIN/AEI D020204FEDER program "Una manera de hacer Europa" PID2022-136471N-B-C21 C22 PID2019-111715GB-I00AEIFSE program "FSE invierte en tu futuro" RYC2018-024363-IJunta de AndaluciaEuropean Union (EU) Postdoc_21_00791European Social Fund (ESF)Junta de Andalucia RNM-131 RNM-37

Strain Localization in Pyroxenite by Reaction-Enhanced Softening in the Shallow Subcontinental Lithospheric Mantle

We report structural evidence of ductile strain localization in mantle pyroxenite from the spinel to plagioclase websterite transition in the Ronda Peridotite (southern Spain). Mapping shows that, in this domain, small-scale shear zones occurring at the base of the lithospheric section are systematically located within thin pyroxenite layers, suggesting that the pyroxenite was locally weaker than the host peridotite. Strain localization is associated with a sudden decrease of grain size and increasing volume fractions of plagioclase and amphibole as a result of a spinel to plagioclase phase transformation reaction during decompression. This reaction also fostered hydrogen extraction (‘dehydroxylation') from clinopyroxene producing effective fluid saturation that catalyzed the synkinematic net-transfer reaction. This reaction produced fine-grained olivine and plagioclase, allowing the onset of grain-size sensitive creep and further strain localization in these pyroxenite bands. The strain localization in the pyroxenites is thus explained by their more fertile composition, which allowed earlier onset of the phase transition reactions. Geothermobarometry undertaken on compositionally zoned constituent minerals suggests that this positive feedback between reactions and deformation is associated with cooling from at least 1000°C to 700°C and decompression from 1·0 to 0·5 GP

High-P metamorphism of rodingites during serpentinite dehydration (Cerro del Almirez, Southern Spain): Implications for the redox state in subduction zones

The transition between antigorite-serpentinite and chlorite-harzburgite at Cerro del Almirez (Betic Cordillera, Southern Spain) exceptionally marks in the field the front of antigorite breakdown at high pressure (~16–19 kbar) and temperature (~650°C) in a paleosubducted serpentinite. These ultramafic lithologies enclose three types of metarodingite boudins of variable size surrounded by metasomatic reaction rims. Type 1 Grandite-metarodingite (garnet+chlorite+diopside+titanite±magnetite±ilmenite) mainly crops out in the antigorite-serpentinite domain and has three generations of garnet. Grossular-rich Grt-1 formed during rodingitization at the seafloor (10 kbar, ~350–650°C, ~FMQ buffer) to influx events of oxidizing fluids (fO ~HM buffer) released by brucite breakdown in the host antigorite-serpentinite. Type 2 Epidote-metarodingite (epidote+diopside+titanite±garnet) derives from Type 1 and is the most abundant metarodingite type enclosed in dehydrated chlorite-harzburgite. Type 2 formed by increasing μSiO (from −884 to −860 kJ/mol) and decreasing μCaO (from −708 to −725 kJ/mol) triggered by the flux of high amounts of oxidizing fluids during the high-P antigorite breakdown in serpentinite. The growth of Grt-4, with low-grandite and high-pyralspite components, in Type 2 metarodingite accounts for progressive reequilibration of garnet with changing intensive variables. Type 3 Pyralspite-metarodingite (garnet+epidote+amphibole+chlorite±diopside+rutile) crops out in the chlorite-harzburgite domain and formed at peak metamorphic conditions (16–19 kbar, 660–684°C) from Type 2 metarodingite. This transformation caused the growth of a last generation of pyralspite-rich garnet (Grt-5) and the recrystallization of diopside into tremolitic amphibole at decreasing fO and μCaO (from −726 to −735 kJ/mol) and increasing μMgO (from −630 to −626 kJ/mol) due to chemical mixing between the metarodingite and the reaction rims. The different bulk Fe/Fe ratios of antigorite-serpentinite and chlorite-harzburgite, and of the three metarodingite types, reflect the highly heterogeneous oxidation state of the subducting slab and likely point to the transfer of localized oxidized reservoirs, such as metarodingites, into the deep mantle.“Ministerio de Economía, Industria y Competitividad” (MINECO), Grant/Award Number: CGL2012-32067, CGL201675224-R; Junta de Andalucía, Grant/ Award Number: RNM-145, P12-RNM3141; Ramón y Cajal, Grant/Award Number: RYC-2012-11314; MINECO, Grant/Award Number: CGL2016-81085-R, PCIN-2015-05

The effect of subduction on the sulphur, carbon and redox budget of lithospheric mantle

Subduction of hydrated lithospheric mantle introduces H O, ferric iron, oxidized carbon and sulphur to the subduction zone system. The fate of these components is poorly known, but is intimately linked to the global geochemical cycles of iron, carbon and sulphur, the genesis of arc-related ore deposits, the temporal evolution of mantle redox state and subduction-related earthquakes and magmatism. thermocalc is used to provide first-order constraints on the effect of subduction zone metamorphism on metamorphic redistribution of iron, carbon, sulphur and water in ultramafic rocks via construction of P−T and T-X(O) pseudosections with open system calculation of the effect of fluid loss. The calculations replicate observed mineral assemblages in high-P to low-T ultramafic rocks at P−T conditions consistent with those suggested by other workers. The results are consistent with open system fluid loss without significant fluid infiltration. Water loss is complete by 850 C, the corresponding depth of fluid loss being consistent with that inferred for earthquakes in subducting slabs. Losses of carbon and sulphur are relatively minor, at around 5 GPa, below the depths of the source zone for arc volcanoes.Oxygen activity for rocks in closed systems that evolve with a fixed redox budget is calculated to change from ΔFMQ −1 at 350 C to over ΔFMQ +3 at 850 C. This result emphasizes the need to consider redox budget as well as oxygen activity when the results of experiments performed at fixed oxygen activity relative to some buffer are interpreted in the context of natural systems. In open systems, devolatilization is calculated to increase the redox budget and oxygen activity of the residue via loss of methane and H S at the brucite-out and serpentine-out reactions respectively. No fluid-induced mechanism for oxidation of sub-arc mantle by transfer of redox budget from hydrated ultramafic lithologies to the overlying sub-arc mantle was identified, although further thermodynamic data on fluid species such as S are required to confirm this

11B-rich fluids in subduction zones: the role of antigorite dehydration in subducting slabs and boron isotope heterogeneity in the mantle

Serpentinites form by hydration of mantle peridotite and constitute the largest potential reservoir of fluid-mobile elements entering subduction zones. Isotope ratios of one such element, boron, distinguish fluid contributions from crustal versus serpentinite sources. Despite 85% of boron hosted within abyssal peridotite being lost at the onset of subduction at the lizardite-to-antigorite transition, a sufficient cargo of boron to account for the composition of island arc magma is retained (c. 7 μg g− 1, with a δ11B of + 22‰) until the down-going slab reaches the antigorite-out isograd. At this point a 11B-rich fluid, capable of providing the distinctive δ11B signature of island arc basalts, is released. Beyond the uniquely preserved antigorite-out isograd in serpentinites from Cerro del Almirez, Betic Cordillera, Spain, the prograde lithologies (antigorite–chlorite–orthopyroxene–olivine serpentinite, granofels-texture chlorite-harzburgite and spinifex-texture chlorite-harzburgite) have very different boron isotope signatures (δ11B = − 3 to + 6‰), but with no significant difference in boron concentration compared to the antigorite-serpentinite on the low P–T side of the isograd. 11B-rich fluid, which at least partly equilibrated with pelagic sediments, is implicated in the composition of these prograde lithologies, which dehydrated under open-system conditions. Serpentinite-hosted boron lost during the early stages of dehydration is readily incorporated into forearc peridotite. This, in turn, may be dragged to sub-arc depths as a result of subduction erosion and incorporated in a mélange comprising forearc serpentinite, altered oceanic crust and pelagic sediment. At the antigorite-out isograd it dehydrates, thus potentially providing an additional source of 11B-rich fluids

Dehydration of subducting slow-spread oceanic lithosphere in the Lesser Antilles

Subducting slabs carry water into the mantle and are a major gateway in the global geochemical water cycle. Fluid transport and release can be constrained with seismological data. Here we use joint active-source/local-earthquake seismic tomography to derive unprecedented constraints on multi-stage fluid release from subducting slow-spread oceanic lithosphere. We image the low P-wave velocity crustal layer on the slab top and show that it disappears beneath 60–100 km depth, marking the depth of dehydration metamorphism and eclogitization. Clustering of seismicity at 120–160 km depth suggests that the slab’s mantle dehydrates beneath the volcanic arc, and may be the main source of fluids triggering arc magma generation. Lateral variations in seismic properties on the slab surface suggest that serpentinized peridotite exhumed in tectonized slow-spread crust near fracture zones may increase water transport to sub-arc depths. This results in heterogeneous water release and directly impacts earthquakes generation and mantle wedge dynamics