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1. Quantifying the volume increase and chemical exchange during serpentinization

   https://doi.org/10.1130/G47289.1  

   Klein, Frieder; Le Roux, Véronique (March 2020, Geology)

   Quantifying the concurrent changes in rock volume and fluid composition during serpentinization remains a major challenge in assessing its physicochemical effects during continental rifting, seafloor spreading, and subduction. Here we conducted a series of 11 hydrothermal laboratory experiments where cylindrical cores of natural dunite, harzburgite, and pyroxenite were reacted with an aqueous solution at 300 °C and 35 MPa for up to 18 months. Using three-dimensional microcomputed tomography and thermogravimetry, we show that rock volume systematically increased with time and extent of reaction, leading to a volume increase of 44% (±8%) in altered rock domains after 10–18 months of serpentinization. The volume expansion was accompanied by Mg-Ca exchange between fluid and rock, while Fe and Si were largely conserved. We find that the protolith composition (olivine/orthopyroxene ratio) plays a significant role in controlling the fluid chemistry and the proportions of hydrous secondary minerals during serpentinization. Agreement between alteration mineralogy, composition of reacting fluids, and measured volume changes suggests that serpentinization under static conditions is a volume-increasing process in spite of demonstrable mass transfer. Volume expansion implies an increased water carrying capacity and buoyancy force of serpentinite per unit mass of protolith, while Mg-Ca exchange during serpentinization may affect the Mg/Ca ratio of seawater on Earth and possibly other ocean worlds. 

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2. Effect of Water‐Rock Ratio on the Stable Isotope Record of Fluid‐Rock‐Deformation Interactions in Detachment Shear Zone

   https://doi.org/10.1029/2023GC011340  

   Gottardi, Raphaël; Mire, Camron; Davis, Niya; Casale, Gabriele (May 2024, Geochemistry, Geophysics, Geosystems)

   Abstract Oxygen and hydrogen stable isotope analyses of quartz and muscovite veins from the footwall of the Raft River detachment shear zone (Utah) provide insight into the hydrology and fluid‐rock interactions during ductile deformation. Samples were collected from veins containing 90%–100% quartz with orientations either at a high angle or sub‐parallel to the surrounding quartzite mylonite foliation. Stable isotope analysis was performed on 10 samples and compared with previous quartzite mylonite isotope data sets. The results indicate that the fluid present during deformation of the shear zone was meteoric in origin, with a δ²H value of approximately −100‰ and a δ¹⁸O value of approximately −13.7‰. Oxygen stable isotope O¹⁸O depletion correlates with the muscovite content of the analyzed rocks. Many of the analyzed samples in this and other studies show an apparent lack of equilibrium between the oxygen and hydrogen isotope systems, which can be explained by hydrogen and oxygen isotope exchange at varying fluid‐rock ratios. Our results suggest that the Raft River detachment shear zone had a low static fluid‐rock ratio (<0.1), yet experienced episodic influxes of fluids through semi‐brittle structures. This fluid was then expelled out into the surrounding mylonite following progressive shearing, causing further¹⁸O‐depletion and fluid‐related embrittlement. 

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3. Record of de-serpentinization and re-serpentinization of an exhumed slab sliver: Implications for fluid circulation in subduction zones

   https://doi.org/10.1016/j.epsl.2025.119213  

   Donoso-Tapia, Damián; Flores, Kennet E; Martin, Celine; Hull, Sarah; Hernández-Uribe, David; Gazel, Esteban (January 2025, Earth and Planetary Science Letters)

   Fluid release associated with serpentinite dehydration (de-serpentinization) during subduction plays a key role in fundamental geological processes such as element transport and recycling, seismicity, and arc magmatism. Although the importance of these fluids is well-known, evidence of de-serpentinization remains scarce in the rock record. Here, we investigated the effects of de-serpentinization and fluid circulation in exhumed metaperidotites from the Raspas Complex (Ecuador). This Early Cretaceous complex records warm subduction (∼13.5 °C/km) and has been hypothesized to represent a coherent slab sliver that preserves the mantle-crust contact (moho) between eclogite-facies metaperidotites and the corresponding crustal section. Petrological observations reveal that titanian-clinohumite-bearing metadunites and banded metaperidotites underwent de-serpentinization after reaching peak pressure–temperatures (P–T) of ∼1.3–1.6 GPa and 620–650 °C. The peak paragenesis is partially obscured by a strong retrograde overprint, driven by crust-derived metamorphic fluids (δ11B ∼ -6 to +8 ‰) that infiltrated at varying fluid/rock ratios, triggering the re-serpentinization of metaperidotites during exhumation (P < 1.3 GPa and 320–400 °C). Thermodynamic forward modeling reveals that fluid release in the Raspas paleo-subduction zone is controlled by brucite breakdown and de-serpentinization, which occur at depths of 25–30 km and ∼50 km, respectively, accounting for a total of up to 10 wt. % H2O of water stored in the rock. Comparatively, dehydration of the crustal section, albeit a minor component, promotes enhanced fluid circulation between 25 and 45 km. During exhumation, circulating crust-derived metamorphic fluids heavily metasomatized the ascending slab sliver and effectively modified its geochemical signature. The depth range of the dehydration reactions overlap the depth of non-volcanic tremors and slow-slip events in warm, active subduction zones worldwide (25–65 km). Thus, the Raspas Complex offers an in-situ window into the fluids responsible for triggering these seismic events. 

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4. Lawsonite and Garnet Oxygen Isotope Record of Fluid‐Rock Interaction During Subduction

   https://doi.org/10.1029/2023GC011389  

   Kang, Patricia; Martin, Laure_A_J; Vitale_Brovarone, Alberto; Whitney, Donna_L (April 2024, Geochemistry, Geophysics, Geosystems)

   Abstract During the subduction of an oceanic plate, fluids are released from metabasaltic crust, metasediment, and serpentinite under high‐pressure/low‐temperature conditions. Although some fluids may eventually leave the slab, some participate in metamorphic reactions within the slab during subduction and exhumation. To identify fluid sources and other controls influencing mineral composition, we report the in situ‐measured δ¹⁸O of lawsonite and garnet in blueschist‐ to eclogite‐facies rocks from 10 subduction zones that represent various field settings, including mélanges, structurally coherent terranes, and an eclogite xenolith derived from a subducted plate. Lawsonite records distinct δ¹⁸O depending on the host rock type and other rock types that were fluid sources during lawsonite growth. In general, lawsonite in metabasalt (7.6 ± 0.2–14.8 ± 1.1‰) is isotopically lighter than in metasediment (20.6 ± 1.4–24.1 ± 1.3‰) but heavier than in metagabbro (4.0 ± 0.4–7.9 ± 0.3‰). The extent of δ¹⁸O fractionation was evaluated for lawsonite–fluid and lawsonite–garnet pairs as a function of temperature (T). Results demonstrate that variations of >1.7‰ in lawsonite and >0.9‰ in garnet are not related to changingT. More likely, the relative contributions of fluids derived from isotopically heavier lithologies (e.g., sediments) versus lighter lithologies (e.g., ultramafic rocks) are the major control. Monte Carlo simulations were performed to investigate the sources of metasomatic fluids and the water/rock ratio that formed lawsonite‐bearing metasomatite. Results indicate that δ¹⁸O_Lwsand δ¹⁸O_Grtrecord interactions with fluids sourced from diverse lithologies (sediment, serpentinite), further supporting that δ¹⁸O_Lwsis a useful indicator of subduction fluid‐rock interactions. 

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5. Reaction-Induced Porosity in an Eclogite-Facies Vein Selvage (Monviso Ophiolite, W. Alps): Textural Evidence and In Situ Trace Elements and Sr Isotopes in Apatite.

   https://doi.org/10.1093/petrology/egac128  

   Hoover, William F; Penniston-Dorland, Sarah; Piccoli, Philip; Kylander-Clark, Andrew (January 2023, Journal of Petrology)

   Porosity generated during fluid–rock reaction can facilitate fluid transport and metasomatism in low permeability high-pressure metamorphic rocks. Evidence for reaction-induced porosity is found in an eclogite-facies clinopyroxene + apatite vein in an undeformed eclogitized Fe–Ti metagabbro from the Monviso Ophiolite (W. Alps) with a distinct garnet-rich selvage. Vein-forming fluids were sourced from adjacent metagabbros and reaction with the host rock removed Ca and P from the selvage and added Fe, REE, Pb and Cr. Textures at the selvage–host rock interface and in the host rock record local heterogeneity in reactivity and porosity during metasomatism linked to variable initial lawsonite abundance. These features reflect a hierarchy of pervasive-to-channelized porosity structures that facilitated widespread metasomatism of the host rock. Development of this metasomatic system in response to locally derived fluids suggests large-scale externally derived fluid transport is not required to drive extensive fluid–rock exchange. The production of porosity during metasomatic reactions could be important in facilitating further fluid–rock reaction and fluid transport in subducting slabs where permeability is low. 

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