The role of brucite in water and element cycling during serpentinite subduction – Insights from Erro Tobbio (Liguria, Italy)

The Erro Tobbio olivine-antigorite serpentinites and associated dehydration veins represent hydrated oceanic mantle rocks that escaped complete dehydration and recycling into the mantle after subduction to ~ 550-600 °C and 2.0-2.5 GPa. These rocks thus offer valuable insights into the petrological evolution of a slice of hydrated oceanic mantle and the geochemical cycling down to intermediate subduction zone depths. Our study emphasises the role of brucite upon rock-buffered hydration and subduction dehydration employing bulk and in situ chemical data sets combined with petrology. Bulk rock data reveal a coherent mantle peridotite slice affected by variable melt depletion and refertilisation. Subsequent fluid-rock interaction stages proceeded isochemically with respect to SiO2, i.e., without significant SiO2 enrichment characteristic for hydrothermal ocean floor serpentinisation. Relicts of low-T mesh textures after olivine and preservation of precursor mineral and low-T hydration geochemical features indicate a lack of subsequent fluid and metamorphic overprinting, even on scales of tens of micrometres. Fluid-mobile element enrichments are modest with exceptions for B and W. Enrichment signatures of U/Cs << 1 and Rb/Cs of 4-26 are characteristic of shallow forearc hydration within or atop the slab by fluids derived from breakdown of clays or first dehydration of altered oceanic crust with a subordinate sedimentary pore fluid component. Overall, the geochemical and petrological changes of the Erro Tobbio peridotites during fluid-rock interactions were rockbuffered, in contrast to fluid-buffered hydration accompanied with significant SiO2 metasomatism at, e.g., mid ocean ridges. Silica-neutral rock-buffered serpentinisation resulted in prominent brucite formation upon olivine hydration. In absence of excess SiO2, subsequent serpentine transformation of chrysotile/lizardite to antigorite likely produced even more brucite. Rock-buffered fluid-rock interactions thus provide a mechanism for stabilising brucite in subduction zone serpentinites, presumably along hydration fronts and within deeper sections of the oceanic lithospheric mantle. Finally, brucite + antigorite dehydration produced up to 40 vol. % of metamorphic olivine and prominent olivine + Ti-clinohumite + magnetite vein networks at temperatures < 550-600 °C, prior to complete antigorite breakdown. Wall rocks released alkali elements, B, Cr, As, Sb, and Ba into the dehydration fluids, along with substantial Sr, REE and HFSE redistribution into vein minerals

Petrology and Trace Element Budgets of High-pressure Peridotites Indicate Subduction Dehydration of Serpentinized Mantle (Cima di Gagnone, Central Alps, Switzerland)

At Cima di Gagnone, garnet peridotite and chlorite harzburgite lenses within pelitic schists and gneisses correspond to eclogite-facies breakdown products of hydrated peridotites and are suitable for studying dehydration of serpentinized mantle. Thermobarometry and pseudosection modelling yield peak temperatures of 750-850°C and pressures <3 GPa. The minimum temperature recorded by the garnet peridotite corresponds to the maximum conditions experienced by the chlorite harzburgite, suggesting that these rocks recrystallized cofacially at ∼800°C. Alternatively, they might have decoupled during subduction, as achieved in tectonically active plate interface boundaries. The major and rare earth element (REE) variability of the peridotites was mostly acquired during pre-subduction mantle evolution as a result of partial melting and reactive melt flow. The ultramafic suite is also characterized by fluid-mobile element enrichments (B, Pb, As, Sb, Cs, Li, U, Be), which confirm derivation from variably serpentinized protoliths. Similarity in the U, Pb, B, Li and Sr contents of the Gagnone peridotites to present-day oceanic serpentinites suggests that these elements were partly taken up during initial serpentinization by seawater-derived fluids. Positive Be, As and Sb anomalies suggest involvement of fluids equilibrated with crustal (metasedimentary) reservoirs during subsequent subduction metamorphism and peridotite entrainment in (meta)sediments. Fluid-mobile element enrichment characterizes all peak eclogitic minerals, implying that multiple hydration events and element influx pre-dated the eclogite-facies dehydration. Peak anhydrous minerals retain B, Li, As and Sb concentrations exceeding primitive mantle values and may introduce geochemical anomalies into the Earth's mantle. The relatively low contents of large ion lithophile elements and light REE in the Gagnone peridotites with respect to much higher enrichments shown by metasomatized garnet peridotite pods hosted in migmatites (Ulten Zone, Eastern Alps) suggest that the crustal rocks at Gagnone did not experience partial melting. The Gagnone garnet peridotite, despite showing evidence for chlorite dehydration, retains significant amounts of fluid-mobile elements documenting that no partial melting occurred upon chlorite breakdown. We propose that the Gagnone ultramafic rocks represent a prime example of multi-stage peridotite hydration and subsequent dehydration in a plate interface settin

OH-bearing planar defects in olivine produced by the breakdown of Ti-rich humite minerals from Dabie Shan (China)

The partial breakdown of Ti-chondrodite and Ti-clinohumite during exhumation from ultra-high pressure to amphibolite facies conditions in garnet-pyroxenites from Dabie Shan (China) produces coronas of olivine coexisting with ilmenite blebs. Fourier transform infrared (FTIR) spectra of this newly formed olivine exhibit absorption bands in the hydroxyl-stretching region. Two intense peaks were observed at 3,564 and 3,394 cm-1, identical in energy to peaks in Ti-clinohumite. Transmission electron microscopy (TEM) of the same olivine domains revealed the presence of a complex (001) planar intergrowth. These interlayers have a 1.35 nm repeat distance, which is characteristic of clinohumite. Such interlayers are also enriched in Ti with respect to the adjacent olivine as shown by energy dispersive spectrometry. The combined evidence from FTIR spectroscopy and TEM indicates that OH is incorporated along Ti-clinohumite planar defects. This study provides evidence that the nominally anhydrous phase olivine may contain OH as a humite-type defect beyond the breakdown of the hydrous humite minerals and confirms earlier suggestions that Ti plays a key role in OH incorporation in mantle olivine. We suggest that olivine containing Ti-clinohumite defects is an important phase for water transport in subduction zones and for the storage of water in cold subcontinental mantle. However, these defects are unlikely to be stable in hotter parts of the oceanic mantle such as where basaltic magmas are generated

Fluid‐mediated mass transfer between mafic and ultramafic rocks in subduction zones

© The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Codillo, E., Klein, F., Dragovic, B., Marschall, H., Baxter, E., Scambelluri, M., & Schwarzenbach‬, E. Fluid‐mediated mass transfer between mafic and ultramafic rocks in subduction zones. Geochemistry Geophysics Geosystems, 23, (2022): e2021GC010206, https://doi.org/10.1029/2021gc010206.Metasomatic reaction zones between mafic and ultramafic rocks exhumed from subduction zones provide a window into mass-transfer processes at high pressure. However, accurate interpretation of the rock record requires distinguishing high-pressure metasomatic processes from inherited oceanic signatures prior to subduction. We integrated constraints from bulk-rock geochemical compositions and petrophysical properties, mineral chemistry, and thermodynamic modeling to understand the formation of reaction zones between juxtaposed metagabbro and serpentinite as exemplified by the Voltri Massif (Ligurian Alps, Italy). Distinct zones of variably metasomatized metagabbro are dominated by chlorite, amphibole, clinopyroxene, epidote, rutile, ilmenite, and titanite between serpentinite and eclogitic metagabbro. Whereas the precursor serpentinite and oxide gabbro formed and were likely already in contact in an oceanic setting, the reaction zones formed by diffusional Mg-metasomatism between the two rocks from prograde to peak, to retrograde conditions in a subduction zone. Metasomatism of mafic rocks by Mg-rich fluids that previously equilibrated with serpentinite could be widespread along the subduction interface, within the subducted slab, and the mantle wedge. Furthermore, the models predict that talc formation by Si-metasomatism of serpentinite in subduction zones is limited by pressure-dependent increase in the silica activity buffered by the serpentine-talc equilibrium. Elevated activities of aqueous Ca and Al species would also favor the formation of chlorite and garnet. Accordingly, unusual conditions or processes would be required to stabilize abundant talc at high P-T conditions. Alternatively, a different set of mineral assemblages, such as serpentine- or chlorite-rich rocks, may be controlling the coupling-decoupling transition of the plate interface.M. Scambelluri acknowledges the Italian Ministry of Research MUR for granting the PRIN project n. 2017ZE49E7. This research was funded by NSF-OISE (Office of International Science & Engineering, Petrology & Geochemistry) PIRE, Award #1545903, and the WHOI Ocean Ventures Fund

Fluid-mediated mass transfer between mafic and ultramafic rocks in subduction zones: Insights from the high-pressure Voltri Massif (Ligurian Alps, Italy)

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U-Pb dating of magmatic zircon and metamorphic baddeleyite in the Ligurian eclogites (Voltri Massif, Western Alps)

U-Pb geochronology with ion microprobe (SHRIMP) analysis has been carried out on eclogite-facies rocks of the Beigua Unit, an ophiolitic slice of the Voltri Massif, Western Alps. The investigated samples are eclogites and high-pressure metasomatic rocks (metarodingites and centimetre-sized Ti-clinohumite-bearing dykes). Zircon contained in an eclogitic metagabbro and a metarodingite preserves magmatic zoning patterns and trace element compositions. The zircon ages of 160 \ub1 1 and 161 \ub1 3 Ma are interpreted to date the crystallization of the gabbroic protoliths. Ti-clinohumite dykes in the same unit contain baddeleyite crystals in textural equilibrium with Ti-clinohumite, diopside, chlorite and magnetite, which form the eclogite-facies assemblage in these rocks. Baddeleyite also contains inclusions of such minerals, indicating its formation at high pressure. The baddeleyite has cathodo-luminescence intensity and chaotic patterns similar to metamorphic zircon. It contains a significant amount of Hf (1.3-1.7 wt% , traces of Ti, Y, Nb, Ta, REE, U and Th. Its chondrite-normalised trace element pattern has strong enrichment in middle REE, positive Ce-anomaly and small negative Eu-anomaly. This represents the first report of baddeleyite formed during regional metamorphism, and suggests that this mineral could (re)crystallize easier than zircon under low-temperature, high-pressure conditions. The age of the baddeleyite is interpreted as likely dating the eclogite-facies metamorphism in the Beigua Unit at 33.6 \ub1 1.0 Ma. This age is very close to the Early Oligocene age of the overlying Tertiary continental breccias and conglomerates, which contains clasts of high-pressure rocks. This sedimentary record, which is unique for Alpine high-pressure units, is direct evidence of fast exhumation of the Beigua eclogites. The young age for the HP metamorphism of the Beigua ophiolite makes a revision of either the palaeogeography prior to collision, or of the subduction setting in the entire region, necessary

Deep fluids in subduction zones

The fluid inclusions preserved in high and ultrahigh pressure rocks provide direct information on the compositions of fluid phases evolved during subduction zone metamorphism, and on fluid-rock interactions occuring in such deep environments. Recent experiments and petrologic studies of eclogite-facies rocks demonstrate that stability of a number of hydrous phases in all rock systems allows fluid transport into the mantle sources of are magmas, as well as into much deeper levels of the Earth's mantle. In eclogite-facies rocks, the presence of large ion lithophile elements (LILE) and light rare earths (LREE)-bearing hydrous phases such as epidote and lawsonite, together with HFSE repositories as rutile and other Ti-rich minerals, controls the trace element budget of evolved fluids and fluid-mediated cycling of slab components into the overlying mantle. Studies of fluid inclusions in eclogite-facies terrains suggest that subduction mainly evolves aqueous solutions, melts being produced only locally. Eclogite-facies rocks diffusely record processes of fluid-melt-rock interactions that exerted considerable control on the element and volatile budget of subduction fluids. Trace element fractionation during such interactions needs to be tested and quantified in more detail to achieve the ultimate compositions actually attained by fluids leaving off the slab. Variably saline inclusions with minor CO2 and N2 are trapped in rock-forming high pressure minerals: Brines with up to 50% by weight dissolved solute are diffusely found in veins. The latter inclusions are residues after fluid-rock interactions and deposition of complex vein mineralogies: this evidence suggests increased mineral solubility into the fluid and formation, at a certain stage, of silicate-rich aqueous solutions whose geochemical behaviour and transport capacity can approach that of a melt phase. This is supported by experimental work showing high solubility of silicate components in fluids at high pressures. However, natural examples of inclusions trapping such a fluid and quantitative analyses of its major and trace element composition are not yet available. Fluids in high and very high pressure rocks do not move over large scales and the channelways of fluid escape from the slab are not yet identified. This suggests that only part of the slab fluid is lost and returned to the surface via magmatism: the remaining trapped fraction being subducted into deeper levels of the upper mantle, to renew its budget of substances initially stored in the exosphere

Boron isotope evidence for shallow fluid transfer across subduction zones by serpentinized mantle

Serpentinites formed by alteration of oceanic and forearc mantle are major volatile and fl uid-mobile element reservoirs for arc magmatism, though direct proof of their dominance in the subduction-zone volatile cycles has been elusive. Boron isotopes are established markers of fl uid-mediated mass transfer during subduction. Altered oceanic crust and sediments have been shown to release in the subarc mantle 11B-depleted fl uids, which cannot explain 11B enrichment of many arcs. In contrast to these crustal reservoirs, we document high 11B values retained in subduction-zone Alpine serpentinites. No 11B fractionation occurs in these rocks with progressive burial: the released 11B-rich fl uids uniquely explain the elevated 11B of arc magmas. B, O-H, and Sr isotope systems indicate that serpentinization was driven by slab fl uids that infi ltrated the slab-mantle interface early in the subduction history