Subduction-zone Metamorphism Research Articles

The distribution and abundance of halogens in eclogites: An in situ SIMS perspective of the Raspas Complex (Ecuador)

AbstractWe present in situ secondary ion mass spectrometry (SIMS) and electron microprobe analyses of coexisting garnet, omphacite, phengite, amphibole, and apatite, combined with pyrohydrolysis bulk-rock analyses to constrain the distribution, abundance, and behavior of halogens (F and Cl) in six MORB-like eclogites from the Raspas Complex (Southern Ecuador). In all cases concerning lattice-hosted halogens, F compatibility decreases from apatite (1.47–3.25 wt%), to amphibole (563–4727 μg/g), phengite (610–1822 μg/g), omphacite (6.5–54.1 μg/g), and garnet (1.7–8.9 μg/g). The relative compatibility of Cl in the assemblage is greatest for apatite (192–515 μg/g), followed by amphibole (0.64–82.7 μg/g), phengite (1.2–2.1 μg/g), omphacite (<0.05–1.0 μg/g), and garnet (<0.05 μg/g). Congruence between SIMS-reconstructed F bulk abundances and yield-corrected bulk pyrohydrolysis analyses indicates that F is primarily hosted within the crystal lattice of eclogitic minerals. However, SIMS-reconstructed Cl abundances are a factor of five lower, on average, than pyrohydrolysis-derived bulk concentrations. This discrepancy results from the contribution of fluid inclusions, which may host at least 80% of the bulk rock Cl. The combination of SIMS and pyrohydrolysis is highly complementary. Whereas SIMS is well suited to determine bulk F abundances, pyrohydrolysis better quantifies bulk Cl concentrations, which include the contribution of fluid inclusion-hosted Cl. Raspas eclogites contain 145–258 μg/g F and at least 7–11 μg/g Cl. We estimate that ~95% of F is retained in the slab through eclogitization and returned to the upper mantle during subduction, whereas at least 95% of subducted Cl is removed from the rock by the time the slab equilibrates at eclogite facies conditions. Our calculations provide further evidence for the fractionation of F from Cl during high-pressure metamorphism in subduction zones. Although the HIMU (high U/Pb) mantle source (dehydrated oceanic crust) is often associated with enrichments in Cl/K and F/Nd, Raspas eclogites show relatively low halogen ratios identical within uncertainty to depleted MORB mantle (DMM). Thus, the observed halogen enrichments in HIMU ocean island basalts require either further fractionation during mantle processing or recycling of a halogen-enriched carrier lithology such as serpentinite into the mantle.

Среднеглубинные землетрясения и связь сейсмичности зоны субдукции с метаморфизмом и глубинным флюидным режимом для Cеверного острова Новой Зеландии

Среднеглубинные землетрясения и связь сейсмичности зоны субдукции с метаморфизмом и глубинным флюидным режимом для Cеверного острова Новой Зеландии

Metamorphism, fluid behavior and magmatism in oceanic subduction zones

Based on the updated results of experimental petrology and phase equilibria modelling and combined with the available thermal structure models of subduction zones, this paper presents an overview on the dehydration and melting of basic, sedimentary and ultrabasic rocks that occur in the different stages during oceanic subduction processes and their influences on magmatism above subduction zones. During the subduction at the forearc depth of the basic and ultrabasic rocks from most oceanic slabs can release very small amounts of water, and significant dehydration may occur in the slab superficial sediments. Strong dehydration occurs in both basic and ultrabasic rocks during subduction at the subarc depth of 90–200 km. For example, more than 90% water in basic rocks is released by the successive dehydration of chlorite, glaucophane, talc and lawsonite in the subarc depths. This is diversely in contrast to the previous results from synthetic experiments. Ultrabasic rocks may undergo strong dehydration through antigorite, chlorite and phase 10 A at the subarc depth of 120–220 km. However, sediments can contribute minor fluids at the subarc depth, one main hydrous mineral in which is phengite (muscovite). It can stabilize to ~ 300 km depth and transform into K-hollandite. After phengite breaks down, there will be no significant fluid release from oceanic slab until it is subducted to the mantle transition zone. In a few hot subduction zones, partial melting (especially flux melting) can occur in both sediments and basic rocks, generating hydrous granitic melts or supercritical fluids, and in carbonates-bearing sediments potassic carbonatite melts can be generated. In a few cold subduction zones, phase A occurs in ultrabasic rocks, which can bring water deep into the transition zone. The subducted rocks, especially the sediments, contain large quantities of incompatible minor and trace elements carried through fluids to greatly influence the geochemical compositions of the magma in subduction zones. As the geothermal gradients of subduction zones cannot cross the solidi of carbonated eclogite and peridotite during the subarc subduction stage, the carbonate minerals in them can be carried into the deep mantle. Carbonated eclogite can melt to generate alkali-rich carbonatite melts at >400 km depth, while carbonated peridotite will not melt in the mantle transition zone below a subduction zone.

The formation of graphite-rich eclogite vein in S.W. Tianshan (China) and its implication for deep carbon cycling in subduction zone

The balance of carbon flux in subduction zones is critical to the deep carbon cycle. Carbonate-bearing lithologies are the major carbon carriers transported from Earth's surface into its interior at subduction zones. Recently, a number of studies have showed that carbon can be released from the subducting slab through metamorphic decarbonation and dissolution into C-H-O fluids. However, the evolution of the released C-H-O fluids during subduction-zone metamorphism is ambiguous and poorly explored. In this study, we found graphite-rich eclogite veins (VE) in the carbonated eclogites from the Southwestern (S.W.) Tianshan subduction zone. The observed graphite with high crystallinity and graphite-bearing fluid inclusions indicate the fluid-deposited origin. Phase equilibrium modelling for the host carbonated-eclogite (HE) in a closed system indicates that it has experienced a retrograde P-T path involving decompression with heating from 26.5 kbar at 487 °C to 20.6 kbar at 565 °C. The calculation showed that about 0.92–2.03 wt% of CO2 (0.25–0.55 g C per 100 g rock) could be released from the carbonated eclogite during its exhumation process, which is enough to provide the carbon source for graphite precipitation in the VE. Combined with petrological and isotopic results, we suggest that the graphites in the VE were precipitated from carbon-bearing fluids derived from the carbonated eclogites during exhumation metamorphism. The overall redox reaction is: FeO (in silicate, Grt, Omp or Gln) + FeS + (H2O + CO2) (released from Lws and Dol) → Fe2O3 (in Ep, Andradite or Hematite) + C (graphite) + SO42− + HCO3– + CO32−. Mass balance calculation indicates that carbonates could also be re-precipitated in the VE during fluid-rock interaction, in addition to the graphite precipitation. The finding of fluid-deposited graphite in the carbonated eclogites provides new insights into the fate of carbonic fluids formed in the subducted oceanic crust. We suggest that carbonic fluids formed in the carbonated eclogites by decarbonation or carbonate dissolution may also precipitate abiotic graphite or carbonates under favorable conditions during their migration in addition to the commonly recognized transportation to the mantle wedge.

Episodic Fluid Action in Chinese Southwestern Tianshan HP/UHP Metamorphic Belt: Evidence from U–Pb Dating of Zircon in Vein and Host Eclogite

Fluid plays a key role in metamorphism and magmatism in subduction zones. Veins in high-pressure (HP) to ultrahigh-pressure (UHP) rocks are the products of fluid–rock interactions and can thus provide important constraints on fluid processes in subduction zones. In this study, we present an integrated study of zircon in situ U–Pb dating, trace element and mineral inclusion analysis for a complex vein and its host eclogite in the southwestern Tianshan UHP terrane, aiming to decipher the episodic fluid action during slab subduction and exhumation. Both zircon in eclogite and vein have euhedral, prismatic morphology similar to those crystallized from metamorphic fluid. Zircon in eclogite shows core–rim structures with distinct bounds and mineral inclusions. Zircon in the vein shows sector zoning or weak zoning, with bright rims around most zircon grains, which suggests recrystallization of the zircon crystals after their formation and multiple evolution of the vein. Eclogite zircon rims yield a weighted mean of 311 ± 3 Ma and cores yield a range from 413 ± 4 to 2326 ± 18 Ma, respectively. Vein zircon yields four groups of age (~355 Ma, ~337 Ma, ~315 Ma, and ~283 Ma), which date four episodes of fluid flow involving zircon growth. The first two groups of age may represent prograde epidote–amphibolite facies and amphibolite/blueschist facies metamorphism stage, respectively. The third group is similar to that of eclogite zircon rims, which is thought to date the eclogitic facie metamorphism (320–305 Ma), and the fourth group dates a later retrograde metamorphism after greenschist facies. The vein-forming fluid system was supposed to be an open system indicated by trace element of vein zircon and mineral assemblage of the vein. The coexistence of rutile, zircon, and garnet in prograde vein and the heavy rare earth elements (HREE) enrichment characteristic of vein zircon suggest that the vein-forming fluid are enriched in high field strength elements (HFSE) and HREE, and such fluid could be formed under low P–T conditions.

Fluorine partitioning between humite-group minerals and aqueous fluids: implications for volatile storage in the upper mantle

Phase equilibrium experiments were performed in the MgO–SiO2–H2O system, along with fluorine (MSH + F), at conditions between 800–1000 °C and 2.0–2.5 GPa to constrain the solubility of fluorine in humite-group minerals and to determine fluorine partitioning between humite-group minerals and aqueous fluid. Fluorine solubility in humite-group minerals ranges between ~ 1 and 11 wt% F and is dependent on the salinity of the fluid (~ 0.2–3.5 wt% F), indicating that humite-group minerals have exceedingly high saturation limits for F and that a full solid solution between F− and OH− is possible within the crystal structure. Raman spectroscopy reveals the preferential ordering of F, promoting the formation of a stable OH–F bond. Mineral-fluid partition coefficients are always greater than unity, with average coefficients of DFclinohumite/fluid = 3, DFhumite/fluid = 2, DFchondrodite/fluid = 4, and DFnorbergite/fluid = 4. Partition coefficients are independent of pressure or temperature, but decrease with increasing fluid salinity. Fluorine is, therefore, highly soluble and compatible within this group of ultramafic mantle minerals. High solubility and mineral-fluid partition coefficients, together with wide stability fields in pressure and temperature space, demonstrate that humite-group minerals are potential storage sites for F, and by extension H2O, during subduction. Upon the breakdown of less stable hydrous and/or fluorine-rich phases during lower grades of subduction zone metamorphism, fluorine may redistribute into phases such as humite-group minerals and be transported beyond the volcanic arc and to the upper mantle.

Evolution of serpentinite from seafloor hydration to subduction zone metamorphism: Petrology and geochemistry of serpentinite from the ultrahigh pressure North Qaidam orogen in northern Tibet

Serpentinite from the North Qaidam ultrahigh pressure metamorphic belt in northern Tibet is studied to provide insight into petro-geochemical evolution of serpentinite from seafloor hydration to subduction zone metamorphism. The North Qaidam serpentinite can be divided into undeformed lizardite serpentinite that was not severely overprinted during subduction and deformed antigorite serpentinite that was well recrystallized during subduction. Petrological and geochemical analyses demonstrate that the serpentinite was originally melt-percolated refractory abyssal harzburgite. Considering the local geodynamic setting, it is inferred that the serpentinite probably originated from the oceanic lithosphere that subducted before continental subduction. Relatively uniform low δ18O (4.0‰–4.5‰) of the antigorite serpentinite indicates high temperature hydrothermal alteration of protolith harzburgite by seawater. In contrast, much lower δ18O (0.6‰–2.7‰) of the lizardite serpentinite is ascribed to exchange with meteoric water at the Earth’s surface. Relict serpentinization textures are well preserved in the lizardite serpentinite, with reactions of olivine to lizardite and magnetite, pyroxenes to talc, tremolite, and lizardite, and spinel to chromite and chlorite. The replacement of lizardite by antigorite during subduction mostly initiates along grain boundaries and interconnecting veinlets, implying fluid-assisted transformation of lizardite into antigorite. Partial decomposition of antigorite produces magnesian secondary olivine in the antigorite serpentinite, while direct breakdown of metastable lizardite generates ferroan secondary olivine in the lizardite serpentinite. The serpentinite is enriched in fluid-mobile elements, with U primarily accumulated during seafloor alteration and alkalis notably introduced by sedimentary fluids at bending faults or in accretionary wedge. Infiltration by fluids equilibrated with sediments is also supported by highly elevated 87Sr/86Sr of the serpentinite. Moreover, 87Sr/86Sr of the antigorite serpentinite (0.710649–0.713996) is higher than that of the lizardite serpentinite (0.707184–0.708502), which implies more intense interaction of sedimentary fluids with the former than the latter. However, the lizardite serpentinite contains more alkalis and less U than the antigorite serpentinite, which indicates that large proportions of alkalis were lost during partial dehydration of serpentinite, while U was not released.

A revised petrological model for subducted oceanic crust: Insights from phase equilibrium modelling

AbstractMany geological and geodynamical studies of metamorphism in subduction zones have relied upon worldwide compilations of modelled slab‐top pressure–temperature (P–T) conditions, although recent evaluation of such data sets suggests that these predictions are ~100–300°C colder at any given pressure than the conditions recorded by exhumed metamorphic rocks. As such, geochemical, petrological and geophysical interpretations formulated using such ‘cold’ assumptions may be subject to error and uncertainty. Here, we apply thermodynamic phase equilibrium calculations to forward‐model how phase assemblages, the P–T conditions of key devolatilization reactions and the effect of densification with depth vary for typical mid‐ocean ridge basalt (MORB) along these newly defined ‘hotter’ subduction zone geotherms for cold, warm and average environments. The depth and extent of devolatilization of MORB is strongly dependent on the geotherm along which the oceanic crust subducts. At the onset of subduction along a warm geotherm, metabasites contain ~3 wt% H2O and release ~45% of this fluid in a single pulse at ~20 km, correlating with chlorite and epidote breakdown. Below these depths, metamorphosed MORB will dehydrate incrementally due to gradual amphibole breakdown, becoming almost completely dehydrated at ~70 km. Oceanic crust subducting along an average geotherm will contain ~3.5 wt% of H2O at the onset of subduction and will release ~40% of the bulk‐rock H2O in two fluid pluses occurring at ~30 and 50 km, correlating with chlorite breakdown. Below these depths, gradual dehydration of ~50% of the bulk‐rock H2O due to amphibole breakdown leads to near‐complete dehydration at ~80 km. By contrast, in cold subduction zones, metamorphosed MORB will typically be H2O‐undersaturated and will dehydrate gradually at different depths, transporting ~0.6 wt% H2O to sub‐arc depths. As the volume of fluid released via these dehydration reactions differs strongly between cold, average and warm scenarios, different degrees of serpentinization of the mantle forearc are expected worldwide and thus, the efficacy of buoyancy‐driven exhumation should vary strongly in space and time. Metabasites subducting along a warm and average geotherm will liberate most of the fluids at shallower depths, suggesting that these lithologies might preferentially exhume, yet MORB subducting along cold geotherms will not dehydrate until greater depths, inhibiting its return to the surface. Critically, while we show that metabasites formed along warmer geotherms are denser than metabasites from colder geotherms at any equivalent depth, buoyancy‐driven exhumation provoked by fluids plays a notably more important role in exhumation potential than the overall bulk‐rock ‘metamorphic’ density. Furthermore, we show that lawsonite does not stabilize in average and warmer subduction zones, which provides a simple but important solution to the mismatch between its predicted abundance in experiments and its rarity in nature and argues against its use as a reliable petrogenetic indicator of subduction throughout deep geological time, as has been suggested by some recent studies.

Mafic whole-rock geochemistry and neodymium isotopes, Green Mountain and Rowe/Prospect Rock slices, Vermont Appalachians

Mafic rocks containing sodic-calcic amphibole in the Green Mountain slice (GMS) and Rowe/Prospect Rock slice (R/PRS), Vermont Appalachians were originally subalkaline basalts emplaced as melts during Neoproterozoic rifting of Rodinia that led to the formation of the Iapetus Ocean basin. Relatively high degrees of partial melting of asthenosphere that was highly depleted in incompatible elements produced R/PRS magma(s), which may have been contaminated locally by continental crust and/or fluids. Trace element chemistry suggests that mafic bodies from different locations in the R/PRS may be fractionated magmatic equivalents. Mafic rocks in the GMS formed from magmas produced by relatively low degrees of partial melting of mantle that was relatively enriched in incompatible elements compared to depleted mantle. These enriched melts may have been derived from a plume and/or enriched lithospheric components, potentially continental crust, embedded in depleted upper mantle. A depleted mantle signature preserved locally in the GMS probably reflects increasing asthenospheric input during crustal thinning, opposed to crustal or fluid contamination. Whole-rock minor and trace element data from the GMS and R/PRS are distinct from analyses of glaucophane schist from the Tillotson Peak Complex in northern Vermont, which may be exhumed Iapetan ocean floor. Exhumed mafic rocks in the GMS and R/PRS were formed as lower plate melts prior to relatively high pressure subduction zone metamorphism, providing evidence for subduction of the Laurentian margin, not subduction erosion. Low pressure greenschist facies mafic rocks that occur structurally between the GMS and R/PRS were sourced from depleted or highly depleted mantle in a supra-subduction zone environment, potentially a forearc or backarc basin; an ophiolitic origin is equivocal. Geochemical and isotopic data and interpretations are compatible with rift-related tectonomagmatic models for the peri-Laurentian realm of the northern Appalachians.

Chlorine and lithium behavior in metasedimentary rocks during prograde metamorphism: A comparative study of exhumed subduction complexes (Catalina Schist and Schistes Lustrés)

Lithium and chlorine concentrations and isotopic compositions of well-characterized metasedimentary suites from the Schistes Lustrés and Lago di Cignana (Western Alps) and the Catalina Schist (southern California, USA) were compared to determine Li and Cl behavior during prograde subduction-zone metamorphism. New data were obtained for Cl from both suites and for Li from the Western Alps. The Catalina Schist contains lawsonite-albite to amphibolite grade rocks recording peak temperatures of 200 to 750 °C and depths of 15 to 45 km, with the higher-grade units representing relatively warm subduction P-T paths. Bulk Cl concentrations decrease from ~100–500 μg/g to ~10–25 μg/g across metamorphic grades, largely due to Cl loss from chlorite and white mica, with most of this loss occurring at the lower grades. This loss mirrors the previously documented decreases in N, B, Cs, As, and Sb concentrations, with relatively little loss at higher metamorphic grade, and contrasts with the behavior of Li showing only modest loss and change in δ7Li values across all grades. Metapelitic rocks from the Western Alps representing a relatively “cool” geothermal gradient of ~8 °C/km, record peak temperatures of 350 to 550 °C and depths of up to 90 km. In this suite, both Cl and Li concentrations are uniform across grade, showing no obvious change in concentration. Lithium concentrations range to somewhat higher values compared to those previously measured in the Catalina Schist. Chlorine isotope compositions of the Schistes Lustrés overlap with those measured in the Catalina Schist, whereas Li isotope compositions of the Schistes Lustrés samples range to somewhat higher values than those from the Catalina Schist. Both suites show significant isotopic heterogeneity within single metamorphic grades and no systematic change in δ37Cl or δ7Li values with increasing grade. These heterogeneities are interpreted to be inherited from the protolith. Lithium isotope compositions correlate well with the chemical index of alteration (CIA), an observation also supporting minimal metamorphic alteration of the isotopic composition reflecting the protolith. These data demonstrate that, although some Cl is retained to great depths during subduction, most Cl is lost from metasedimentary rocks at shallow depths, similar behavior to that of B, Cs, As, and Sb. In contrast, Li loss is minimal across the full range of grade, more similar in behavior to Rb, Ba, and K.

Halogens in Atlantis Bank gabbros, SW Indian Ridge: Implications for styles of seafloor alteration

The processes controlling halogen (F, Cl, Br, I) abundances in gabbroic ocean crust recovered from the 809-m deep Hole U1473A drilled on the Atlantis Bank during International Ocean Discovery Program (IODP) Expedition 360 were investigated. The aims were to provide new constraints on hydrothermal alteration and the abundances of halogens potentially transported to subduction zones in oceanic crust produced on a slow spreading ridge.Halogens in 51 gabbros and felsic veins have concentrations of ∼20-260 ppm F, 15-840 ppm Cl, 44-1230 ppb Br and 1-2490 ppb I. On average the gabbros retain a melt-derived magmatic F component of 58 ± 26% but are dominated by ∼96% hydrothermal Cl, Br, I and H2O. The abundances of hydrothermal Cl, Br and I are consistent with alteration at a seawater/rock ratio of <1. However, hydrothermal F is more enriched than expected and some amphiboles have high F/Cl ratios of 10-30 that provide evidence for the minor additional involvement of F-rich magmatic fluids. The abundant late-stage felsic veins that transect the gabbros and account for 1.5 vol.% of Hole U1473A lithologies are suggested as the most likely source of F-rich magmatic fluids.Downhole variations show F, Cl, Br and H2O are most abundant in amphibole- and clay-rich alteration zones at the top of the hole. The highest I concentrations of 1-2.5 ppm delineate an oxidised CO2-rich alteration zone in which seawater iodate was incorporated into carbonate and Fe-oxyhydroxide alteration. The role of iodate, which is more reactive than other halides, in generating I-rich alteration can be distinguished from alteration by I-rich sedimentary pore waters because the oxidised alteration is characterised by high I/Cl together with low Br/Cl, whereas organic matter in pore waters is enriched in both Br/Cl and I/Cl.The halogens have inferred compatibilities of F− > IO3− > OH− > Cl− ≥ Br− ∼ ≥ I− in the investigated alteration assemblage. EPMA and SHRIMP analyses indicate amphibole contains 1000-3000 ppm Cl in amphibolite facies alteration at the top of the Hole. Amphibole, chlorite and talc in greenschist facies alteration have much lower concentrations, typically in the range of 20-800 ppm Cl (median ∼100 ppm Cl), and F/Cl ratios of <4. In comparison, low temperature limonite (FeOOH.nH2O) has 160-8500 ppm Cl (median ∼840 ppm Cl). Amphibole is the dominant host of Cl and F in amphibolite facies alteration, but chlorite and limonite are important at lower grades. The samples have fairly constant Br/Cl ratios suggesting that Br excluded from the amphibole lattice is retained in minerals such as chlorite and/or non-structural sites. High I concentrations of 10's of ppm are inferred for some carbonate and limonite. Overall amphibole is a less dominant host of halogens than has been suggested previously, which has important implications for the eventual release and availability of halogens during subduction zone metamorphism.

Neodymium isotope disequilibria in subducted sediments, and potential consequences for subduction-zone recycling

Neodymium isotope geochemistry is pivotal to understanding magma genesis and crustal recycling processes at convergent plate margins. Here, we present Nd isotope compositions of rare earth element (REE)–rich minerals from blueschist- to eclogite-facies rocks that represent previously subducted continental sediments. We find Nd isotope heterogeneity in all of our samples. Apatite preserves diverse detrital isotopic compositions despite metamorphism up to at least 600 °C and 3.0 GPa, whereas lawsonite appears to be isotopically homogenous. Epidote and monazite are major REE hosts under eclogite-facies conditions; in our samples these phases also retain Nd isotope heterogeneity, even up to ultrahigh-pressure conditions of 700 °C and 4.0 GPa. These findings contest the assumption of Nd isotope equilibration during subduction-zone metamorphism, so caution is needed when using Nd isotopes to calculate subducted sediment contributions to arc magmas or for determining rates of crustal recycling through subduction zones.

Metamorphic consequences of secular changes in oceanic crust composition and implications for uniformitarianism in the geological record

Cooling of the Earth's mantle since the Meso-Archean is predicted by thermal and petrological models to have induced a secular change in the composition of primary mantle-derived magmas – and thus bulk oceanic crust; in particular, suggesting a decrease in maficity over time. This hypothesis underpins several recent studies that have addressed key geological questions concerning evolving plate tectonic styles, the rates and timing of continental crust formation, comparative planetology, and the emergence of complex life on Earth. Major, minor, and trace element geochemical analyses of (meta)mafic rocks preserved in the geological record allows exploration of this theory, although no consensus currently exists about the magnitude of this change and what compositions – if anything – constitute representative examples of Paleo-, Meso-, or Neo-Archean primitive oceanic crust. In this work, we review the current state of understanding of this issue, and use phase equilibria to examine the different mineral assemblages and rock types that would form during metamorphism of basalt of varying maficity in subduction zone environments. The presence (or absence) of such metamorphic products in the geological record is often used as evidence for (or against) the operation of modern-day subduction-driven plate tectonics on Earth at particular time periods; however, the control that secular changes in composition have on the stability of mineral assemblages diagnostic of subduction-zone metamorphism weakens such uniformitarianistic approaches. Geodynamic interpretations of the Archean metamorphic rock record must therefore employ a different set of petrological criteria for determining tectonothermal histories than those applied to Proterozoic or Phanerozoic equivalents.

Halogens and noble gases in serpentinites and secondary peridotites: Implications for seawater subduction and the origin of mantle neon

Ophiolitic serpentinites and secondary peridotites formed by serpentinite dehydration were investigated to improve constraints on the fates of noble gases and halogens during subduction zone metamorphism. The work extends previous studies to encompass F and four stages of serpentinization and serpentinite dehydration including: (i) oceanic serpentinites preserving the features of seafloor serpentinization; (ii) subducted high grade (olivine bearing) antigorite-serpentinites; (iii) spinifex and granofels textured chlorite harzburgites; and (iv) a garnet peridotite.Serpentinites and secondary peridotites from different ophiolites are shown to have characteristic ranges of 40Ar/36Ar: chrysotile and antigorite serpentinites from Erro Tobbio (Western Alps) have 40Ar/36Ar of ∼ 296–390; antigorite serpentinites and chlorite harzburgites from Cerro del Almirez (Betic Cordillera) have 40Ar/36Ar of ∼ 340–600, and chlorite harzburgites and garnet peridotites from Cima di Gagnone (Swiss Alps) have 40Ar/36Ar of ∼ 600–1100. The variation of 40Ar/36Ar is unrelated to metamorphic grade at each locality but is broadly correlated with variation in other radiogenic isotopes (206Pb/204Pb and 87Sr/86Sr) between localities. This suggests excess 40Ar was derived from terrigenous sediments with characteristic ranges of 40Ar/36Ar and 87Sr/86Sr in different subduction zones.The secondary chlorite harzburgites have 20Ne/36Ar ratios of greater than seawater, contain parentless (or excess) 4He, and have higher F concentrations than any of the serpentinites investigated. The 20Ne/36Ar is broadly correlated with 40Ar/36Ar in samples from Cerro del Almirez suggesting derivation of excess 40Ar and atmospheric 20Ne from a common source. The chlorite is shown to have higher concentrations of F, Ne and other noble gases than coexisting olivine and enstatite, which contain fluid-related inclusions. The high F content and high 20Ne/36Ar ratios of the chlorite harzburgites are ascribed to fluxing of dehydrating serpentinites with F-, 40Ar-, 4He- and 20Ne-rich fluids derived from metasediments in the subducting slab, and an inferred high compatibility of F and Ne in chlorite.The garnet peridotite from Cima di Gagnone records the final and complete dehydration of serpentinite. Based on the analysis of mineral separates minimally affected by retrogression (marked by garnet breakdown and the appearance of Cl-rich hornblende), nominally anhydrous garnet peridotite retains Cl, Br, I and non-radiogenic noble gas concentrations up to an order of magnitude higher than average depleted mantle.The data are consistent with serpentinised lithosphere and related secondary peridotites as major sources of deeply subducted seawater-derived volatiles in the Earth’s mantle. The data also demonstrate that the relative abundances of volatiles subducted into the mantle are controlled by multiple factors including: original seafloor alteration, the relative compatibilities of different noble gases and halogens in minerals forming during different stages of subduction and chemical exchange between different lithologies during subduction. The combination of these processes has produced elevated 20Ne/36Ar in chlorite harzburgites from two unrelated localities. This suggests that subduction of atmospheric Ne could be significantly more efficient than previously realised, which has implications for interpretation of the mantles primordial 20Ne/22Ne ratio and how the Earth accreted.

Intra-slab COH fluid fluxes evidenced by fluid-mediated decarbonation of lawsonite eclogite-facies altered oceanic metabasalts

The interplay between the processes controlling the mobility of H2O and C-bearing species during subduction zone metamorphism exerts a critical control on plate tectonics and global volatile recycling. Here we present the first study on fresh, carbonate-bearing, lawsonite eclogite-facies metabasalts from Alpine Corsica, France, which reached the critical depths at which important devolatilization reactions occur in subducting slabs. The studied samples indicate that the evolution of oceanic crustal sequences subducted under present-day thermal regimes is dominated by localized fluid-rock interactions that are strongly controlled by the nature and extent of inherited (sub)seafloor hydrothermal processes, and by the possibility of deep fluids to be channelized along inherited or newly-formed discontinuities. Fluid channelization along inherited discontinuities controlled local rehydration and dehydration/decarbonation reactions and the stability of carbonate and silicate minerals at the blueschist-eclogite transition. Fluid-mediated decarbonation was driven by upward, up-temperature fluid flow in the inverted geothermal gradient of a subducting oceanic slab, a process that has not been documented in natural samples to date. We estimate that the observed fluid-rock reactions released 20–60 kg CO2 per m3 of rock (i.e. ~0.7–2.1 wt% CO2), which is in line with the values predicted from decarbonation of metabasalts in open systems at these depths. Conversely, the estimated time-integrated fluid fluxes (20–50 t/m2) indicate that the amount of carbon transported by channelized fluid flow within the volcanic part of subducting oceanic plates is potentially much higher than previous numerical estimates, testifying to the percolation of C-bearing fluids resulting from devolatilization/dissolution processes operative in large reservoirs.

A tectonized ultramafic-mafic-pelitic package in Stockbridge, Vermont: Metamorphism resulting from subduction and exhumation

A tectonized ultramafic-mafic-pelitic package southwest of the Burgess Branch Fault Zone in the Rowe/Prospect Rock slice in Stockbridge, Vermont preserves Taconian subduction zone metamorphism. The polydeformed package consists of carbonatized and chloritized serpentinite lozenges that are faulted between graphitic phyllite and an intercalated zone of mafic greenstones and pelitic schists that retain primarily Taconian structures. Amphiboles zoned chemically in greenstones display decreases in PL (NaM4) and TK (AlVI + Fe3+ + 2Ti + Cr) from cores to rims. Pseudosection and amphibole isopleth calculations show that different greenstone bodies experienced peak subduction zone metamorphism at different depths between ∼19 and 32 Km (0.55–0.95 GPa) and/or at different temperatures between ∼425 and 500 °C. Barroisite and winchite cores preserve the highest pressure and lowest temperature peak metamorphism, which is interpreted as lower blueschist facies. All greenstones followed decompression cooling paths to lower greenschist facies where actinolite rims grew. Assembly of the ultramafic-mafic-pelitic package probably occurred in a Taconian exhumation channel containing mantle serpentinite, oceanic crust, and clastic rocks of the Laurentian margin and Iapetan Ocean basin.

Zircon geochemical constraints on the protolith nature and metasomatic process of the Mg-rich whiteschist from the Western Alps

The Mg-rich silicic crustal rocks characterized by high SiO2 and MgO contents are widespread in the Alps, providing rare targets to investigate the origin of Mg-rich fluids in the continental subduction zone. However, it is a prerequisite to elucidate the protolith nature of such Mg-rich rocks, including the possible alteration process experienced before the Alpine metamorphism. For this purpose, we carried out a detailed study of trace elements, O-Hf isotopes and U-Pb ages for zircons from the coesite-bearing whiteschist and its country rock metagranite at Dora-Maria in Western Alps. The whiteschist is characterized by much higher MgO contents than the adjacent metagranite. Relict magmatic zircons from the two types of rocks give essentially the same U-Pb ages of ~262Ma, similar REE contents and patterns, the same range of εHf(t1) values from −6.4 to 2.8 and δ18O values from mostly 9 to 11‰. These features provide compelling evidence that the whiteschist and metagranite share the same protolith, i.e., the Permian granite. All the above geochemical compositions are consistent with the argument that the high MgO content of the whiteschist was acquired from high Mg fluids from dehydration of the serpentinized peridotite at the slab-mantle interface in the continental subduction channel. The hypothesis of a pre-Alpine hydrothermal alteration of the granitic protolith to cause the MgO enrichment is not favorable. Zircon in the metagranite does not show any metamorphic overgrowth during the Alpine orogeny, in contrast to the extensive overgrowth of metamorphic rims at ~35Ma in the whiteschist. The metamorphic rims show relatively low REE contents with variably flattened HREE patterns, different from the relict magmatic zircons that exhibit relative high REE contents with steep HREE patterns. This difference suggests that the breakdown of hydrous minerals plays a crucial role in dictating mineral reactions for zircon growth during the continental subduction-zone metamorphism. This interpretation is also consistent with the local occurrence of garnet coronae along the grain margins of biotite in the metagranite. Therefore, this study provides not only the constraints on the protolith nature and metasomatic process of Mg-rich whiteschist from the Western Alps, but also insights into the role of metamorphic fluids in controlling mineral reactions for the metamorphic growth of both zircon and garnet in the continental subduction zone.

Different stages of chemical alteration on metabasaltic rocks in the subduction channel: Evidence from the Western Tianshan metamorphic belt, NW China

To understand the geochemistry of subduction zone metamorphism, especially the large-scale mass transfer at forearc to subarc depths, we carried out a detailed study of a ∼1.5m size metabasaltic block with well-preserved pillow structures from the Chinese Western Tianshan high- to ultrahigh-pressure metamorphic belt. This metabasaltic block is characterized by omphacite-rich interiors gradually surrounded by abundant channelized (veins) glaucophane-rich patches toward the rims. The glaucophane-rich rims share the same peak metamorphic conditions with omphacite-rich interiors, but have experienced stronger blueschist-facies overprinting during exhumation. Representative samples from the glaucophane-rich rims and omphacite-rich interiors yield a well-defined Rb-Sr isochron age of 307±23Ma, likely representing this overprinting event. Both glaucophane-rich rims and omphacite-rich interiors show elevated K-Rb-Cs-Ba-Pb-Sr contents relative to their protolith, reflecting a large-scale enrichment of these elements and formation of abundant phengite during subduction. Compared with the omphacite-rich interiors, the glaucophane-rich rims have gained rare earth elements (REEs, >25%), U-Th (∼75%), Pb-Sr (>100%) and some transition metals like Co and Ni (25–50%), but lost P (∼75%), Na (>25%), Li and Be (∼50%); K-Rb-Cs-Ba show only 10% loss. These chemical changes would be caused by serpentinite-derived fluids during the exhumation in the subduction channel. Therefore, there are two stages of fluid action in the subduction channel. As the formation of phengite stabilizes K-Rb-Cs-Ba at the first stage, the residual fluids released from the phengite-rich metabasaltic rocks would be depleted in these elements, which are unlikely to contribute to elevated contents of these elements in arc magmas if phengite remains stable at subarc depths. In addition, the decrease of U/Pb ratios as the preferred enrichment of Pb over U in the eclogitic rocks during the first stage chemical alteration may further lead to the lower radiogenic Pb isotope component of the deeply subducted ocean crust with time, which is inconsistent with the high radiogenic Pb isotope component of high µ (=238U/204Pb) basalts.

Noble gases recycled into the mantle through cold subduction zones

Subduction of hydrous and carbonated oceanic lithosphere replenishes the mantle volatile inventory. Substantial uncertainties exist on the magnitudes of the recycled volatile fluxes and it is unclear whether Earth surface reservoirs are undergoing net-loss or net-gain of H2O and CO2. Here, we use noble gases as tracers for deep volatile cycling. Specifically, we construct and apply a kinetic model to estimate the effect of subduction zone metamorphism on the elemental composition of noble gases in amphibole – a common constituent of altered oceanic crust. We show that progressive dehydration of the slab leads to the extraction of noble gases, linking noble gas recycling to H2O. Noble gases are strongly fractionated within hot subduction zones, whereas minimal fractionation occurs along colder subduction geotherms. In the context of our modelling, this implies that the mantle heavy noble gas inventory is dominated by the injection of noble gases through cold subduction zones. For cold subduction zones, we estimate a present-day bulk recycling efficiency, past the depth of amphibole breakdown, of 5–35% and 60–80% for 36Ar and H2O bound within oceanic crust, respectively. Given that hotter subduction dominates over geologic history, this result highlights the importance of cooler subduction zones in regassing the mantle and in affecting the modern volatile budget of Earth's interior.

Early Carboniferous subduction-zone metamorphism preserved within the Palaeo-Tethyan Rasht ophiolites (western Alborz, Iran)

A polyphase history of oceanic construction and consumption is documented by the distribution of the Tethyan ophiolitic suture zones in Iran. Despite the geodynamic significance of these suture zones, few modern petrological and geochronological data are available from these ophiolitic domains, hampering a full assessment of the timing, thermobaric regimes and palaeotectonic scenarios leading to oceanic suturing and continental assembly in Iran and, more in general, along the southern margin of Eurasia. In this paper, we describe a newly discovered HP ophiolite mélange within the Rasht ophiolites, at the NW termination of the Palaeo-Tethyan suture in Iran. Petrological investigations on the metamorphic units embedded within the ophiolite mélange are integrated with whole-rock geochemistry and Ar–Ar phengite geochronology to constrain the geotectonic setting of formation and to define the associated P – T – t paths. We provide evidence that the Rasht ophiolite domain corresponds to an exhumed subduction complex formed during Early Carboniferous ( c. 350 Ma) subduction of a branch of the Palaeo-Tethyan oceanic realm, with peak metamorphism equilibrated under blueschist- to eclogite-facies metamorphic conditions. Implications of these data for the palaeotectonic reconstruction during closure of the Palaeo-Tethyan ocean and the terminal collisional assembly along the southern margin of the Eurasia plate are also discussed. Supplementary material: Analytical methods and protocols are available at https://doi.org/10.6084/m9.figshare.c.3706852