Ulten Zone Research Articles

Reaction‐Induced Mantle Weakening at High‐Pressure Conditions: An Example From Garnet Pyroxenites of Ulten Zone (Eastern Alps, N Italy)

AbstractPeridotites of Ulten Zone (Eastern Alps, N Italy) show a transition from coarse protogranular spinel lherzolites to fine‐grained amphibole + garnet peridotites, recorded by the crystallization of garnet coronas around spinel. Pyroxenite veins, transposed along the peridotite foliation, show a similar metamorphic evolution from coarse‐grained (garnet‐free) websterites to fine‐grained garnet websterites. In both peridotites and websterites, garnet previously exsolved from porphyroclastic high‐temperature pyroxenes and later crystallized along the foliation. This evolution has been interpreted to reflect cooling and pressure increase of websterites and host peridotites from spinel‐ to garnet‐facies conditions. Microstructures and crystallographic orientation data indicate that the re‐equilibration of garnet websterites in the garnet stability field occurred during deformation. Porphyroclastic pyroxenes have been interpreted to deform by dislocation glide and creep. In particular, TEM observations indicate the activation of the (100)[010] slip system in orthopyroxene. Core‐and‐mantle microstructures also suggest that dislocation creep was aided by subgrain rotation recrystallization, leading to the formation of neoblastic pyroxenes. These recrystallized grains deformed by diffusion‐accommodated grain boundary sliding, as indicated by the occurrence of quadruple junctions and straight, aligned grain boundaries. The transition from dislocation creep to diffusion creep in websterites was accompanied by the crystallization of garnet along foliation, which triggered the pinning of the recrystallized matrix and stabilized the fine‐grained microtexture for diffusion creep, promoting rheological weakening. Garnet websterites of Ulten Zone thus offer a unique opportunity to investigate the effects of reaction softening during the corner flow in the supra‐subduction lithospheric mantle induced by the descending slab.

Crustal fluids cause strong Lu-Hf fractionation and Hf-Nd-Li isotopic provinciality in the mantle of continental subduction zones

Abstract Metasomatized mantle wedge peridotites exhumed within high-pressure terranes of continental collision zones provide unique insights into crust-mantle interaction and attendant mass transfer, which are critical to our understanding of terrestrial element cycles. Such peridotites occur in high-grade gneisses of the Ulten Zone in the European Alps and record metasomatism by crustal fluids at 330 Ma and high-pressure conditions (2.0 GPa, 850 °C) that caused a transition from coarse-grained, garnet-bearing to fine-grained, amphibole-rich rocks. We explored the effects of crustal fluids on canonically robust Lu-Hf peridotite isotope signatures in comparison with fluid-sensitive trace elements and Nd-Li isotopes. Notably, we found that a Lu-Hf pseudo-isochron is created by a decrease in bulk-rock 176Lu/177Hf from coarse- to fine-grained peridotite that is demonstrably caused by heavy rare earth element (HREE) loss during fluid-assisted, garnet-consuming, amphibole-forming reactions accompanied by enrichment in fluid-mobile elements and the addition of unradiogenic Nd. Despite close spatial relationships, some peridotite lenses record more intense fluid activity that causes complete garnet breakdown and high field strength element (HFSE) addition along with the addition of crust-derived unradiogenic Hf, as well as distinct chromatographic light REE (LREE) fractionation. We suggest that the observed geochemical and isotopic provinciality between peridotite lenses reflects different positions relative to the crustal fluid source at depth. This interpretation is supported by Li isotopes: inferred proximal peridotites show light δ7Li due to strong kinetic Li isotope fractionation (−4.7–2.0‰) that accompanies Li enrichment, whereas distal peridotites show Li contents and δ7Li similar to those of the depleted mantle (1.0–7.2‰). Thus, Earth's mantle can acquire significant Hf-Nd-Li-isotopic heterogeneity during locally variable ingress of crustal fluids in continental subduction zones.

Multi-stage sulfur and carbon mobility in fossil continental subduction zones: New insights from carbonate-bearing orogenic peridotites

The volatile transfer in subduction zones and the role of sulfate as a vector for the mobilization of oxidized components from down-going slabs remain hotly debated issues. Orogenic spinel and garnet peridotite lenses from the Ulten Zone (Eastern Alps, Italy), exhumed as part of felsic metamorphic terranes in continental collision zones, bear witness to mass transfer processes in these pivotal environments.In this study, we carried out a multi-method investigation of mantle sulfides coexisting with four generations of carbonates, indicating coupled sulfur and carbon mobility throughout the peridotites’ metamorphic evolution as part of the Variscan subduction architecture. Detailed petrography, bulk rock measurements, in situ chemical and geochemical analyses of sulfides as well as Sr isotope analyses of associated clinopyroxene and amphibole are combined with the aim to constrain the origin, nature and effect of multiple C-O-H-S-bearing fluids and melts the peridotites interacted with. The first, pre-peak, metasomatic pulse (Stage 1) is represented by an H2S-CO2-bearing melt from the subduction-modified hot mantle wedge, which formed a pyroxenite layer hosting matrix pentlandite with δ34S of +2.77‰. Matrix carbonates occasionally occur in the coarse-grained peridotite under eclogite-facies conditions (Stage 2), with heavier δ34S (up to +3.43‰), radiogenic Sr (87Sr/86Srclinopyroxene > 0.7052) and elevated Pb abundances. These are ascribed to interaction with isotopically heavy melts carrying recycled crustal component, permissive of, but not requiring, involvement of oxidized S species. Conversely, isotopically lighter matrix pentlandite (δ34S = −1.62 to +0.67‰), and radiogenic Sr in amphibole (87Sr/86Sr = 0.7056) and associated dolomite (published data) from fine-grained garnet-amphibole peridotites may point to involvement of H2S-CO2-bearing crustal fluids, which variably equilibrated with the mantle before interacting with the peridotites. The post-peak Stage 3 marks the entrapment of peridotites into a tectonic mélange. Here, kelyphitization of garnet is catalyzed by further ingress of a S-bearing fluid (δ34S = −0.38‰), while carbonate veining with occasional sulfides bear witness to channelized fluid flow. Sulfide and amphibole grains in retrogressed spinel peridotites reveal the highest contents of fluid-mobile elements (As, Sb) and 87Sr/86Sramphibole up to 0.7074, suggesting late interactions with isotopically heavy crustal fluids at high fluid-rock ratios. Textural observations indicate that, during Stage 4, serpentinization of peridotites at low ƒS2 played an active role not only in CO2 release by conversion of dolomite to calcite + brucite intergrowths, but also in local removal of 32S during the final exhumation stage. Late channelized sulfur remobilization is evidenced by the serpentine + magnetite (±millerite ± calcite) vein carrying > 300 ppm S.Overall, the relatively narrow range of sulfur isotope composition (δ34S = −1.62 to +3.76‰) is indicative of limited interaction with isotopically heavy crustal liquids, and points to a subordinate role of subduction-derived sulfate throughout the extended fluid(melt)/rock evolution of the Ulten Zone peridotites, first in the mantle wedge and then as part of a tectonic mélange.

Polymineralic inclusions as tracers of multistage metasomatism in a paleo mantle wedge

Paleosubduction zones are key areas where slab-derived fluids interact with the overlying mantle wedge. Slab fluids play therefore an important role in the deep element cycle and can metasomatize ultramafics showing particular mineral assemblages. The nature of slab fluids is usually investigated from fluid inclusions and/or multiphase solid inclusions, as well as from incompatible elements in mantle minerals. We have made a study on a garnet-peridotite from the Variscan Ulten Zone (Eastern Alps, Italy) in which peculiar polymineralic inclusions (PI) in garnet provide a wealth of information on the interaction between mantle wedge and slab fluids. The selected sample shows a fine-grained amphibole-olivine-orthopyroxene-spinel-clinopyroxene matrix and a fractured large garnet porphyroclast, surrounded by a kelyphitic corona. Garnet core and rim host randomly distributed PI, which may be as large as 284,000 μm2. The PI show irregular, fracture-controlled shapes and often contain unusual mineral associations. Many PI are directly associated with Mg-hornblende- or chlorite-sealed micro-fractures crosscutting garnet. The most abundant PI contain spinel and amphibole as the main minerals. Spinel-bearing PI consists of high-Cr spinel (Cr# = 0.31–0.41) surrounded by amphiboles (magnesio-hornblende), locally associated with dolomite, sapphirine, calcite, sulphides and kinoshitalite (i.e. a Ba-rich phlogopite). Amphibole-bearing PI contain zoned amphiboles (tschermakitic cores surrounded by Mg-hornblende, which is rimmed by tremolite and Mg-amphibole), dissakisite (an REE-bearing epidote), apatite, dolomite, calcite, spinel, sapphirine, chlorite, kinoshitalite, and sulfides. The retrieved mineral reaction history and the major and some incompatible elements (Cl, Ba, Sr) of PI minerals provide clues about the composition of metasomatic fluids. The studied PI formed in garnet fractures during exhumation by reactions between garnet and (1) slab-derived COH fluids and (2) late-stage saline brines. Metasomatic fluids/brines were rich in volatile elements and had a crustal signature (enrichment in LILE and LREE) with variable Cl contents and CO2/H2O ratios. Products of early garnet-fluid reactions became reactants of later reactions, thus generating complex textures, including replacement textures of sapphirine over spinel, calcite over dolomite and chlorite over Mg-hornblende. Textures and compositions of the PI testify to a multistage metasomatic overprint at peak P-T conditions above 2 GPa (M1), during the first exhumation stage at 775–1000 °C, below 2 GPa (M2) and finally at 775 °C and 1 GPa (M3). In this study we demonstrate that Gibbs free energy minimization may aid in distinguishing between multiphase solid inclusions and polymineralic inclusions; the latter do provide valuable information on the evolution of retrograde P-T paths in the paleosubduction channel, the relative chronology of metasomatic events and clues on the chemical signature of the fluids.

In situ Sr isotope analysis of mantle carbonates: Constraints on the evolution and sources of metasomatic carbon-bearing fluids in a paleo-collisional setting

Carbonate-bearing wedge peridotites attest the mobilization of carbon (C) by slab fluids/melts circulating in a subduction setting. In general, COH fluids are thought to derive from the dehydration/partial melting of the crustal portions of slabs, especially during the exhumation of crust-mantle mélanges along continental subduction channels. In this study we combined textural observations with in-situ Sr isotope analyses of mantle carbonates occurring in different microstructural sites to test whether the fluids responsible for the carbonation of a mantle wedge are derived from the subducted continental crust or not. We focus on the Ulten Zone peridotites (Eastern Italian Alps) associated with high-grade felsic rocks, where carbonates occur mainly as dolomite and minor magnesite and calcite. In situ laser MC-ICP-MS analysis of peridotites representing different episodes of a complex metasomatic history, indicates that Sr isotopic variations can be linked to the different microstructural positions of carbonates. The C-metasomatism of the UZ peridotites is proposed to have occurred in two stages. The first stage is the HP‑carbonation at peak (eclogite-facies) conditions, with formation of interstitial matrix dolomite in textural equilibrium with hornblende to pargasite amphibole and Cl-apatite. This dolomite exhibits relatively unradiogenic 87Sr/86Sr present day values of 0.70487±0.00010, requiring different sources with respect to the associated migmatites and the overhanging mantle wedge. Carbonation continued during exhumation, with local injection of C-rich fluids forming a dolomite vein in association with tremolite and chlorite. The dolomite vein shows a wide range of 87Sr/86Sr (0.7036–0.7083), reflecting both the primary composition of carbonates and the consequent interaction with crustal fluids as expected in a crust-mantle mélange. The second stage is C-remobilization by dolomite dissolution and precipitation of brucite intergrowths with calcite during the final exhumation. This remobilization event has resulted in a similar Sr composition to the precursor dolomite.The mantle wedge is therefore capable of storing carbonates which have been shown to represent a complex metasomatic evolution from eclogite-facies conditions to very shallow structural levels. Therefore, fluids released from subducting slabs of continental lithosphere might be responsible for the crystallization of metasomatic minerals such as amphibole, phlogopite and zircon in the overlying ultramafic rocks. Conversely, the role of these metasomatic fluids on the carbonation of mantle wedge is likely overestimated. The combination of geochemical, isotopic and textural evidence suggests that dolomite inclusions and interstitial dolomite are derived in large part from a distinct source of C-bearing fluids that could be related to depleted mantle wedge sources and/or trondhjemitic igneous activity. In contrast, at the end of exhumation, residual COH-fluids released by the associated stromatic gneisses and orthogneisses resulted in late-stage dolomite veins having the highest Sr isotope values in the Ulten Zone peridotites.

Element Transfer and Redox Conditions in Continental Subduction Zones: New Insights from Peridotites of the Ulten Zone, North Italy

The orogenic peridotites and pyroxenites of the Ulten Zone (north Italy) record multistage metasomatism by crust-derived melts and fluids within a Late-Variscan mantle wedge. We acquired new major and trace element data as well as garnet and whole-rock iron speciation for a representative suite of samples, with the aim to further constrain element cycling and the redox state attending the development of the major mineralogical and textural rock types that occur within the Ulten Zone. Initially, spinel peridotites were refertilized by mafic melts in the hot and shallow mantle wedge, followed by garnet formation as the peridotites were carried towards a cool, subducting slab of continental crust by corner flow. Upon exhumation, ingress of aqueous, crust-derived fluids provoked amphibole-forming reactions, which caused gradual consumption of garnet and clinopyroxene and transformation from coarse- to fine-grained assemblages. Since Si, Al, Na, Ti, Ca and HREE formerly stored in reactants were not fully accommodated in newly-formed phases, these elements were partially removed from the bulk-rock, generating more depleted compositions resembling residues after partial melting. Unexpectedly, the remaining garnet retains low Fe3+/Sigma Fe (<0046) even after the bulk-rocks became strongly enriched in Fe3+ during metasomatism and retrogression (Fe3+/Sigma Fe = 011-023), which was mostly stored in coexistent amphibole and interstitial serpentine. Low Fe3+/Sigma Fe in garnet is consistent with Delta logfO(2) = FMQ-1.7 to FMQ-0.3 at 2GPa. Combined with previous studies, this is evidence for garnet growth within a heterogeneously oxidized mantle wedge, reflecting a variable extent of percolation by oxidizing aqueous fluids. During metasomatism, concomitant variable enrichment in LILE, LREE and some HFSE, and significant compositional differences between sampling localities, reflect both variable fluid/rock ratios at small spatial scales but also indicate chromatographic effects that likely relate to different positions relative to the subducting crust releasing fluids into the mantle wedge. Hydration by dilute fluids during retrogression did not result in additional enrichment in fluid-mobile elements, but caused further replacement of garnet and clinopyroxene. This study highlights the control that changing mineralogies, developed in response to interaction with various crustal melts and fluids under variable pressure-temperature and redox conditions in a continental subduction zone, exert on the retention or release of major and trace elements in peridotite. In particular, formation and/or persistence of amphibole and dolomite, as documented in the present study, suggest that the subduction-modified mantle wedge is an efficient trap for volatiles and fluid-mobile elements.

A petrographic study of carbonate phases in the Ulten Zone ultramafic rocks: insights into carbonation in the mantle wedge and exhumation-related decarbonation

We present a comprehensive petrographic study on carbonates in orogenic mantle wedge-derived peridotites from the Ulten Zone (UZ) in the Eastern Italian Alps representing a fragment of the Variscan belt. These peridotites are found in ultramafic bodies incorporated in high-grade crustal rocks from a former continental slab and are characterized by highly variable mineral assemblages and microstructures, which reflect their evolution from spinel peridotite in a hot mantle wedge, to garnet peridotite after incorporation into the subducting slab and finally exhumation accompanied by retrogression. Carbonate phases in UZ peridotites are observed in diverse textural sites and can be related to particular petrographic peridotite types. Inclusions of dolomite and dolomite-breakdown products in primary spinel from coarse-grained protogranular peridotites indicate that carbon-bearing liquids were introduced into the mantle wedge at a time before achieving garnet stability. Discrete dolomite grains occur in fine-grained deformed garnet-bearing peridotite and are suggested to have formed simultaneously with hydrous phases (amphibole, apatite) from a carbon-bearing aqueous crustal slab-derived fluid during garnet stability. Intergrowths of calcite and brucite occur mainly in serpentinized fine-grained garnet-amphibole peridotites and are interpreted to be products of dedolomitization (CaMg(CO 3 ) 2 + H 2 O → CaCO 3 + Mg(OH) 2 + CO 2 ), thus decarbonation, during exhumation. Veins of dolomite and calcite-brucite indicate secondary dolomite formation from carbon-bearing fluids due to interaction with slab-derived crustal fluids during retrogression on the exhumation path of the UZ peridotite. Magnesite veins and calcite veins that are texturally linked to alteration features are probably of low-temperature origin. In summary, this petrographic study reveals multi-stage carbonation of the UZ peridotites during residence in the mantle wedge and decarbonation with the release of a carbon species during low-temperature peridotite reaction with aqueous fluids leading to serpentinization accompanied by dolomite breakdown, thus providing important constraints on the carbon budget and carbon cycling in collisional settings. Overall, the ubiquity of carbonates in a variety of textural settings in the UZ peridotites suggests that the supra-subduction zone mantle in continental settings represents an efficient carbon trap.

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 setting.

The role of C-O-H and oxygen fugacity in subduction-zone garnet peridotites

C-O-H fluids are released by dehydration, partial melting and/or decarbonation of the slab and transferred to the mantle, where they interact with the surrounding rocks, prompting the growth of carbonates, hydrous minerals and C polymorphs. In the pure C-O-H system, C-saturated fluid speciation is a function of the oxygen chemical potential. Therefore, in natural systems, the fluid speciation can be imposed by the redox state of the rock-forming phases. Alternatively, C-O-H fluids may control the bulk oxidation state of the rock system by redox reactions with the mineral phases. We selected three case studies of garnet-bearing ultramafic rocks (Ulten zone, Italy; Sulu, China; Bardane, Norway), which record metasomatic processes driven by C-O-H fluids at the interface between a subducting slab and the overlying mantle wedge. All these rocks contain carbonates (dolomite-only at P , 1.9 GPa at 900 � C, magnesite-only at P. 2.4 GPa at 900 � C, dolomite þ magnesite in between) and hydrous phases (amphibole, phlogopite) equilibrated at some stages in the garnet stability field. The f O2 values, estimated by analysing the Fe 3þ content (skiagite mole fraction) in garnet, indicate that the Ulten and Sulu peridotites record high oxygen fugacities (FMQ to FMQþ2) and a retrograde path with decreasing P and T. The f O2 values obtained for the Bardane garnet websterites, which record a prograde path with increasing T and P, are up to � 2 log units lower than the FMQ. When combined with data for subduction-zone systems (arc lavas and their mantle sources), the studied ultramafic rocks define a trend of decreasing f O2 with increasing pressure. The Bardane websterites contain C-polymorphs in polyphase inclusions, which precipitated from entrapped metasomatic fluids at ultrahigh pressures. The calculated C-O-H fluid phase in equilibrium with the solid phases consists of mixtures of H2O and CO2. Semi-quantitative estimates for the Ulten and Sulu peridotites, in which C-polymorphs have not been found, and petrographic constraints for the Ulten peridotites indicate that the C-O-H component of the fluid could consist of H2OþCO2.

Petrogenesis of the Miocene volcanism along the İzmir-Balıkesir Transfer Zone in western Anatolia, Turkey: Implications for origin and evolution of potassic volcanism in post-collisional areas

The Miocene volcanic rocks along the İzmir-Balıkesir Transfer Zone along the western margin of the Menderes Core Complex (MCC) in western Anatolian Volcanic Province (WAVP), where strike–slip deformation is dominant, comprise: (Group 1) early-middle Miocene high-K to shoshonitic rocks with high-Mg# and relatively low SiO2, (Group 2) middle Miocene phonolitic rocks with low-Mg# and intermediate SiO2, (Group 3) early-middle Miocene medium- to high-K series from andesites to rhyolites, (Group 4) middle Miocene rhyolites with distinct trace element compositions; and (Group 5) late Miocene high-MgO basalts, K-trachybasalts and (Group 6) late Miocene high-MgO basaltic andesites. The geochemical features of these rocks are comparable with the other Oligocene to Miocene volcanic rocks, but differ from the Eocene volcanic rocks in WAVP.The geochemical features of the most primitive early-middle Miocene Group 1 rocks indicate that they were derived from an anomalously metasomatized lithospheric mantle. The mineralogical and geochemical properties of garnet–amphibole peridotite from the Ulten Zone (UZP), Eastern Alps, which is thought to represent a fossil metasomatic mantle wedge contaminated by continental subduction, is similar to the model mantle composition previously proposed for the genesis of the mafic rocks. Together with the presence of Eocene to early Miocene continental subduction beneath the Aegean-west Anatolia region, this strongly suggests that continental subduction was an important factor in the genesis of the high-MgO shoshonitic to ultrapotassic volcanism in this post-collisional area. The origin of the Group 3 andesitic to rhyolitic rocks includes; (1) lower crustal melting, (2) mixing between lower crustally-derived and mantle-derived melts, and (3) FC-AFC processes. The late Miocene Group 5 and 6 rocks, however, derived from a more depleted mantle source, indicating that the mantle became depleted over time. The rhyolites of Group 4 are most probably crustally-derived.OIB-type Quaternary Kula volcanics (QKV) were emplaced near the centre of the MCC. Among the late Miocene basalts in the region, only the basalts located close to the QKV show transitional geochemistry between the Miocene volcanic rocks and QKV, indicating that asthenospheric contribution to lavas in the region occurred only near the centre of the MCC.

Preservation of old (prograde metamorphic) U–Th–Pb ages in unshielded monazite from the high-pressure paragneisses of the Variscan Ulten Zone (Italy)

Three samples of garnet–kyanite paragneiss from the Variscan Ulten Zone (Northern Italy) were studied in detail for U–Th–Pb monazite dating. Monazite in these gneisses is abundant, shows highly variable grain size and occupies different textural positions: within the matrix, as inclusion in garnet and kyanite, within apatite aggregates. Monazite shows different deformation features as a function of the textural position: enclosed (shielded) monazite is generally more fractured than matrix (unshielded) monazite. The integration of textural information with deformation features and in situ U–Th–Pb analyses by LA–ICP-MS indicates that there is no direct correlation between textural site and monazite ages. Old ages of 351–343Ma, determined on portions of large matrix (unshielded) monazite and on rare domains of monazite shielded by garnet, have been related to a prograde stage of the Variscan metamorphic evolution of the Ulten Zone. Ages of 330–326Ma, which are related to the thermal peak, are recorded by small matrix monazite, external domains of large matrix monazite, and by (domains of) fractured monazite enclosed in garnet and kyanite. Large, old unshielded grains formed as blasts during the prograde metamorphic history and survived the peak metamorphism during which crystallisation/re-crystallisation partially occurred.

H2O content of deep-seated orogenic continental crust: the Ulten Zone, Italian Alps

To estimate the amount of H2O stored at lower crustal levels after burial, we considered the pile of migmatitic paragneisses in the Variscan Ulten Zone as a case study area. We constructed a pseudosection in the system K2O-Na2O-CaO-FeO-MnO-MgO-Al2O3-SiO2-TiO2-H2O for an average paragneiss, a relevant prograde PT path (8.5 kbar, 600°C; 11.5 kbar, 750°C; 14.0 kbar, 1000°C) and H2O contents between 0 and 10 wt.%. Based on an assemblage of garnet + biotite + white mica + kyanite + 20–30 vol.% former melt (now represented mainly by leucosomes composed of plagioclase + quartz), a bulk H2O content of 3.2 ± 1.1 wt.% was estimated for a peak temperature ranging between 770 and 800°C. Before melting, somewhat less than 1.8 wt.% H2O was stored in minerals. Thus, a considerable amount of H2O must have either resided in pore spaces along grain boundaries or, much less likely, infiltrated the paragneisses from below. Evidently, significant quantities of H2O as a free phase may be stored in buried sialic crust, resulting in considerable melting of deep-seated rocks during continent–continent collision.

Metasomatic tourmaline in hybrid contact-bands between gneiss and peridotite in the Ulten zone of the Eastern Italian Alps: chemistry and boron isotopic composition

Ultramafic rocks in the Ulten Zone (UZ) high-pressure melange, in the Eastern Italian Alps, embedded in crustal gneisses, preserve a series of metasomatic hybrid bands generated by infiltration of aqueous fluids. These hybrid bands at the peridotite–gneiss contact comprise phlogopite and anthophyllite with accessory zircon, apatite and allanite. Here, we report the rare occurrence of centimeter-sized crystals of metasomatic tourmaline in two different UZ outcrops, at Mt. Hochwart and Malga Preghena. Tourmaline has a dravite–uvite-rich composition and shows optical and chemical zoning, with slightly variable Ti, Ca and Fe contents. Secondary-ion mass spectrometry (SIMS) analyses provide information on the intragrain B-isotopic zonation of the grains, which is correlated with optical and chemical zoning. The range in δ 11 B is from −7.4 to +0.3‰ for the Mt. Hochwart tourmaline, generally with an isotopically lighter core and heavier rim. The δ 11 B range for Malga Preghena tourmaline is from +1.2‰ in the core to −3.9‰ in the rim. Variable proportions of fluids derived from both the local crustal gneisses and a subducting slab control the B-isotope composition in the metasomatic tourmaline from the UZ. Fluid mixing in hybrid crustal–ultramafic bands can be monitored by metasomatic tourmaline, which may also have a significant impact on the B isotope budget of the subducted slab and the slab–mantle interface.

The peculiar crystal-chemistry of phlogopite from metasomatized peridotites: evidence from laboratory and nature

Periodico di Mineralogia (2011), 80, 1 (Special Issue), 181-197 - DOI: 10.2451/2011PM0015 Special Issue in memory of Sergio Lucchesi The peculiar crystal-chemistry of phlogopite from metasomatized peridotites: evidence from laboratory and nature Paola Comodi 1,* , Sabrina Nazzareni 1 , Patrizia Fumagalli 2 and Gian Carlo Capitani 3 1 Dipartimento di Scienze della Terra, Universita di Perugia, Italy 2 Dipartimento di Scienze della Terra, Universita di Milano, Italy 3 Dipartimento di Scienze Geologiche e Geotecnologie, Universita di Milano Bicocca, Italy *Corresponding author: comodip@unipg.it Abstract Experimental petrology suggested that phlogopite has a peculiar mineral chemistry at high pressure: excess of Si coupled with a decrease in IV Al and deficiency in K+Na. This K-edenite exchange, □ XII Si(K+Na) -1 Al -1 , where □ XII is a vacancy in the interlayer, should imply that phlogopites incorporate significant amount of talc component. At high pressure conditions, however, in a fluid saturated system, a talc component might translate into a 10 A phase component, being the latter phase the product of the reaction talc + H 2 O = 10 A phase occurring at P = 4 - 5 GPa and at T = 600-700 °C. We aim to study the structure of natural and synthetic phlogopites showing this peculiar mineral chemistry. Samples were analysed by single-crystal X-ray diffraction, powder X-ray diffraction with full profile fitting, EMP, SIMS, TEM and Mossbauer spectroscopy. The natural samples were recovered from spinel and garnet wedge peridotites of the Ulten Zone Eastern Italian Alps, (Italy), whereas synthetic ones were obtained from high pressure synthesis in a K-doped lherzolite system. The single crystal X-ray refinements of natural phlogopites, together with the EMP analysis, showed two coupled substitutions: Tschermak (Si + Mg = IV Al + VI Al) and talc exchanges (□ + Si = K + Al), with no octahedral vacancies. The Rietveld refinement of the synthetic samples confirmed the ipersilicic character and K deficiency found with EMPA and SIMS analysis. The c lattice parameter of both synthetic and natural phlogopites positively correlates with the increase of vacancies at the interlayer site, pointing toward the c lattice parameter of the 10A phase. The tetrahedral α rotation angle of natural phlogopites was about 9°, lower than that expected by Tscherma substitution. The present data indicate that the 10 A phase component, instead of the talc component, stabilizes the phlogopite structure by reducing the α rotation under high pressure condition. This increases the pressure conditions needed to reach the upper limit value for the tetrahedral rotation. Key words : phlogopite; 10 A phase; single crystal X-ray refinements; EMPA; SIMS.

Mantle wedge peridotites: Fossil reservoirs of deep subduction zone processes: Inferences from high and ultrahigh-pressure rocks from Bardane (Western Norway) and Ulten (Italian Alps)

The garnet websterites from Bardane (Western Gneiss Region, Norway) derive from cold Archean subcontinental lithosphere involved in Scandian continental subduction to ultrahigh-pressures. Subduction zone metamorphism was promoted by slab fluid infiltration into the cold overlying mantle wedge. The earliest subduction transformation (M3-1) consists of garnet/clinopyroxene exsolution from old pre-subduction orthopyroxene. This stage was likely coeval with fluid input and formation of phlogopite and dolomite rods in the exsolution structures. Magnesite formation after dolomite and entrapment of fluid-related diamond-bearing polyphase inclusions in corona structures around the exsolved orthopyroxenes point to pressure increase to 4.5 GPa (M3-2). Peak pressures of 6.5–7 GPa (c.a. 200 km depth) are witnessed by crystallization of majoritic garnet (M3-3), mostly in veins cutting all the above microstructures. When such veins infiltrate the corona domains, formation of majoritic garnet in coronas is enhanced. This multistage evolution thus envisages episodic fluid influx, favouring rock recrystallization and formation of microdiamond-bearing inclusions and of majoritic garnet veins. These mantle rocks thus record fluid circulation along grain boundaries and microfractures down to 200 km depth in subduction environments. The Ulten Zone peridotites are slices of Variscan mantle wedge. Infiltration of metasomatic subduction fluids favoured transition from spinel-facies to garnet + amphibole ± dolomite parageneses at pressures below 3 GPa. Formation of metasomatized garnet-bearing peridotite mylonites suggest channelled influx of subduction fluids. The incompatible element-enriched signature of all subduction minerals in Bardane indicate that previously depleted websterites have been refertilized by COH subduction fluids. Comparison with the Ulten Zone garnet + amphibole ± dolomite peridotites outlines striking similarities in the metasomatic style and in the COH fluid phase involved. Comparable geochemical fingerprints observed in HP and UHP Ulten and Bardane mantle rocks call for concomitant subduction of the continental crust, that would provide the incompatible element-enriched fluids. For Bardane this implies subduction of crustal slabs to 200 km depth, to release the fluid phases necessary for UHP metasomatism and for majoritic garnet crystallization. Mantle refertilization by crust-derived COH subduction fluids thus operates over a large depth range, down to 200 km depth. The textural features of the Bardane and Ulten Zone mantle rocks indicate that rock recrystallization and refertilization is concomitant with fluid infiltration along channelways, outside which the rocks preserve pre-subduction, long-lasting stories and pristine geochemical characteristics. Comparably with uprising magmas, the subducted continental crust appears to be a quite efficient carrier to the surface of ultradeep mantle tectonic ‘xenoliths’ representing major observatories of diverse metamorphic and geodynamic histories recorded by the Earth's mantle at variable depths.

The Variscan garnet peridotites from the Eastern Alps (Ulten Zone): records of subduction metasomatism in the mantle wedge

The Variscan garnet peridotites from the Eastern Alps (Ulten Zone): records of subduction metasomatism in the mantle wedge

The Variscan garnet peridotites from the Eastern Alps (Ulten Zone): records of subduction metasomatism in the mantle wedge

The Variscan garnet peridotites from the Eastern Alps (Ulten Zone): records of subduction metasomatism in the mantle wedge

The Oxidation State of Metasomatized Mantle Wedge: Insights from C-O-H-bearing Garnet Peridotite

Oxygen fugacity (fO2) is an important parameter in determining the relative stabilities of phase assemblages. Whereas a number of studies have been devoted to determining the redox state of low-pressure assemblages in the mantle system, the fO2 of the supra-subduction mantle wedge is still poorly known. An essential input for fO2 estimates is the determination of the ferric–ferrous iron content of key mantle minerals such as garnet, which can be measured using the ‘flank method’ technique on an electron microprobe. We selected samples of orogenic peridotites from the ultrahigh-pressure Sulu belt (Eastern China) and from the Ulten Zone (Italian Alps) for detailed case studies; these correspond to slices of metasomatized mantle wedge sampled at different depths. They are characterized by the assemblage phlogopite + magnesite +amphibole in equilibrium with olivine, orthopyroxene and Fe3+-bearing garnet. The ‘flank method’ measurements indicate that these pyrope-rich garnets contain Fe3+/ΣFe up to 0·12–0·14. For peridotite mineral assemblages fO2 can be evaluated from equilibria involving the Fe3+-garnet component skiagite (Fe2+3Fe3+2Si3O12) on the basis of Fe3+–Al substitution on the octahedral site, which is sensitive to the garnet oxidation state. We modelled non-ideal mixing of Al and Fe3+ on the octahedral site and non-ideal mixing on the dodecahedral site, with a symmetric regular solution model for reciprocal solid solutions of Ca–Fe2+–Mg–Al–Fe3+-garnet. This allowed us to calculate garnet-peridotite fO2, given the presence of Fe3+ in garnet. Our results indicate that the Sulu and Ulten peridotites record high oxygen fugacities (FMQ to FMQ + 2) compared with garnet peridotite xenoliths from the sub-cratonic mantle equilibrated at similar pressures. The determination of the oxygen fugacity of these hydrate–carbonate-bearing garnet peridotites allowed us to estimate the speciation of C–O–H metasomatic fluids derived from the subducting slab, which are enriched in CO2. The fO2 evaluation of the metasomatized mantle-wedge peridotites, representing the oxygen chemical potential μO2, provides a first step in unravelling the relationship between μO2 and the metasomatic phase assemblage.

Dolomite-bearing orogenic garnet peridotites witness fluid-mediated carbon recycling in a mantle wedge (Ulten Zone, Eastern Alps, Italy)

We document the presence of dolomite ± apatite in orogenic peridotites from the Ulten Zone (UZ, Italian Alps), the remnants of a Variscan mantle wedge tectonically coupled with eclogitized continental crust. These dolomite peridotites are associated with dominant carbonate-free amphibole peridotites, which formed in response to infiltration of aqueous subduction fluids lost by the associated crustal rocks during high-pressure (HP) metamorphism and retrogression. Dolomite-free and dolomite-bearing peridotites share the same metamorphic evolution, from garnet- (HP) to spinel-facies (low-pressure, LP) conditions. Dolomite and the texturally coexisting phases display equilibrium redistribution of rare earth elements and of incompatible trace elements during HP and LP metamorphism; clinopyroxene and amphiboles from carbonate-free and carbonate-bearing peridotites have quite similar compositions. These features indicate that the UZ mantle rocks equilibrated with the same metasomatic agents: aqueous CO2-bearing fluids enriched in incompatible elements released by the crust. The P–T crystallization conditions of the dolomite peridotites (outside the field of carbonatite melt + amphibole peridotite coexistence), a lack of textures indicating quench of carbonic melts, a lack of increase in modal clinopyroxene by reaction with such melts and the observed amphibole increase at the expense of clinopyroxene, all suggest that dolomite formation was assisted by aqueous CO2-bearing fluids. A comparison of the trace element compositions of carbonates and amphiboles from the UZ peridotites and from peridotites metasomatized by carbonatite and/or carbon-bearing silicate melts does not help to unambiguously discriminate between the different agents (fluids or melts). The few observed differences (lower trace element contents in the fluid-related dolomite) may ultimately depend on the solute content of the metasomatic agent (CO2-bearing fluid versus carbonatite melt). This study provides strong evidence that C–O–H subduction fluids can produce ‘carbonatite-like’ assemblages in mantle rocks, thus being effective C carriers from the slab to the mantle wedge at relatively low P–T. If transported beyond the carbonate and amphibole solidus by further subduction, dolomite-bearing garnet + amphibole peridotites like the ones from Ulten can become sources of carbonatite and/or C-bearing silicate melts in the mantle wedge.

Metasomatic reaction bands at the Mt. Hochwart gneiss-peridotite contact (Ulten Zone, Italy): insights into fluid-rock interaction in subduction zones

We investigated the contact zone between peridotite lenses and host gneisses located on the northern side of the Hochwart peak, also known as Vedetta Alta (Ulten Zone, Alto Adige -Sudtirol) where metasomatic contact bands occur. The country rocks are gneisses consisting mainly of quartz, K-feldspar, garnet, kyanite, biotite and muscovite. The ultramafic body consists of a hectometre-sized garnet peridotite and harzburgite lens. The reaction zone shows mineralogic zoning from phlogopite-rich to tremolite-anthophyllite-talc-rich rocks from the host gneiss towards the peridotite. In some cases, lenses of serpentine and talc in association with chlorite, and trondhjemitic pods develop at the ultramafic rocks border to the gneisses. Trondhjemite dikes with pegmatoid texture also crosscut the peridotite body. Phlogopite aggregates with accessory zircon, Cl-apatite and tourmaline and phlogopite-hornblende aggregates also occur. The combination of petrography, mineral chemistry and mass balance calculations constrains the gains and losses of elements during metasomatism. Reaction zone formation involved extensive addition of H2O, K2O and LILE from the fluid, whereas MgO, CaO and Al2O3 were removed from the peridotite. Thus, the formation of the reaction zones between the mantle rocks and the gneisses was triggered by considerable fluid/melt circulation, causing crystallisation of mainly phlogopite, anthophyllite and talc, and the release of a trondhjemitic residual melt. Field mapping provides evidence that the internal structures of the host migmatites (folds) and those of the peridotites (foliation, fluid texture) are discordant. Pseudosection calculations give insights into the P-T conditions (T 660–700°C; P 0.5–0.7 GPa) of metasomatism responsible for the formation of reaction zones, which is related to the retrograde path of the Ulten Zone peridotites. Our results suggest that the redistribution of major and trace elements in subduction zones is strongly influenced by metasomatic reactions occurring at the slab-mantle interface.