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 Fe ³⁺ /ΣFe (<0·046) even after the bulk-rocks became strongly enriched in Fe ³⁺ during metasomatism and retrogression (Fe ³⁺ /ΣFe = 0·11–0·23), which was mostly stored in coexistent amphibole and interstitial serpentine. Low Fe ³⁺ /ΣFe in garnet is consistent with ΔlogfO 2 = FMQ-1·7 to FMQ-0·3 at 2 GPa. 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.