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.