Description: 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.

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

Description: Subduction zones provide a key link between the surficial biogenic, atmospheric and hydrospheric geochemical cycles with the Earth’s internal reservoirs. Sediment compaction and dehydration of variably altered oceanic lithosphere during subduction release volatile species (containing e.g., S, H, C, N) to the overlying mantle wedge. In particular, sulfur plays a key role in the formation of porphyry ore deposits and has a major control on redox processes in subduction zones, given it occurs in variable oxidation states from oxidized sulfate (S6+) to reduced sulfide (S2-). Here we studied samples from a contact between serpentinite and partly metasomatized eclogitic metagabbros in the Voltri Massif (Italy). We determined the bulk rock and in situ sulfur isotope composition of pyrite grains and combined this with detailed mineralogic and petrologic investigations. Along the serpentinite-metagabbro contact, the metagabbros are metasomatized to actinolite-chlorite schists and metagabbros rich in epidote and Na- and Na-Ca amphiboles. The serpentinites as well as the actinolite-chlorite schists along the serpentinite-metagabbro contact have very low sulfide contents and provide evidence for the oxidation of sulfides, including formation of Fe-oxides. Sulfur input from the serpentinite-metagabbro contact towards the less metasomatized eclogitic metagabbros is observed. This sulfur input is reflected by bulk rock δ34S values that increase from initially around +1.5‰ in samples distant from the contact to +7.3 to +12.5‰ in samples near the contact. This trend correlates with a general increase in the in situ δ34S values from core to rim of individual pyrite grains. Distinct Co and Ni growth zones in pyrite and variations in the in situ δ34S values indicate multiple phases of pyrite growth during subduction and exhumation of these rocks, with the last stage of pyrite growth clearly related to Mg-metasomatism along the serpentinite-metagabbro contact. Thus, this study provides new insight into processes of sulfur migration during metasomatism of gabbroic rocks within the subducting slab and at the slab–mantle interface.

Description: Primitive arc magmas are more oxidized and enriched in sulfur-34 (34S) compared to mid-ocean ridge basalts. These findings have been linked to the addition of slab-derived volatiles, particularly sulfate, to arc magmas. However, the oxidation state of sulfur in slab fluids and the mechanisms of sulfur transfer in the slab remain inconclusive. Juxtaposed serpentinite and eclogitic metagabbro from the Voltri Massif (Italy) provide evidence for sulfur mobilization and associated redox processes during infiltration of fluids. Using bulk rock and in situ δ34S measurements, combined with thermodynamic calculations, we document the transfer of bisulfide-dominated, 34S-enriched fluids in equilibrium with serpentinite into adjacent metagabbro. We argue that the process documented in this study is pervasive along the subduction interface and infer that subsequent melting of these reacted slab-mantle interface rocks could produce melts that display the characteristic oxygen fugacity and sulfur isotope signatures of arc magmas worldwide.