The oxygen fugacity ( fO 2 ) of the Earth's mantle at subduction zones exerts a primary control on the genesis of mineral deposits in the overlying magmatic arcs and on speciation of volcanic gases emitted into the atmosphere. However, the processes governing mantle fO 2 such as the introduction of oxidised material by subduction are still unresolved. Here, we present evidence for the reduction of oxidised fluid-borne sulphur and carbon during alteration of depleted mantle by slab fluids at ultra-high pressure in the Bardane peridotite (Western Gneiss Region, Norway). Elevated ferric iron in metasomatic garnet, determined using synchrotron X-ray absorption near edge structure (XANES) spectroscopy, indicates that this process drove oxidation of the silicate assemblage. Our finding indicates that subduction oxidises the Earth's mantle by cycling of sulphur and carbon. LetterPlate tectonics drives recycling of surface material into the Earth's interior, introducing hydrated and oxidised oceanic lithosphere into the mantle at subduction zones (Wood et al., 1990;Evans, 2012). Fluids liberated during dehydration of subducted crust trigger partial melting of the overlying mantle leading to the formation of volcanic arcs, dominated by oxidised rocks (Ballhaus, 1993;Kelley and Cottrell, 2009). Correlation between oxidation of arc lavas and addition of slab material by aqueous fluids to their mantle source has been quantitatively established (Kelley and Cottrell, 2009; Brounce et al., 2014) fluids are somehow responsible for the observed oxidation. However, although calculations suggest that fluid-borne oxidised sulphur may be important (Evans and Tomkins, 2011), the process has not been resolved with physical evidence. Determination of redox processes associated with fluid-mantle interaction cannot be indisputably resolved by studying the product of the arc system (i.e. arc lavas); it is best approached by examining rocks from the deep portion of mantle wedge close to the slab-mantle interface that have been altered by slab fluids, which are preserved as orogenic peridotites.The Western Gneiss Region of Norway hosts several orogenic peridotite bodies that represent a portion of transition zone mantle that upwelled, melted (Stage M1) and accreted to cratonic lithosphere (Stage M2;Spengler et al., 2006). Subsequently, during the Caledonian orogeny, fluids derived from subducting slab locally promoted metasomatism (Stage M3), as recorded by the Bardane peridotite on Fjørtoft island (Brueckner et al., 2002;Van Roermund et al., 2002;Scambelluri et al., 2008). Other portions have not been infiltrated by slab fluids and preserve the original mantle assemblage (M1-M2), exemplified by the Ugelvik peridotite on the island of Otrøy (Brueckner et al., 2002;Spengler et al., 2006). Although there is debate on the origin of metasomatism at Bardane, the trace element and isotopic signature of the metasomatic assemblage are comparable to the effects of typical subduction zone fluids sensu lato (cf. Brueckner et al., 2002;Scambelluri et...

The world-class San Rafael tin (-copper) deposit (central Andean tin belt, southeast Peru) is an exceptionally large and rich (>1 million metric tons Sn; grades typically >2% Sn) cassiterite-bearing hydrothermal vein system hosted by a late Oligocene (ca. 24 Ma) peraluminous K-feldspar-megacrystic granitic complex and surrounding Ordovician shales affected by deformation and low-grade metamorphism. The mineralization consists of NW-trending, quartz-cassiterite-sulfide veins and fault-controlled breccia bodies (>1.4 km in vertical and horizontal extension). They show volumetrically important tourmaline alteration that principally formed prior to the main ore stage, similar to other granite-related Sn deposits worldwide. We present here a detailed textural and geochemical study of tourmaline, aiming to trace fluid evolution of the San Rafael magmatic-hydrothermal system that led to the deposition of tin mineralization. Based on previous works and new petrographic observations, three main generations of tourmaline of both magmatic and hydrothermal origin were distinguished and were analyzed in situ for their major, minor, and trace element composition by electron microprobe analyzer and laser ablation-inductively coupled plasma-mass spectrometry, as well as for their bulk Sr, Nd, and Pb isotope compositions by multicollector-inductively coupled plasma-mass spectrometry. A first late-magmatic tourmaline generation (Tur 1) occurs in peraluminous granitic rocks as nodules and disseminations, which do not show evidence of alteration. This early Tur 1 is texturally and compositionally homogeneous; it has a dravitic composition, with Fe/(Fe + Mg) = 0.36 to 0.52, close to the schorl-dravite limit, and relatively high contents (10s to 100s ppm) of Li, K, Mn, light rare earth elements, and Zn. The second generation (Tur 2)—the most important volumetrically—is pre-ore, high-temperature (>500°C), hydrothermal tourmaline occurring as phenocryst replacement (Tur 2a) and open-space fillings in veins and breccias (Tur 2b) and microbreccias (Tur 2c) emplaced in the host granites and shales. Pre-ore Tur 2 typically shows oscillatory zoning, possibly reflecting rapid changes in the hydrothermal system, and has a large compositional range that spans the schorl to dravite fields, with Fe/(Fe + Mg) = 0.02 to 0.83. Trace element contents of Tur 2 are similar to those of Tur 1. Compositional variations within Tur 2 may be explained by the different degree of interaction of the magmatic-hydrothermal fluid with the host rocks (granites and shales), in part because of the effect of replacement versus open-space filling. The third generation is syn-ore hydrothermal tourmaline (Tur 3). It forms microscopic veinlets and overgrowths, partly cutting previous tourmaline generations, and is locally intergrown with cassiterite, chlorite, quartz, and minor pyrrhotite and arsenopyrite from the main ore assemblage. Syn-ore Tur 3 has schorl-foititic compositions, with Fe/(Fe + Mg) = 0.48 to 0.94, that partly differ from those of late-magmatic Tur 1 and pre-ore hydrothermal Tur 2. Relative to Tur 1 and Tur 2, syn-ore Tur 3 has higher contents of Sr and heavy rare earth elements (10s to 100s ppm) and unusually high contents of Sn (up to >1,000 ppm). Existence of these three main tourmaline generations, each having specific textural and compositional characteristics, reflects a boron-rich protracted magmatic-hydrothermal system with repeated episodes of hydrofracturing and fluid-assisted reopening, generating veins and breccias. Most trace elements in the San Rafael tourmaline do not correlate with Fe/(Fe + Mg) ratios, suggesting that their incorporation was likely controlled by the melt/fluid composition and local fluid-rock interactions. The initial radiogenic Sr and Nd isotope compositions of the three aforementioned tourmaline generations (0.7160–0.7276 for 87Sr/86Sr(i) and 0.5119–0.5124 for 143Nd/144Nd(i)) mostly overlap those of the San Rafael granites (87Sr/86Sr(i) = 0.7131–0.7202 and 143Nd/144Nd(i) = 0.5121–0.5122) and support a dominantly magmatic origin of the hydrothermal fluids. These compositions also overlap the initial Nd isotope values of Bolivian tin porphyries. The initial Pb isotope compositions of tourmaline show larger variations, with 206Pb/204Pb(i), 207Pb/204Pb(i), and 208Pb/204Pb(i) ratios mostly falling in the range of 18.6 to 19.3, 15.6 to 16.0, and 38.6 to 39.7, respectively. These compositions partly overlap the initial Pb isotope values of the San Rafael granites (206Pb/204Pb(i) = 18.6–18.8, 207Pb/204Pb(i) = 15.6–15.7, and 208Pb/204Pb(i) = 38.9–39.0) and are also similar to those of other Oligocene to Miocene Sn-W ± Cu-Zn-Pb-Ag deposits in southeast Peru. Rare earth element patterns of tourmaline are characterized, from Tur 1 to Tur 3, by decreasing (Eu/Eu*)N ratios (from 20 to 2) that correlate with increasing Sn contents (from 10s to >1,000 ppm). These variations are interpreted to reflect evolution of the hydrothermal system from reducing toward relatively more oxidizing conditions, still in a low-sulfidation environment, as indicated by the pyrrhotite-arsenopyrite assemblage. The changing textural and compositional features of Tur 1 to Tur 3 reflect the evolution of the San Rafael magmatic-hydrothermal system and support the model of fluid mixing between reduced, Sn-rich magmatic fluids and cooler, oxidizing meteoric waters as the main process that caused cassiterite precipitation.

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Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ11B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ11B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO2 and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).

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