doi: 10.7185/geochemlet.2011 Oxygen fugacity ( fO 2 ) is a controlling factor of the physics of Earth's mantle; however, the mechanisms driving spatial and secular changes in fO 2 associated with convergent margins are highly debated. We present new thermodynamic models and petrographic observations to predict that oxidised sulfur species are produced during the subduction of altered oceanic crust. Sulfur loss from the subducting slab is a function of the protolith Fe 3+ /ΣFe ratio and subduction zone thermal structure, with elevated sulfur fluxes predicted for oxidised slabs in cold subduction zones. We also predict bi-modal release of sulfur-bearing fluids, with a low volume shallow flux of reduced sulfur followed by an enhanced deep flux of sulfate and sulfite species, consistent with oxidised arc magmas and associated copper porphyry deposits. The variable SO x release predicted by our models both across and among active margins may introduce fO 2 heterogeneity to the upper mantle.
The Greater Himalayan Sequence (GHS) has commonly been treated as a large coherently deforming high‐grade tectonic package, exhumed primarily by simultaneous thrust‐ and normal‐sense shearing on its bounding structures and erosion along its frontal exposure. A new paradigm, developed over the past decade, suggests that the GHS is not a single high‐grade lithotectonic unit, but consists of in‐sequence thrust sheets. In this study, we examine this concept in central Nepal by integrating temperature–time (T–t) paths, based on coupled Zr‐in‐titanite thermometry and U–Pb geochronology for upper GHS calcsilicates, with traditional thermobarometry, textural relationships and field mapping. Peak Zr‐in‐titanite temperatures are 760–850°C at 10–13 kbar, and U–Pb ages of titanite range from c. 30 to c. 15 Ma. Sector zoning of Zr and distribution of U–Pb ages within titanite suggest that diffusion rates of Zr and Pb are slower than experimentally determined rates, and these systems remain unaffected into the lower granulite facies. Two types of T–t paths occur across the Chame Shear Zone (CSZ). Between c. 25 and 17–16 Ma, hangingwall rocks cool at rates of 1–10°C/Ma, while footwall rocks heat at rates of 1–10°C/Ma. Over the same interval, temperatures increase structurally upwards through the hangingwall, but by 17–16 Ma temperatures converge. In contrast, temperatures decrease upwards in footwall rocks at all times. While the footwall is interpreted as an intact, structurally upright section, the thermometric inversion within the hangingwall suggests thrusting of hotter rocks over colder from c. 25 to c. 17–16 Ma. Retrograde hydration that is restricted to the hangingwall, and a lithological repetition of orthogneiss are consistent with thrust‐sense shear on the CSZ. The CSZ is structurally higher than previously identified intra‐GHS thrusts in central Nepal, and thrusting duration was 3–6 Ma longer than proposed for other intra‐GHS thrusts in this region. Cooling rates for both the hangingwall and footwall of the CSZ are comparable to or faster than rates for other intra‐GHS thrust sheets in Nepal. The overlap in high‐T titanite U–Pb ages and previously published muscovite 40Ar/39Ar cooling ages imply cooling rates for the hangingwall of ≥200°C/Ma after thrusting. Causes of rapid cooling include passive exhumation driven by a combination of duplexing in the Lesser Himalayan Sequence, and juxtaposition of cooler rocks on top of the GHS by the STDS. Normal‐sense displacement does not appear to affect T–t paths for rocks immediately below the STDS prior to 17–16 Ma.
Subduction is a key component of Earth's long‐term sulfur cycle; however, the mechanisms that drive sulfur from subducting slabs remain elusive. Isotopes are a sensitive indicator of the speciation of sulfur in fluids, sulfide dissolution‐precipitation reactions, and inferring fluid sources. To investigate these processes, we report δ34S values determined by secondary ion mass spectroscopy in sulfides from a global suite of exhumed high‐pressure rocks. Sulfides are classified into two petrogenetic groups: (1) metamorphic, which represent closed‐system (re)crystallization from protolith‐inherited sulfur, and (2) metasomatic, which formed during open system processes, such as an influx of oxidized sulfur. The δ34S values for metamorphic sulfides tend to reflect their precursor compositions: −4.3 ‰ to +13.5 ‰ for metabasic rocks, and −32.4 ‰ to −11.0 ‰ for metasediments. Metasomatic sulfides exhibit a range of δ34S from −21.7 ‰ to +13.9 ‰. We suggest that sluggish sulfur self‐diffusion prevents isotopic fractionation during sulfide breakdown and that slab fluids inherit the isotopic composition of their source. We estimate a composition of −11 ‰ to +8 ‰ for slab fluids, a significantly smaller range than observed for metasomatic sulfides. Large fractionations during metasomatic sulfide precipitation from sulfate‐bearing fluids, and an evolving fluid composition during reactive transport may account for the entire ~36 ‰ range of metasomatic sulfide compositions. Thus, we suggest that sulfates are likely the dominant sulfur species in slab‐derived fluids.
Titanite is a potentially powerful U–Pb petrochronometer that may record metamorphism, metasomatism, and deformation. Titanite may also incorporate significant inherited Pb, which may lead to inaccurate and geologically ambiguous U–Pb dates if a proper correction is not or cannot be applied. Here, we present laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS)‐derived titanite U–Pb dates and trace element concentrations for two banded calcsilicate gneisses from south‐central Maine, USA (SSP18‐1A and SSP18‐1B). Single spot common Pb‐corrected dates range from 400 to 280 Ma with ±12–20 Ma propagated 2SE. Titanite grains in sample SSP18‐1B exhibit regular core‐to‐rim variations in texture, composition, and date. We identify four titanite populations: (1) 397 ± 5 Ma (95% CL) low Y + HREE cores and mottled grains, (2) 370 ± 7 Ma high Y + REE mantles and cores, (3) 342 ± 6 Ma cores with high Y + REE and no Eu anomaly, and (4) 295 ± 6 Ma LREE‐depleted rims. We interpret the increase in titanite Y + HREE between ca. 397 and ca. 370 Ma to constrain the timing of diopside fracturing and recrystallization and amphibole breakdown. Apparent Zr‐in‐titanite temperatures (803 ± 36°C at 0.5 ± 0.2 GPa) and increased XDi suggest a thermal maximum at ca. 370 Ma. Population 3 domains dated to ca. 342 Ma exhibit no Eu anomaly and are observed only in compositional bands dominated by diopside (>80 vol%), suggesting limited equilibrium between titanite and plagioclase. Finally, low LREE and high U/Th in Population 4 titanite dates the formation of hydrous phases, such as allanite, during high XH2O fluid infiltration at ca. 295 Ma. In contrast to the well‐defined date–composition–texture relationships observed for titanite from SSP18‐1B, titanite grains from sample SSP18‐1A exhibit complex zoning patterns and little correlation between texture, composition, and date. We hypothesize that the incorporation of variable amounts of radiogenic Pb from dissolved titanite into recrystallized domains resulted in mixed dates spanning 380–330 Ma. Although titanite may reliably record multiple phases of metamorphism, these data highlight the importance of considering U–Pb data along with chemical and textural data to screen for inherited radiogenic Pb.
Siderite (FeCO 3 ) and rhodochrosite (MnCO 3 ) are two interesting carbonate minerals, which normally occur in hydrothermal deposits on deep-sea altered oceanic crust. Despite the ubiquity of carbonates in the slab, little is known of the physicochemical behavior of siderite and rhodochrosite at high-pressure (P) and high-temperature (T) conditions during slab subduction. In this study, we characterized the Raman vibrational spectra of natural siderite and rhodochrosite up to 47 GPa and 1100 K in an externally-heated diamond-anvil cell (DAC). Experimental results show that the Raman frequency shifts ( i ) for siderite and rhodochrosite are a function of both P and T, and the effect of the P-T cross derivative term cannot be neglected, especially at high-P and high-T conditions.Based on the functional relationship of i -P-T, the P-T calibrants of siderite and rhodochrosite are developed, respectively. This is significant for studying the water-carbonate interaction at high P-T conditions in a DAC because the undesired change of the experimental system from traditional pressure sensors (e.g., ruby, quartz) in a reaction chamber can be avoided. Like previous studies, we observed a sharp spin transition at ~ 45 GPa in siderite and a phase transition from MnCO 3 -I to MnCO 3 -II at ~ 46 GPa for rhodochrosite at room temperature. Furthermore, we determined the isobaric and isothermal equivalents of the mode Grüneisen parameter ( iT , iP ) and the anharmonic parameter (a i ) for each Raman mode of siderite and rhodochrosite. The i /P, i /T, iT, This is the peer-reviewed, final accepted version for American Mineralogist, published by the Mineralogical Society of America.The published version is subject to change. Cite as Authors (Year) Title. American Mineralogist, in press.
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