fO2 Values Research Articles

The Significance of Hypermagnesian Clinopyroxene in the Yanisvaara Ultrabasic Complex, Kola Peninsula, Russia

Abstract Two generations of hypermagnesian clinopyroxene [92 < Mg# < 98] are found in the Yanisvaara ultrabasic complex in the northwestern Lapland–Belomorian Belt, Kola Peninsula, Russia. Grains of a first generation (Wo47.3–50.7En46.5–49.4Fs2.5–3.5), 0.2–0.4 mm across, are attributed to a reaction in which tremolite + clinopyroxene replaced orthopyroxene. The second generation generally attains even more strongly magnesian compositions (Wo46.5–50.9En47.5–50.8Fs1.0–3.2). It is sporadically developed as submicrometric rim- or veinlet-like grains associated with tremolite and domains of fresh olivine with Mg# in the range 80.5–82.5 to 87.7–88.0. The later generation of clinopyroxene crystallized at elevated values of fO2 under closed-system autometasomatic conditions rather than during regional metamorphism. The compositions attained in three representative samples are highly magnesian, but characteristically poor in Cr compared to primary clinopyroxene. Compositions of the accompanying silicate, oxide, and sulfide minerals are provided. A novel Ni-Mn oxyspinel may be related to hausmannite. Yanisvaara and coeval subvolcanic komatiitic complexes are inferred to have degassed, which promoted the rapid rise in fO2 and indirectly promoted the buildup of Mg in the late clinopyroxene.

First widespread occurrence of rare phosphate chladniite in a meteorite, winonaite Graves Nunataks (GRA) 12510: Implications for phosphide–phosphate redox buffered genesis in meteorites

Abstract The first widespread occurrence of rare Na-, Ca-, and Mg, Mn, Fe-bearing phosphate chladniite was observed in meteorite Graves Nunataks (GRA) 12510, which is a primitive achondrite that sits within the winonaite class. Numerous 1–500 µm chladniite grains were found, often on the margins between silicate clasts and the kamacite portions of the large metal veins that permeated through the sample. The largest chladniite grains are associated with merrillite, kamacite, taenite, troilite, albite, forsterite, diopside, and enstatite, with a few tiny chladniite grains and an apatite grain enclosed within merrillite. GRA 12510s average chladniite composition is Na2.7Ca1.25(Mg10.02Mn0.69Fe0.20)Σ10.91(PO4)9. Electron backscattered diffraction (EBSD) patterns indicate varying degrees of nucleation and growth of chladniite grains. Additionally, the first pure Raman spectrum of chladniite is described here, revealing primary ν1 bands at 954, 974, and especially 984 cm–1. The co-occurrence and close association of merrillite, apatite, chladniite, and P-bearing metallic phases within GRA 12510 suggests that the fO2 of IW-2 to IW-4 is an intrinsic property of the precursor chondritic material, and the phosphate-phosphide reaction may have buffered the final winonaite and IAB iron meteorite phase assemblages. Altogether, chladniite appears to form alongside other phosphates, with their chemistries reflecting the diverse environment of their formation. Meteoritic chladniite likely formed through subsolidus oxidation of schreibersite, scavenging Na from albite, Ca from diopside, Mg from enstatite/forsterite, Fe from kamacite/taenite, and Mn from alabandite/chromite when available. A P0-P5+ redox-buffered environment also has implications for thermometry and fast cooling rates, although more experiments are needed to extrapolate powder reaction rates to those of larger crystals. Furthermore, phosphide-phosphate buffered experiments may aid in investigating equilibrium chemistry at fO2 values between IW-2 and IW-4, which have been challenging to explore experimentally due to the limited availability of solid metal-metal oxide buffers between IW (Fe-FeO) and IW-5 (Cr-Cr2O3) at temperatures and pressures relevant to planetary interiors. Future investigations of phosphide-phosphate redox-buffered genesis at fO2 values between IW-2 and IW-4 have important implications for primitive meteorite constituents (e.g., CAI values), partially differentiated planetesimals and planets, including Mercury and core formation on Earth.

Quantitative redox measurements for hydrothermal experiments conducted in cold-seal pressure vessels

The cold-seal pressure vessel (CSPV) is a commonly-used apparatus for hydrothermal experiments performed at crustal temperature (T)–pressure (P) conditions. The redox states of the samples in CSPV hydrothermal experiments are normally controlled by the pressure medium, by using oxygen buffers, or with the Shaw membrane technique. Although these techniques have been widely used, the actual redox states of the samples are not necessarily the expected values and need to be quantitatively measured. In this study, by using CoPd, NiPd, and (NiMn)O redox sensors, quantitative redox measurements have been conducted in H2O-pressurized Ni-superalloy (Inconel 713 LC) CSPVs at 700–800 °C and 200 MPa. Oxygen fugacities (fO2) of the H2O pressure medium in three CSPVs used in this study were measured, and their log fO2 values were − 13.11 ± 0.06 (Ni–NiO (NNO) + 0.7), − 13.05 ± 0.06 (NNO + 0.8) and − 12.68 ± 0.07 (NNO + 1.1), comparable with those reported previously. By placing an open capsule containing Ni powder below the sample capsule, the fO2 of the H2O pressure medium can be adjusted to reach that of the NNO buffer (NNO to NNO + 0.2). For the MnO–Mn3O4, Ni–NiO, and Co–CoO oxygen buffers, a steady-state fO2 was always achieved for each buffer at a fixed P-T condition. Measured log fO2 values for the Ni–NiO and Co–CoO buffers are in good agreement with theoretical values calculated from thermodynamic data and also with previous results obtained from vessels pressurized with Ar. The log fO2 values determined for the MnO–Mn3O4 buffer, about 0.3 log unit lower than the theoretical values, are consistent with previous values obtained from vessels pressurized with Ar. These results suggest that the use of H2O pressure medium would not perturb the equilibrium redox states of the oxygen buffers. In addition, we developed a miniature sensor that is small enough to be loaded together with other sample material, allowing the monitoring of fO2 in actual experiments.

Using zircon and apatite chemistry to fingerprint porphyry Cu – Mo ± Au mineralization in the Delamerian Orogen, South Australia

To evaluate the fertility of porphyry mineralization in the Delamerian Orogen (South Australia), zircon and apatite from four prospects, including Anabama Hill, Netley Hill, Bendigo, and Colebatch, have been analyzed by LA-ICP-MS and electron microprobe. The zircon is characterized by heavy REEs enrichment relative to light REEs, high (Ce/Nd)N (1.3–45), and weak to moderate negative Eu/Eu* (0.2–0.78). The apatite has right-sloped REE patterns with variably negative to positive Eu anomalies. Low Mg (< 670 ppm) and Sr/Y ratios (< 5) in apatite likely illustrate fractional crystallization trends for the granitic melts in shallow crust. The Yb/Gb and Eu/Eu* in zircon reveal that intrusions at Anabama Hill, Netley Hill, and Bendigo underwent fractional crystallization controlled by amphibole (< 50–60%), garnet (< 15%), apatite (< 0.6%), and/or titanite (< 0.3%). These stocks have average fO2 values reported relative to fayalite-magnetite-quartz buffer (ΔFMQ), from 0.7 ± 0.9 to 2.1 ± 0.4, ascribed to prolonged magmatic evolution or sulfur degassing during post-subduction processes. Our data imply that both Anabama and Bendigo complexes experienced prevalent (garnet-) amphibole crystallization from hydrous melts that have moderately high oxidation (ΔFMQ + 1 to + 3) and elevated sulfur-chlorine components (Anabama, 37 ± 9 to 134 ± 83 ppm S and 0.30 ± 0.24 to 0.64 ± 0.89 wt% Cl; Bendigo, 281 ± 178 to 909 ± 474 ppm S and 0.45 ± 0.47 to 3.01 ± 1.54 wt% Cl). These are crucial ingredients to form porphyry Cu–Mo ± Au ores with economic significance, which provides encouragement for mineral exploration in this orogen.

Zircon compositional systematics from Devonian oxidized I-type granitoids: examination of porphyry Cu fertility indices in the New Brunswick Appalachians, Canada

Zircon is a common, widely distributed accessory mineral in most igneous rocks and its refractory nature records magmatic evolution in terms of oxygen and U-Th-Pb isotopes, and trace-element contents all of which reflect the intrinsic physio-chemical evolution of the magmatic systems in which it crystallized. Zircon compositions can be used as an indicator of relative fertility of hypabyssal intrusions in terms Cu ± Mo ± Au porphyry mineralization. To further characterize syn- to post-collisional adakitic Devonian oxidized I-type granitoids in the New Brunswick (specifically, those with Cu ± Mo ± Au porphyry-style mineralization), LA-ICP-MS analyses (guided by µXRF-EDS mapping and SEM-BSE imaging of polished thin sections) of zircons from 13 granitoids was conducted. The zircons studied were similar in terms of their textures (homogenous cores, patchy zoning, oscillatory zoning, and some unzoned zircon); however, they have a wide range of trace- and minor-element (Hf, HREE, Y, Th, U) compositions. Specifically, Zr/Hf ranges between 24–60, whereas Th/U ranges between 0.15 and 5.37. The presence of inherited zircon affects the concentrations of Th and U, as well as other key elements. Estimated crystallization temperatures of granitoids, ranging from 737 to 899°C, were calculated via Ti-in-zircon geothermometry assuming reduced TiO2 and SiO2 activities. The calculated log fO2 values for zircons from some of these granitoids indicate a highly oxidized magmatic signature. Zr/Hf, Eu/Eu⁎, and (Eu/Eu⁎)/Y in zircon, as well as zircon (Ce/Nd)/Y are some of the best indicators of porphyry fertility. The Ce/Ce* in zircon exhibit a large range (1.1–590), with higher Ce/Ce* reflecting more metallogenically favourable oxidizing conditions. If Eu/Eu⁎ in zircon is ≥0.4 (relatively oxidized conditions), it indicates a high potential for an ore-forming porphyry Cu mineralizing system. Lower Eu contents reflect relatively reducing conditions, as Eu anomalies vary with oxygen fugacity as well, and the relative abundance of Eu2+ is higher, but does not substitute into the zircon lattice. The evidence extracted from analyzing the zircon composition within New Brunswick’s I-type granitoids indicates the fertility of these hypabyssal intrusions.

Contrasting Tectonomagmatic Conditions for Coexisting Iron Oxide-Apatite Deposits and Porphyry and Skarn Cu ± Au Deposits in the Middle-Lower Yangtze River Metallogenic Belt, China

Abstract Porphyry Cu ± Mo ± Au and iron oxide-apatite (IOA) deposits rarely occur in spatial and temporal proximity in Phanerozoic arc-related settings, and the formation of these mineral deposit types in an evolving arc setting remains poorly understood. Specifically, the roles of magma composition and the tectonic regime remain the subject of some debate. Here, we systematically estimated the P-T-fO2 conditions and H2O-S-Cl contents for dioritic to granodioritic source magmas for porphyry and skarn Cu ± Au (150–135 Ma) and IOA deposits (~130 Ma) that formed in transpressional and transtensional settings in the Middle-Lower Yangtze River metallogenic belt, China. Our estimates show that, compared to IOA deposits, the porphyry- and skarn-related magmas were relatively felsic, cooler, and more hydrous. These geochemical features are consistent with the tectonic transition from subduction to slab rollback of the paleo-Pacific plate in the East Asia continental margin at &amp;lt;135 Ma and concomitant crustal extension and steepening of the regional geothermal gradient. Apatite data reveal that the silicate melts associated with the porphyry and skarn Cu ± Au and IOA deposits had comparable predegassed S concentrations (~0.13 ± 0.06 wt % vs. ~0.16 ± 0.09 wt % on average), but that IOA-related melts contained higher predegassed Cl/H2O ratios (~0.11 ± 0.03 vs. ~0.04 ± 0.03 for porphyry- and skarn-related magmas) that decreased by one order of magnitude after magmatic degassing. Magmatic fO2 estimated using zircon and amphibole, reported in log units relative to the fayalite-magnetite-quartz (FMQ) redox buffer, gradually increased during cooling of the porphyry- and skarn-related magmas (ΔFMQ +0.7 to +2.5) at 950° to 800°C and decreased to ΔFMQ +1 at 700°C owing to fractionation of Fe2+-rich minerals and subsequent S degassing, respectively. In contrast, the magmatic fO2 values for the IOA-related source magmas varied significantly from ΔFMQ –1.5 to ΔFMQ +2.5 but generally show an increasing trend with cooling from 970° to 700°C that probably resulted from variable degrees of evaporite assimilation, fractionation of Fe2+-rich minerals, and Cl degassing. These results are consistent with the hypothesis that Cl enrichment of the IOA-related source magmas played a determinant role in their formation. We propose that the porphyry and skarn Cu ± Au deposits in the Middle-Lower Yangtze River metallogenic belt formed in a transpressional setting in response to paleo-Pacific flat-slab subduction that favored storage and evolution of S-rich hydrous ore-forming magmas at variable crustal levels. A subsequent extensional setting formed due to slab rollback, leading to rapid degassing of Cl-rich IOA-related magmas. For the latter scenario, assimilation of evaporite by mafic to intermediate magmas would lead to an enrichment of Cl in the predegassed magmas and subsequent exsolution of hypersaline magmatic-hydrothermal fluid enriched in Fe as FeCl2. This Fe-rich ore fluid efficiently transported Fe to the apical parts of the magma bodies and overlying extensional normal faults where IOA mineralization was localized. The concomitant loss of S, H2O, and Cu with Cl by volcanic outgassing may have inhibited sulfide mineralization at lower temperatures.

The Olivine-Spinel-aSiO2melt (OSaS) Oxybarometer: A New Method for Evaluating Magmatic Oxygen Fugacity in Olivine-Phyric Basalts

Abstract The compositions of cotectic olivine-spinel pairs in mafic magmas provide information on the oxygen fugacity of their host liquid, which can be accessed with a thermodynamic analysis of the olivine-spinel-liquid peritectic reaction: 3 F e 2 S i O 4 o l i v + O 2 s y s = 2 F e 3 O 4 s p + 3 S i O 2 m e l t The extraction of redox information from cotectic olivine-spinel pairs requires a well-defined silica activity value (aSiO2melt) for the melt of interest, as well as a method to calculate aFe2SiO4oliv and aFe3O4sp from chemical analyses of olivine and spinel, respectively. In this work, we develop a new olivine-spinel-aSiO2melt (OSaS) oxygen barometer that utilizes MELTS to obtain values of aSiO2melt, which are used with values aFe2SiO4oliv and aFe3O4sp determined from established solution models for olivine and spinel. We find that two implementations of the spinel-liquid peritectic equilibria can successfully generate magmatic oxygen fugacity values, (1) using a combination of mineral activity models from the literature (classical-OSaS) and aSiO2melt determined from MELTS, and (2) directly from chemical potentials obtained from MELTS, where a correction is added to the MELTS-derived chemical potentials for the magnetite component of the spinel (MELTS-OSaS). The two implementations of the OSaS were tested by using each model to recover the experimentally reported fO2 values for a dataset consisting of 50 olivine-spinel-glass assemblages derived from 14 published experimental studies. This dataset was filtered to remove potential disequilibrium phase assemblages, experiments with failed redox buffers, and poor-quality EMP analyses. Data quality metrics for the dataset filtration included Fe-Mg partitioning between olivine and melt, Fe-Mg partitioning between olivine-spinel, and an examination of whether aSiO2melt values were consistent with the reported phase assemblages. The classical-OSaS implementations reproduced the fO2 values reported from the experimental dataset with a standard error estimate (SEE) of ±0.39, root mean standard error (RMSE) of ±0.40 and average deviation of ±0.31. In testing the MELTS-OSaS model, we identified that the solution model for magnetite underpredicted the values of aFe3O4sp; therefore, we used the 50 experiments to assign a correction to the MELTS-predicted chemical potentials of magnetite. We tested 35 the MELTS-OSaS model with the magnetite correction on a dataset of 18 additional buffered experiments, filtered for redox equilibrium and not included in the original experimental dataset. We find that the MELTs-OSaS model, which includes the correction for the magnetite chemical potential, reproduces fO2 values for the 18 experiments with an SEE of ±0.20, root mean standard error (RMSE) of ±0.23 and average deviation of ±0.18. The OSaS oxybarometer can return magmatic fO2 values with a standard error of ± 0.20 to 0.39 log units, depending on the model selected, provided that the olivine-spinel cotectic temperature is known to an accuracy of ±25°C, the H2O content of the melt can be estimated within ±1.5wt%, and that the crystallization pressure of the olivine-spinel pair is &amp;lt; 500 MPa. We also propose that the OSaS models can be applied to experimental run products to determine or confirm oxygen fugacity values. We additionally suggest that the careful application of the OSaS oxybarometer can provide a reliable and robust alternative for performing redox studies on samples that do not contain sufficient glassy material to support the application of spectroscopic techniques (i.e., XANES and Mössbauer).

Fluids in the Shallow Mantle of Southeastern Australia: Insights from Phase Equilibria

Abstract Small amounts of water (10s to 100s of ppm) can have a profound effect on the properties of mantle peridotites, including viscosities, conductivities, and melting temperatures. Measuring the water content of nominally anhydrous minerals (NAMs) has provided insight into the amounts of water contained within mantle rocks. However, converting from NAM water contents to the activity of H2O is non-trivial. Equilibria involving amphibole can be used to determine values of the activity of H2O (aH2O) at the time of mineral equilibration. This approach yields low values of the activity of H2O (&amp;lt; 0.3) for four peridotite xenoliths from Southeastern Australia. These four xenoliths also record values of oxygen fugacity (fO2) that range from -0.2 to -1.2 (Log units relative to FMQ). All these values of fO2 are inconsistent with the presence of a CH4-rich fluid (too oxidizing), and the lowest value of oxygen fugacity, as recorded by one sample, is inconsistent with the presence of a CO2-rich fluid.

Mineral chemistry and thermobarometry of Jurassic arc granitoids: implications for petrotectonic and unroofing history of the southern Colombian Andes

Abstract The Jurassic magmatic record in the southern Colombian (Northern Andes) includes numerous subduction-related I-type calc-alkaline granitoids with diverse structures and textures, formed in two main episodes at ∼195 to 165 Ma and ∼165 to 145 Ma. We provide new insights into the mineral chemistry, estimates of intensive parameters and petrogenetic processes of 12 plutonic occurrences in the region, grouped in 4 petrographic associations. Primary mineral assemblages include labradorite-to-oligoclase, alkali feldspars, ferroan enstatite, Mg-rich augite to ferroan-diopside, tschermakite to hastingsite and hornblende and Mg-rich annite; Fe-rich phlogopite and actinolite are post-magmatic phases. Amphibole chemistry indicates that the older (195–165 Ma) Jurassic bodies formed from relatively highly oxidized (fO2 values buffered at −0.1 ≤ NNO ≤ +1.4) hydrous (∼4 to 6 wt % H2O) magmas and their differentiation involves significant crustal assimilation and/or magma mixing, fractional crystallization and late-magmatic re-equilibration processes. In contrast, the younger (165–145 Ma) Jurassic intrusives, derived from subducted-modified mantle sources, record moderately lower oxidized hydrous conditions (fO2 values −0.7 to 0.8 ≤ NNO; ∼5 wt % H2O) with magma evolution mainly controlled by fractional crystallization and late-magmatic re-equilibration processes. Clinopyroxene-only, amphibole-only and amphibole-plagioclase thermobarometry estimations suggest that the Jurassic occurrences crystallized over variable temperature (647°C–1087°C) and pressure (0.7–6.3 kbar) conditions, corresponding to emplacement depths ranging from ∼15, ∼8 to 11, ∼5 to 7 and &lt;4 km along the arc crustal column. The obtained data combined with time evolution allow the identification of exhumed and fragmented arc blocks in the Jurassic magmatic system and provide an essential link between the orogenic deformation event poorly constrained in the Northern Andes.

Mantle plumes sample heterogeneous mixtures of oxidized and reduced lithologies

Constraining the heterogeneity of oxygen fugacity (fO2) in the upper mantle is important for understanding the role of the deep Earth in determining the redox state of the atmosphere. Measuring the fO2 of primitive, mantle-derived basalts is a means with which to constrain mantle fO2 heterogeneity. Trace element systematics of 721 primitive olivine crystals from fifteen Icelandic picrites are reported, and these data are used with previously published bulk rock compositions to constrain their magmatic fO2. These fO2 values were compared with previously reported ocean island basalt (OIB) fO2 data calculated using identical methods, showing that fO2 is negatively correlated with parental magma MgO and positively correlated with bulk rock La/Yb, trends which were not evident in previous, smaller, global ocean island basalt datasets. These correlations cannot reasonably be the result of fractional crystallization, differential volcanic degassing, or differential partial melting of a typical homogenous mantle peridotite. Instead, differential partial melting of a heterogeneous source which preferentially sampled oxidized fusible lithologies at low melt fractions and diluted such signatures with depleted peridotite melts at high melt fractions likely caused the observed fO2-MgO-isotopic trends. These conclusions further reinforce that the mantle should not be modeled as a homogenous peridotite, but instead as a heterogeneous, non-equilibrated mixture of enriched “blebs” in a matrix of depleted peridotite, and that degree of partial melting is an important control on what portions of the mantle are detectable in igneous rocks.

The role of high oxygen fugacity on genesis of the late Cenozoic Abaga basalts in Xilin Gol League, Inner Mongolia, China

ABSTRACT The Abaga basalts, which erupted within an intraplate background in the late Cenozoic, are situated in eastern central Inner Mongolia. Previous studies have explored the genesis of these basalts, which were influenced by the subduction of slab. Although trace element ratios demonstrate that altered oceanic crust (AOC) and sediments have contributed to the genesis of the basalts, limited information about the detailed percentages of mixing among sediments, AOC, and depleted mantle (DM) based on Sr‒Nd‒Pb isotopic values has been reported. In this study, we modelled the possible mixing percentages among AOC, DM, and sediments. The calculated results illustrate that a proportion of 80% DM, 16% AOC, and 4% sediments is appropriate for interpreting the Sr‒Nd‒Pb isotopic variation of the basalts. In addition, the associated major and trace elements of olivine and the partition coefficient of V between olivine and melt are used to estimate the crystallization temperatures of the olivine phenocrysts and oxygen fugacity of the basalts. The calculated results display that the olivine mainly crystallized between 1248 and 1293°C (standard error estimate: 51°C), and the fO2 values of the Abaga basalts range from FMQ + 0.14 to FMQ + 1.46 (FMQ, fayalite–magnetite–quartz buffer). The estimated oxygen fugacity values plot in the range of island arc basalts (from FMQ to FMQ + 2) but are higher than those of both mid-ocean ridge basalt (MORB) (from FMQ-0.4 to FMQ + 0.5) and Abaga xenoliths (from FMQ-1.55 to FMQ + 0.53), which indicates that the basaltic melts were more oxidized than those of MORB and the Abaga lithospheric mantle. Furthermore, the primary magma and the corresponding mantle source were more oxidized than MORB. The Ba/Th and Ce/Pb ratios of the basalt present positive correlations with fO2 values, demonstrating that the addition of sediments and oceanic crust into the mantle source may have contributed to increasing the fO2 values of the basalts.

Variations of Sr–Nd–Hf–O isotopes and redox conditions across a Neoproterozoic arc magmatic belt in the western margin of the Yangtze craton

We use zircon trace elements and HfO isotopes, plus whole-rock chemical and SrNd isotope compositions to investigate the controls on the chemistry of Neoproterozoic arc magmas. The samples are from the gabbrodiorite intrusion of the Gaojiacun mafic-ultramafic complex and from the Tongde diorite batholith of the Panxi Neoproterozoic magmatic belt in the western margin of the Yangtze craton, western China. Zircon UPb ages reveal that both intrusions are coeval, emplaced at ∼820 Ma. Major element compositions of whole rocks and major silicate minerals indicate that the Tongde batholith formed from more evolved magma than the parental magma for the Gaojiacun intrusion. The mantle-normalized trace element patterns of whole rocks from both intrusions are similar, showing light REE enrichments and pronounced negative NbTa anomalies. The SrNd isotopic compositions of the whole rocks are also similar, plotting within or very close to the mantle array, indicating no to minor contamination with the upper crust. Zircon HfO isotopes indicate that the Gaojiacun magma has much higher ƐHf (6.26 ± 0.52) and δ18O (7.0 ± 0.3 ‰) than the Tongde magma (ƐHf = 4.81 ± 0.39; δ18O = 5.7 ± 0.2 ‰). The δ18O values of the Gaojiacun zircons are also higher than the normal mantle (δ18O = 5.3 ± 0.6 ‰). Zircon trace element compositions show that, despite their close spatial association (<10 km), the coeval intrusions have contrasting redox states, with the estimated fO2 values of ΔFMQ+1.0 and ΔFMQ-0.7 for Tongde and Gaojiacun, respectively. The former is within the range of modern arc basalts, whereas the latter is lower than the average value of MORBs. The very low fO2 of the Gaojiacun magma could be due to the presence of subducted oceanic sediments enriched in organic matter (OM) in the source or due to contamination with OM-rich sedimentary rocks in the upper crust. Since such crustal rocks have not been reported for the region, we prefer the former explanation. The preferred model is also supported by Sr–Nd–Hf–O isotopes. The results from this study reveal that both reduced and oxidized magma could be produced simultaneously in a subduction zone.

Cristobalite Clinker and Paralavas of Ferroan and Melilite–Nepheline Types in the Khamaryn-Khural–Khiid Combustion Methamorphic Complex, East Mongolia: Formation Conditions and Processes

Abstract —Rock samples from the Khamaryn-Khural–Khiid combustion metamorphic (CM) complex, including cristobalite clinker, ferroan tridymite–sekaninaite and cristobalite–fayalite paralavas, which are rock types new to the complex, as well as clinker xenoliths in melilite–nepheline paralava, have been studied in terms of chemistry and mineralogy. The obtained data on rock-forming, minor, accessory, and rare phases (silica polymorphs, cordierite-group minerals, fayalite, Fe and Ti oxides, ferrosilite, etc.) have implications for the formation conditions and processes of the CM rocks. The Raman spectra of sekaninaite, indialite, ferroindialite, mullite, and anhydrous Fe–Ca–Mn phosphate, presumably from the graftonite group, have several specific features. The diversity of mineral assemblages in the CM rocks is due to heterogeneous lithology of the sedimentary protolith and to local effects in the multistage history of the Khamaryn-Khural–Khiid complex. According to geochemical data, all CM rocks of the complex are derived from the Early Cretaceous Dzunbain Formation, their protolith molten to different degrees. The cristobalite clinker and tridymite–sekaninaite and cristobalite–fayalite paralavas were produced by partial melting of pelitic rocks containing different amounts of iron in a wide temperature range. The formation of mullite developed from dehydration–dehydroxylation and incongruent partial melting of amorphous pelitic matter. Large-scale crystallization of mullite in clinker, occurred from the high-silica potassic aluminosilicate melt at &amp;gt;850 °C. Combustion of subsurface coal seams heated the overburden to &amp;gt;1050 °C or locally to &amp;gt;1300–1400 °C (melting point of detrital quartz) or even, possibly, to &amp;gt;1470 °C corresponding to the stability field of β-cristobalite. Melilite–nepheline paralava was formed by incongruent melting of silicate (pelitic) and carbonate (calcite) components of marly limestone under elevated CO2 partial pressure. Oxygen fugacity (fO2) during combustion metamorphism changed from strongly reducing conditions favorable for crystallization of Fe phosphides (barringerite, schreibersite) and metallic iron from silica-undersaturated melts parental to melilite–nepheline paralava to high fO2 values that can maintain the formation of hematite in Fe-rich CM rocks.

Determination of the oxidation state of primary melts using two proxies

Although many studies have demonstrated that arc magmas are more oxidized than mid-ocean ridge (MORB) and oceanic island basalts (OIB), the oxidation state of their mantle source is still debated. This ongoing debate is mainly due to contradictory fO2 values obtained from different proxies (e.g., Fe3+/ΣFe of olivine-hosted melt inclusions and glasses; Zn/ΣFe, V/Sc, V/Ga of lavas). On the one hand, some studies using V/Sc, V/Ga and Zn/ΣFe of lavas tend to show that the oxidation state of the mantle beneath arcs cannot be distinguished from that of the MORB mantle. On the other, Fe3+/ΣFe of glasses and olivine-hosted melt inclusions suggest that the sub-arc mantle is more oxidized than the mantle beneath ridges. Here, we estimate the oxygen fugacity of high-Mg olivine-hosted melt inclusions from various mid-ocean ridges and arcs, from one hot spot (Reunion Island) and Mount Etna using two fO2 proxies: the Fe3+/ΣFe of melts and the partition coefficient of V between olivine and melt (DvOl/Melt). After assessing the role of secondary processes such as volatile degassing and fractional crystallization on the fO2 of melts and reconstructing primary melt compositions, we show that (1) fO2 values derived from Fe3+/ΣFe and DvOl/Melt are comparable and (2) arc and Mount Etna primary melts are more oxidized than mid-ocean ridge and Reunion Island primary melts. We then demonstrate, from Zr/Nb, that the observed variability in primary melt fO2 is not due to chemical variability of the mantle source. Finally, the correlations between incompatible trace element ratios such as Th/La, Ba/La, Ba/Th and La/Yb and the fO2 of primary melts reveal a link between the oxidized nature of arc and Mount Etna primary magmas to slab fluid and/or sediment melt influence. Our arc dataset displays a variety of subduction influences, from fluid-dominated (Aoba and Mount Meager) to sediment melt-dominated (La Sommata) influences. The origin of the oxidation of Mount Etna magmas is more complicated to identify and the nature of the oxidized metasomatic fluids that likely percolated through the mantle source before magma generation is yet to be determined.

The Roles of Various Types of Crustal Contamination in the Genesis of the Jinchuan Magmatic Ni-Cu-PGE Deposit: New Mineralogical and C-S-Sr-Nd Isotope Constraints

Abstract Addition of crustal sulfur to the Jinchuan magma or oxidation of the magma associated with carbonate assimilation has been considered to be the main cause of sulfide saturation in the magma by two opposing groups of researchers. To address this controversy, we have carried out an integrated mineralogical and C-S-Sr-Nd isotope study of the Jinchuan magmatic Ni-Cu-platinum group element (PGE) sulfide ore deposit. Pure marble, olivine marble, serpentine marble, and hybrid rocks occur in the contact zone. The δ13Ccarb values of the Jinchuan sulfide-bearing ultramafic rocks containing calcite xenocrysts are from –4.7 to –2.9‰, which are similar to or slightly lower than those of the marbles and associated hybrid rocks (–3.9 to 0.8‰) but significantly higher than those of the calcite-barren intrusive rocks (–9.3 to –8.0‰). This, together with the calcite xenocrysts and calcium-silicate minerals in hybrid rocks and some intrusive rocks, indicates that carbonate assimilation took place during magma-carbonate interaction. Only less than several hundred ppm of the CO2 gas produced in the reaction zone could be added to the Jinchuan magma. Such a trace amount of additional CO2 was rapidly swamped by the much greater mass of FeO in the magma, resulting in little change in the FeO/Fe2O3 of the magma, and thereby negligible change of magma redox state. This is evident from similar calculated fO2 values for the calcite-bearing (~QFM+0.7) and calcite-barren (~QFM+0.6) intrusive rocks. The new results rule out the possibility that sulfide saturation in the Jinchuan magma resulted from in situ carbonate assimilation. The Sr-Nd isotope data from this study and previous studies are consistent with up to 20% bulk contamination with siliceous crustal materials at depth, followed by minor amounts of in situ carbonate assimilation by the Jinchuan magma. Our new sulfur isotope data expand the range of δ34S for the Jinchuan deposit significantly. The new range is from −7.6 to 3.0‰, with an average of −1.8‰, which is generally lower than the mantle value (0 ± 2‰). The new result supports the premise that crustal sulfur was involved in the genesis of the Jinchuan deposit. Very high, crustal-like S/Se ratios (as high as 8080) for some of the samples from the deposit provide additional support for the interpretation. The country rocks in the vicinity of the Jinchuan deposit analyzed to date have δ34S values varying from −4.0 to 11.3‰, with an average of 2.9‰, which is higher than both the mantle value and the average value of the Jinchuan deposit, suggesting that the Jinchuan magma acquired some crustal sulfur at depth, likely concurrent with the siliceous assimilation. Numerical modeling of δ34S-S/Se of sulfide ores and country rocks further illustrates that the observed variations of δ34S and S/Se ratios are related to the assimilation of S-rich rocks located at depth, followed by progressive dilution of the contaminated δ34S-S/Se signature. Based on the new results, we conclude that contamination with siliceous crustal materials as well as addition of crustal sulfur at depth played a critical role in triggering sulfide saturation in the Jinchuan magma.

Geochemistry and Mineralogy of Peridotites and Chromitites from Zhaheba Ophiolite Complex, Eastern Junggar, NW China: Implications for the Tectonic Environment and Genesis

The Zhaheba ophiolite is an ocean relic of the Zhaheba-Aermantai oceanic slab, a branch of the early Paleozoic Paleo-Asian Ocean. The peridotites consist mainly of harzburgite, lherzolite and minor dunite, chromitite. This study describes the whole-rock geochemistry and mineral chemistry of the Zhaheba peridotite and chromitite for the purpose of constraining their tectonic environment and genesis. The major oxides and the trace element concentrations of the peridotites are comparable with abyssal peridotite, but fall outside the field of SSZ (suprasubduction zone) peridotite and the fore-arc peridotite. The massive chromites belong to the high-Cr group, with an average Cr# (Cr/(Cr + Al)) atomic ratio) value of chromian spinel of 0.77, whereas the average Mg# value is 0.60. The disseminated chromites give a lower concentration of Cr2O3 (38.96–42.15 wt.%, average 40.35 wt.%) and lower Cr# values (0.50–0.56, average 0.53), but slightly higher contents of MgO (13.23 wt.%) and Mg# (0.61) than the massive chromites. In the diagrams of Cr#-Mg#, NiO-Cr# and TiO2-Cr#, the massive chromites fall in the field of boninite, and the disseminated chromite in the peridotite plot fall in the field of abyssal peridotite and mid-oceanic ridge basalt (MORB). The massive chromitites, with high-Cr, display a boninite affinity, whereas the disseminated chromite plot in the high-Al and abyssal peridotite type field may be generated by the extension of the Zhaheba ocean in the MOR environment then experienced deep subduction and exhumation. The calculated degrees of partial melting for the massive chromites are 21%−22%, and for the disseminated chromites in peridotites the degrees are 17%−18%. The calculated values of fO2 for the massive chromites range from −1.44 to +0.20, and the values for the disseminated chromites range from −0.32 to +0.18. The inferred parental melt composition for massive chromitite falls in the field of boninite in an arc setting, whereas the disseminated chromite in peridotites are in the field of a MORB setting. This indicates that the parental magmas of the former were more refractory than the latter. A two-stage evolution model for the chromites was proposed, in which disseminated chromites were first formed in an MOR environment and then modified by later-stage melts and fluids, and formed massive chromites were formed in an SSZ setting during intra-oceanic subduction.

In-situ redox conditions in hydrothermal diamond-anvil cell experiments using various metal gaskets

Hydrothermal diamond-anvil cells (HDACs) have been widely used in various research fields since they were introduced in 1993. Unlike temperature (T) and pressure (P), the redox states of the samples in HDAC experiments were poorly controlled or measured; they were usually estimated by observing the reduction/disappearance of redox-sensitive mineral(s) (e.g., Mo metal) and corresponding formation and growth of such mineral(s) (e.g., MoO2) without in-situ redox measurement. In this study, we demonstrated the generation of H2 during experiments using various metal gaskets, including inert (Re) and chemically more reactive metals (Ni, Co, Mo, and W), in the pure H2O system under various P-T conditions. A technique for quantitative Raman spectroscopic analysis of H2 in HDAC is designed. Based on this technique, the oxygen fugacity (fO2) values of Mo-MoO2 buffer at the experimental P-T conditions were then calculated from these measured H2 pressures. We demonstrated that steady-state redox control can be maintained at a fixed T between 400 and 500 °C in HDAC experiments using a Mo gasket for durations of up to two hours and for those using a Re gasket with an additional Mo rod in the sample between 400 and 800 °C for durations of up to 90 min, regardless of the considerable changes in sample pressure. This demonstration was established by the balance between the rates of H2 generation and H2 loss from the sample chamber. The loss of H2 enhanced the consumption of H2O and therefore reduced the sample pressures during the experiments.We believe that hydrogen contents in every HDAC experiment, which attempt to control the redox state, need in situ measurement, then estimate the real redox state and compare it to thermodynamic equilibrium prediction. To enhance in situ redox control and measurements, modifications of HDAC are required for improving the quantitative Raman spectroscopic analysis technique in both sensitivity and accuracy.

Different B[sbnd]Mo isotopic fractionation processes controlled by redox conditions in the subduction zone

The control of redox conditions on the geochemical recycling process in subduction zones is still poorly understood due to large uncertainties in oxygen fugacity (fO2) for subducted slabs. We present the first systematic geochemical and B-Mo-Sr-Nd-Hf-Pb isotopic data for continental arc basalts (CABs) and back-arc basalts (BABs) from Sumatra to investigate the relationships between oxygen fugacity and BMo isotopic fractionation processes during subduction. The Sumatran CABs and BABs yield high FeOT/MgO ratios and low K2O contents (0.48–1.42 wt%) and can be classified as tholeiitic. They have variable Sr-Nd-Hf-Pb isotopic compositions, consistent with the input of different amounts of melt from subducted terrigenous sediments into mantle sources. The BAB samples show much lower δ11B (−9.0‰ to −7.3‰) values than the CABs (δ11B = −7.0‰ to +0.17‰), reflecting significant B isotopic fractionation during multistage melting of subducted sediments. This is distinct from the similar δ98/95Mo values for the Sumatran CABs (−0.21‰ to −0.01‰) and BABs (−0.17‰ to −0.08‰), suggesting limited Mo isotopic fractionation during subduction. The Sumatran CABs show low V/Yb ratios, suggesting that melts from subducted sediments were possibly generated at fO2 values lower than FMQ + 1.5. The limited Mo isotopic fractionation could be induced by the relatively low fO2 during melting of subducted sediments, which would significantly decrease the mobility of Mo but have no influence on B. Alternatively, rocks from highly oxidized arcs, such as the Izu arc (e.g., >FMQ + 3), exhibit across-arc lightening trends for both B and Mo isotopes, which is consistent with enhanced Mo isotopic fractionation due to elevation of fO2 during subduction. Thus, the BMo isotopes of arc rocks could provide diagnostic indicators for distinct geochemical recycling processes controlled by changes in redox conditions in subduction zones.

Geochronology, petrogenesis, and mineralization potential of the syenogranites in the Yama fluorite deposit, Tataleng granitic batholith, Qilian Orogen, NW China

The Yama fluorite deposit in the Qilian Orogen in NW China is characterized by predominant granitic magmatism and fluorite mineralization. The wall rocks hosting the fluorite–quartz veins in the Yama area consist of the Yama porphyritic syenogranite and the Wulandawu syenogranite. In this study, the major and trace element compositions, zircon U–Pb ages, and zircon Hf isotopes and trace element compositions were investigated. Two samples for the Yama porphyritic syenogranite yielded weighted mean 206Pb/238U zircon ages of 440.7 ± 4.8 and 447.9 ± 6.0 Ma, and one sample for the Wulandawu syenogranite yielded a weighted mean 206Pb/238U zircon age of 441.2 ± 5.0 Ma, all of which indicate a Late Ordovician to Early Silurian crystallization age. Geochemically, both syenogranites are peraluminous, with high alkali contents, low Zr + Nb + Ce + Y contents, relatively low (K2O + Na2O)/CaO ratios, and high Rb/Sr and Rb/Ba ratios, suggesting that they are fractionated S-type granites. They have zircon εHf( t) values of −14.9 to −4.4 and −12.2 to −4.5, respectively, suggesting that they were derived from the partial melting of pelitic-rich sources within the relatively shallow Paleoproterozoic reworked crust. The detailed geochronological and geochemical data suggest that the studied syenogranites were emplaced in a post-collisional setting related to the closure of the South Qilian Ocean. Finally, they have relatively low quantitative oxygen fugacity values, indicating relatively reduced redox states, but their very low zircon Ce4+/Ce3+ ratios, low whole-rock K/Rb ratios, relatively high Nb/Ta ratios, and low Zr/Hf ratios suggest that they are not likely to form important W–Sn deposits and related fluorite deposits.

Key Factors Controlling Biotite–Silicate Melt Nb and Ta Partitioning: Implications for Nb−Ta Enrichment and Fractionation in Granites

AbstractBiotite–melt Nb and Ta partition coefficients (DNb and DTa) are crucial for understanding Nb−Ta enrichment and fractionation in rare metal granites (RMGs). However, the key factor(s) affecting biotite–melt DNb, DTa, and DNb/DTa values remain unclear. To elucidate the physicochemical factors that control the partition coefficients, we performed piston−cylinder experiments at 0.5−1.0 GPa and 850−1000°C with H2O‐added (4−10 wt.%) mixtures of granitic and biotitic glasses as starting materials. Two series of experiments (graphite‐buffered and unbuffered fO2 conditions) were conducted with calculated fO2 values ranging from ∼FMQ–1.5 to ∼FMQ+4. Under these experimental conditions, biotite–melt DNb, DTa, and DNb/DTa values are 0.30–2.63, 0.24−1.02, and 1.01−2.15, respectively. Biotite–melt DNb, DTa, and DNb/DTa values increase with decreasing melt NBO/T value (non‐bridging oxygens per tetrahedron), melt H2O content, and biotite Mg#T value [molar 100 × MgO/(MgO + FeOT)]. In addition, DNb and DTa exhibit good correlations with DTi, suggesting that DNb and DTa are predictable via DTi values. With our and literature data, we used multiple linear regressions to obtain empirical expressions of DNb and DTa as functions of the three parameters. By applying the empirical models to granite differentiation process, we found that ∼99% crystallization of biotite ± muscovite‐bearing assemblages results in an enrichment in magma Ta contents by &gt;10 times with a decrease in Nb/Ta values from 10−13 to ∼1, which reproduces the Ta–Nb/Ta features of most RMGs. However, additional processes, such as columbite‐group mineral precipitation, may be required to account for the extremely low Nb/Ta values (&lt;1) of some RMGs.