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The Gaching high-sulfidation epithermal deposit in the Maletoyvayam ore field features a wide range of Se-containing minerals and selenides, as well as complex gold oxides, Au tellurides (calaverite, krennerite) and native gold typical for epithermal deposits. Pyrite included in quartzites and quartz-alunite rocks was probably formed during an early stage of the ore-forming process. During the following Au-rich stage, the fSe2/fS2 increased with fO2 being relatively high, resulting in the formation of very rare compounds that have not been previously described in nature. These include Au2Te4(Se,S)3, Se3Te2, AuSe and Au(Te,Se,S) phases. The Au2Te4(Se,S)3 compounds have some variations in composition: the complete isomorphic series between Au2Te4Se3 and Au2Te4S3 was observed. The gold and Au-minerals at the main ore stage can be stable within a range of logfO2 of -27.3 and atmospheric oxygen (?); logfS2 between -12.4 and -5.7; logfTe2 between -10.5 and -7.8; and logfS2 between -12.8 and -6.8 (at 250°C). The increasing oxygen fugacity during the final stage of mineralization resulted in the formation of complex Sb,As,Te,S-bearing Au oxides. Gold-oxide formation occurs due to oxidation of Au-tellurides. The final products of this process are newly-formed secondary mustard gold and Te-Se solid solutions.

The behavior of C, H, and S in the solid Earth depends on their oxidation states, which are related to oxygen fugacity (fO₂). Volcanic degassing is a source of these elements to Earth’s surface; therefore, variations in mantle fO₂ may influence the fO₂ at Earth’s surface. However, degassing can impact magmatic fO₂ before or during eruption, potentially obscuring relationships between the fO₂ of the solid Earth and of emitted gases and their impact on surface fO₂. We show that low-pressure degassing resulted in reduction of the fO₂ of Mauna Kea magmas by more than an order of magnitude. The least degassed magmas from Mauna Kea are more oxidized than midocean ridge basalt (MORB) magmas, suggesting that the uppermantle sources of Hawaiian magmas have higher fO₂ than MORB sources. One explanation for this difference is recycling of material from the oxidized surface to the deep mantle, which is then returned to the surface as a component of buoyant plumes. It has been proposed that a decreasing pressure of volcanic eruptions led to the oxygenation of the atmosphere. Extension of our findings via modeling of degassing trends suggests that a decrease in eruption pressure would not produce this effect. If degassing of basalts were responsible for the rise in oxygen, it requires that Archean magmas had at least two orders of magnitude lower fO₂ than modern magmas. Estimates of fO₂ of Archean magmas are not this low, arguing for alternative explanations for the oxygenation of the atmosphere.

Magma oceans were once ubiquitous in the early solar system, setting up the initial conditions for different evolutionary paths of planetary bodies. In particular, the redox conditions of magma oceans may have profound influence on the redox state of subsequently formed mantles and the overlying atmospheres. The relevant redox buffering reactions, however, remain poorly constrained. Using first-principles simulations combined with thermodynamic modeling, we show that magma oceans of Earth, Mars, and the Moon are likely characterized with a vertical gradient in oxygen fugacity with deeper magma oceans invoking more oxidizing surface conditions. This redox zonation may be the major cause for the Earth’s upper mantle being more oxidized than Mars’ and the Moon’s. These contrasting redox profiles also suggest that Earth’s early atmosphere was dominated by CO 2 and H 2 O, in contrast to those enriched in H 2 O and H 2 for Mars, and H 2 and CO for the Moon. Applying first-principles molecular dynamic simulations and thermodynamic modelling, the authors suggest a vertical oxygen fugacity gradient in magma oceans of Earth, Mars, and the Moon. Consequently, the study proposes larger planets like Earth to have stronger oxidized upper mantles than smaller bodies such as Mars or the Moon.

The Gejiu ore district (~ 3.2 Mt Sn) is located in eastern Yunnan Province, southwest China, and is one of the largest Sn polymetallic ore districts in the world. Athough it has been widely studied, the petrogenesis of ore-related granites is still unclear. In this paper, we present petrological, geochemical, and geochronological data on the granites associated with the Kafang Cu–Sn deposit in the Gejiu ore district (65 Mt Cu ore at a grade of 1.2% and 32 Mt Sn ore at a grade of 0.6%). We use these data to constrain the source, evolution, oxygen fugacity, and tectonic setting of the granitic magmatism. Zircon U–Pb dating yielded an age of 82.8 ± 0.6 Ma for the Kafang granite. The high zircon δ18O values (7.45–9.74‰; mean = 8.80‰) and narrow range of εNd(t) values (–9.0 to –7.7) of the Kafang granite indicate a highly evolved S-type granite derived by partial melting of metamorphic basement rocks of the Jiangnan orogenic belt. Rayleigh fractional crystallization modeling, along with the increase in Hf and Sn contents and decrease in Eu/Eu* values of zircons, record extensive fractional crystallization, and Sn enrichment during magmatic evolution. The Kafang granite was relatively reduced, as evidenced by low zircon Ce/Ce* (10.0–366; mean = 171), (Ce/Nd)N (0.76–8.32; mean = 4.41), △FMQ (–2.5 to 1.2) values, and Fe3+-depleted biotite compositions (Fe3+/(Fe3+  + Fe2+) = 0–0.10), which were favorable for Sn mineralization but not for Cu mineralization. Copper in the Kafang deposit may not have been derived from the granite. Our results suggest that biotite and zircon geochemical compositions, particularly biotite Mg# and A/CNK values and zircon Hf contents, Eu anomalies, and Ce/Ce* and (Ce/Nd)N ratios, are robust tracers of different types of magmatic-hydrothermal ore deposits (i.e., Cu, Mo, W, and Sn). Late Cretaceous magmatism in the Gejiu region and other areas along the southern margin of South China formed an E–W-trending igneous belt that was likely related to northward subduction of the Neo-Tethyan plate rather than northwestward subduction of the Paleo-Pacific plate.

The origin of the more oxidized nature of arc magmas as compared to that of mid-ocean ridge basalts (MORB) is debated, considered to be either a feature of their mantle source, or produced during crustal transit and eruption. Fe3+/FeT ratios (Fe3+/[Fe3+ + Fe2+]) in arc volcanic rocks and glasses and thermodynamic oxybarometry on mantle xenoliths from arc lavas indicate elevated magmatic oxygen fugacity (\\[f_{{{\\text{O}}_{ 2} }}\\]), whereas, redox-sensitive trace elements ratios and abundances in arc volcanic rocks have been used to suggest that arcs have source regions with \\[f_{{{\\text{O}}_{ 2} }}\\] similar to the MORB source. Here, we take an alternative approach by calculating the \\[f_{{{\\text{O}}_{ 2} }}\\] of the uppermost mantle and lowermost ultramafic cumulates from the accreted Jurassic Talkeetna arc (Alaska). This approach allows us to quantify the \\[f_{{{\\text{O}}_{ 2} }}\\] of the sub-arc mantle and of primary arc magmas crystallizing at the base of an island arc, which have not been affected by processes during crustal transit and eruption which could affect their \\[f_{{{\\text{O}}_{ 2} }}\\]. Implementing olivine–spinel oxybarometry, we find that the upper mantle (harzburgites and lherzolites) and ultramafic cumulates (clinopyroxenites and dunites) crystallized between + 0.4 and + 2.3 log units above the fayalite-magnetite-quartz buffer, consistent with previous studies suggesting that the sub-arc mantle is oxidized relative to that of MORB. In addition, the Talkeetna paleo-arc allows us to examine coeval lavas and their redox-sensitive trace element ratios (e.g., V/Sc). The average V/Sc ratios of high MgO (> 6 wt%) lavas are 6.7 ± 1.6 (2σ), similar to that of MORB. However, V/Sc ratios must be interpretted in terms the degree of partial melting, as well as, the initial V/Sc ratio of the mantle source in order to derive information about \\[f_{{{\\text{O}}_{ 2} }}\\] of their mantle source. The V/Sc ratios of Talkeetna lavas are consistent with the elevated \\[f_{{{\\text{O}}_{ 2} }}\\] recorded in the sub-arc mantle and primitive cumulates (olivine Mg# [Mg/(Mg + Fe)] × 100 > 82) if a depleted mantle source underwent 15–20% melting. Our results suggest that the arc mantle is, on average, more oxidized than the MORB source and that V/Sc ratios must be interpreted in the context of a partial melting model where all model parameters are appropriate for arc magma genesis. This study reconciles V/Sc ratios in arc volcanic rocks with \\[f_{{{\\text{O}}_{ 2} }}\\] of primary arc basalts and the sub-arc mantle from the same locality.

Refractory oxygen bound to cations is a key component of the interior of rocky exoplanets. Its abundance controls planetary properties including metallic core fraction, core composition, and mantle and crust mineralogy. Interior oxygen abundance, quantified with the oxygen fugacity (fO₂), also determines the speciation of volatile species during planetary outgassing, affecting the composition of the atmosphere. Although melting drives planetary differentiation into core, mantle, crust, and atmosphere, the effect of fO₂ on rock melting has not been studied directly to date, with prior efforts focusing on fO₂-induced changes in the valence ratio of transition metals (particularly iron) in minerals and magma. Here, melting experiments were performed using a synthetic iron-free basalt at oxygen levels representing reducing (log fO₂ = −11.5 and −7) and oxidizing (log fO₂ = −0.7) interior conditions observed in our solar system. Results show that the liquidus of iron-free basalt at a pressure of 1 atm is lowered by 105 ± 10 °C over an 11 log fO₂ units increase in oxygen abundance. This effect is comparable in size to the well-known enhanced melting of rocks by the addition of H₂O or CO₂. This implies that refractory oxygen abundance can directly control exoplanetary differentiation dynamics by affecting the conditions under which magmatism occurs, even in the absence of iron or volatiles. Exoplanets with a high refractory oxygen abundance exhibit more extensive and longer duration magmatic activity, leading to more efficient and more massive volcanic outgassing of more oxidized gas species than comparable exoplanets with a lower rock fO₂.

The Surface Ocean CO2 Atlas (SOCAT) of CO2 fugacity (fCO2) observations is a key resource supporting annual assessments of CO2 uptake by the ocean and its side effects on the marine ecosystem. SOCAT data are usually released with a lag of up to 1.5 years which hampers timely quantification of recent variations of carbon fluxes between the Earth System components, not only with the ocean. This study uses a statistical ensemble approach to analyze fCO2 with a latency of one month only based on the previous SOCAT release and a series of predictors. Results indicate a modest degradation in a retrospective prediction test for 2021–2022. The generated fCO2 and fluxes for January–August 2023 show a progressive reduction in the Equatorial Pacific source following the La Niña retreat. A breaking‐record decrease in the northeastern Atlantic CO2 sink has been diagnosed on account of the marine heatwave event in June 2023. Plain Language Summary There is a growing need to monitor carbon emissions and removals over the globe in near real time in order to correctly interpret changes in CO2 concentrations as they unfold. For the oceans, the best information comes from measurements of the surface ocean CO2 fugacity (fCO2) by the international marine carbon research community. So far, this data is mostly available 6 to 18 months behind real time after collection, qualification, harmonization, and processing. Here, we show that a set of biological, chemical, and physical predictors available in near real time, allows the information contained in the “old” fCO2 measurements to be transferred over time. Based on a statistical technique, we combine all these data sources to estimate global monthly maps of fCO2 and of CO2 fluxes at the air‐sea interface within one month behind real time and with good accuracy. Key Points We demonstrate the capacity of statistical models to generate global maps of fCO2 and air‐sea flux with a latency reduced to one month A decrease in the CO2 source for January to August 2023 diagnosed in the tropical Pacific coheres with the retreat of the La Niña event An unusual northeastern Atlantic sink reduction diagnosed for June 2023 is linked to record heat and exceptionally low winds

Vanadium is a multivalent element that may speciate as V 2+ ; V 3+ ; V 4+ and V 5+ in silicate and oxide phases. The relative abundance of V in planetary materials can be used as a proxy for oxygen fugacity ( f O 2 ) when its partitioning behavior has been calibrated with controlled laboratory experiments. Here we present the results of 20 piston-cylinder experiments executed over a 10-log unit range of f O 2 at temperatures from 800 to 1230 °C, at 1.8–2 GPa, to quantify the partitioning of V between garnet, clinopyroxene, rutile and hydrous silicate melt under conditions relevant to eclogite melting in subduction zones. In all experiments, the partitioning of V between phases is controlled nearly equally by f O 2 and by temperature (and/or compositional effects that are directly related to temperature). Vanadium is most compatible in experimental rutile, followed by clinopyroxene, then garnet. Calculated mineral/melt partition coefficients are ≥ 1 for all three phases in our experimental series. The high compatibility of V in eclogitic minerals results in negligible mass transfer of V during eclogite melting under all f O 2 conditions investigated. Oxidized species of V are more soluble in rutile compared to garnet and clinopyroxene, leading to a linear increase in rutile/cpx and rutile/garnet inter-mineral partition coefficients as f O 2 increases. We calibrate the partitioning of V among rutile-cpx and rutile-garnet pairs as an f O 2 proxy for natural rocks and test its application to eclogitic xenoliths from the Koidu kimberlite suite (Sierra Leone). Our application yields spurious f O 2 values for Koidu, indicating the V systematics of natural systems are likely much more complex than predicted by our experiments. Further work is needed to characterize the partitioning of V between eclogitic minerals over an extended range of mineral solid solutions, pressures, and temperatures before a V-oxybarometer may be applied to natural metamorphic systems with confidence.

The genetic link between subduction- and collision-related porphyry Cu deposits (PCD) is still not well understood. The Gangdese porphyry Cu belt (GPCB) in southern Tibet hosts two parallel E–W-oriented metallogenic subbelts, including a southern Jurassic subduction-related and a northern Miocene post-collision PCD subbelt. In this study, we combine new and published whole-rock major and trace element data, Cu isotopic compositions and zircon trace element data of Jurassic magmatic rocks from the GPCB. Combined Sr/Y and La/Yb crustal thickness proxies confirm the south to north geometry of the Jurassic arc-back-arc system across the GPCB. The southern Jurassic magmatic arc rocks have systematically higher whole-rock V/Yb ratios, δ65Cu values and zircon Eu/Eu* ratios compared to those of the northern back-arc region. This suggests that Jurassic southern arc magmas had higher oxygen fugacity and H2O concentration than the contemporaneous northern back-arc magmas, which was controlled by a steep subduction geometry of the Neo-Tethyan oceanic slab. Hydrous and oxidized magmas resulted in Cu enrichment during magma evolution and generation of Jurassic PCD in the southern magmatic arc by inhibiting early sulfide saturation at deep crustal levels. In contrast, the northern back-arc magmas were less oxidized and less hydrous, which triggered early sulfide saturation, resulting in segregation of Cu-bearing sulfides in lower crustal cumulates that provided a favorable metal source for later Miocene PCD in the northern subbelt. Our study indicates that the Jurassic subduction geometry controlled the formation and distribution of Jurassic subduction-related and Miocene post-collision-related PCD in the GPCB.

Ilmenite-, magnetite- and clinopyroxene−melt trace element partition coefficients were investigated experimentally as a function of oxygen fugacity and melt composition in a range of synthetic ferrobasaltic bulk compositions. The experiments were performed at a constant temperature (1080 °C) and pressure (1 atm) over a range of oxygen fugacity ( f O 2 ) conditions from ca. 2 log units below to ca. 2 log units above the FMQ buffer. The partitioning behaviour of the divalent cations Zn, Mn, Co and Ni are found to be controlled by the degree of polymerisation of the coexisting melt; the partitioning behaviour of rare earth elements, Y and Sc can be explained well by the lattice strain model and the partitioning of the high-field strength elements Zr, Hf, Ta and Nb is influenced by the TiO 2 content of the melt. Vanadium partitioning is strongly influenced by oxygen fugacity and a series of linear regression equations are presented to express the dependence of the mineral−melt partitioning behaviour of the multivalent cation V on oxygen fugacity. Furthermore, calibration of the partitioning of vanadium between magnetite–ilmenite pairs as an oxybarometer is proposed and applied to a ferrobasaltic layered intrusion—the Skaergaard intrusion—to provide an estimate of oxygen fugacity.