Oxygen Fugacity Research Articles

Tracing the Oxidizing State and Element‐Mobilizing Fluids in Continental Subduction Zones: Insights From the Granitic Melt‐Eclogite Interface

AbstractFluids in subduction zones significantly influence element mobility, isotope fractionation, and mass transfer. However, unraveling the source, composition, and redox state of fluids in continental subduction zones poses a significant challenge. This study focuses on a granitic melt‐eclogite contact interface, along with adjacent granite and eclogite from the Sulu ultrahigh‐pressure metamorphic belt in East China. The interface exhibits complex mineral assemblages, enriched rare earth elements (REEs), and high field strength elements (HFSEs). Zircon grains from the interface show an age of ∼217 ± 9 Ma, slightly later than peak metamorphism, along with the presence of coesite inclusions. These findings suggest that the interfacial fluid likely formed from the mixing of granitic anatectic melt and aqueous fluid from the eclogite during the initial exhumation of the Sulu terrane. The interaction resulted in the eclogite acquiring substantial REEs and HFSEs, suggesting the interfacial fluid's effective element‐transporting capability and potential supercritical fluid properties. Zircon Ce anomaly and Fe3+/Fe2+ oxybarometer data indicate a highly oxidizing interfacial fluid, analogous to arc magmas in oxygen fugacity. This led to the preferential loss of isotopically heavier Cr from the eclogite during fluid‐eclogite interaction, evidenced by heavier Cr isotopic compositions in the interface (δ53Cr = −0.04 to −0.05‰) compared to adjacent eclogite (δ53Cr as low as −0.11‰). In summary, our results highlight the presence of strong oxidizing and element‐mobilizing fluids in continental subduction zones, offering insights into supercritical fluid recognition and the genesis of oxidizing arc magmas in subduction zones.

Geochemical and geochronological evidences from Cambrian to Ordovician protracted magmatism in the Istranca Massif, NW Türkiye

Plutonic rocks in different ages are cropted out and form the basement rocks in the Istranca Massif. One of the plutons located at the basement is the Cambrian-Ordovician Vize pluton (Vize-Kırklareli) and is distinguished from other plutons by some of its characteristic features. This pluton intruded into the high-grade metamorphic sedimentary rocks, and is unconformably overlay by Triassic low-grade metamorphic rocks and Eocene aged coral reef limestones (Soğucak Formation). Based on new whole rock geochemical and zircon UPb data concentrated in two different ages, it can be said that the Vize pluton was affected by protracted magmatic activity. The igneous minerals and texture of Vize pluton are partly preserved, It has a mylonitic texture, a distinct foliation consisting of light and dark zones. In addition, metagranites contain mafic magmatic enclaves (MMEs) in some places.The Vize pluton is an I-type pluton with predominantly peraluminous and slightly metaluminous character. It is also High-K, calc-alkaline, and reflecting volcanic arc and post-collisional tectonic settings. Mineral chemical analyses show that the mafic minerals in the Vize pluton consist of Fe-biotite and calcic amphibole (hornblende). Ti-in biotite thermometry shows that the temperature of the pluton in the final crystallization temperatures are between 834 and 850 °C (mean = 845 ± 4 °C), while the crystallization temperatures of amphiboles are between 876 and 910 °C (mean = 893 ± 22 °C). Crystallization depths are estimated to be a range of 6.5 to 7.9 km. It can be assumed that the oxygen fugacity of calcic amphiboles (logƒO2) is stabilized between −10.7 and − 11.3 bar (mean = −11.05 ± 0.4 bar). ∆NNO values are between 0.72 and 1.11 (mean = 0.96 ± 0.12) and H2O melt content is between 4.63 % and 5.43 % (mean = 5.04 ± 0.4 %). Oxygen fugacity values are among the typical values of calc-alkaline magma crystallization.The Vize pluton was crystallized in Cambrian to Ordovician times according to zircon UPb dating is concentrated in two different populations as 526.16 ± 3.26 Ma and 452.93 ± 2.76 Ma. All data obtained are consistent with the ages of the magmatism that produced the Vize Pluton in the Balkanides and Istranca Massif of 420–470 Ma (mean 447.17 ± 3.24 Ma) and indicate that it probably formed in the northern Gondwana. It was affected by the magma-mixing processes of coeval felsic and mafic magmas, and anatexis processes. Geochronological and geochemical data indicate the existence of a protracted magmatic activity related to convergent setting (long-lived magmatic arc) that forced the Vize-Pluton to undergo multi-stage melting-crystallization processes.

Zinc partitioning between mantle minerals and basaltic melts: Application to revisit the Zn/FeT redox proxy

Zn/FeT (FeT=Fe2+ + Fe3+) ratios in primitive melts have been proposed as a redox proxy to assess the redox states of the upper mantle. However, to effectively use the melt Zn/FeT ratio as a redox proxy, it is necessary to compare variations of melt Zn/FeT ratios induced by changes in oxygen fugacity (fO2) with variations due to changes in Zn-Fe contents and mineralogy of the sources. Here we show that the melt Zn/FeT ratio variation caused by fO2 change can be expressed as Δ(Znm/FemT) = (Znper/FeperT)* Δ(Fem2+/FemT)/(DZnper/m/DFe2+per/m). Zn/FeT ratios in most arc and MORB peridotites (Znper/FeperT) are 9.0 ± 1.0*10−4, and melt Fe2+/FeT ratio variation resulted from fO2 change [Δ(Fem2+/FemT)] can be easily obtained by the existing model. Hence, if the Zn and Fe2+ partition coefficients (DZnper/m and DFe2+per/m) between melt and peridotite are known, the melt Zn/FeT ratio variation resulting from fO2 change can be estimated. In this study, we determined DZn between olivine, orthopyroxene, clinopyroxene and basaltic melts at 0.75–2.5 GPa and 1250–1450 ℃. Our data show that melt composition (expressed as MgO content) dominantly controls the mineral-melt Zn partitioning under peridotite melting conditions. These data, along with published mineral-melt DFe2+ data, enable us to calculate appropriate DZnper/m/DFe2+per/m, which is 0.78 ± 0.02 under arc and MORB spinel peridotite melting conditions. Based on these parameters, the calculated average melt Zn/FeT ratio variation caused by per log unity fO2 change in typical fO2 span of arc and MORB mantles is only ∼ 0.69 ± 0.20*10−4. Alternatively, melt Zn/FeT ratio variations caused by changes in Zn-Fe contents and mineralogy of peridotites are ±1.10*10−4. These findings indicate that melt Zn/FeT ratio variation induced by one log units fO2 change is on the same order of magnitude as those caused by changes in Zn-Fe contents and mineralogy of peridotites. Therefore, unless the precise chemical and mineralogical compositions of the mantle sources can be determined independently, the melt Zn/FeT redox proxy is unsuitable for tracing the mantle fO2. Our study, combined with recent works on melt Cu and V/Sc redox proxies, suggests that these redox proxies, previously considered as the strongest evidence for a reduced arc mantle, might not support the idea of a reduced arc mantle.

Prolonged arc accretion during growth of juvenile crust in the Arabian Nubian Shield: Insights from the granitoids of northern Ethiopia

The Arabian Nubian Shield (ANS) is one of the largest juvenile continental crust formed after the Archean. To determine the timing and understand the mechanism of its early crustal growth, we conducted geochronological and geochemical studies on granitoids from northern Ethiopia. A plagiogranite, dated at 929.7 ± 2.2 Ma, represents one of the early granitoids from the ANS. It shows low K2O, TiO2, and REE contents, flat REE pattern and absence of Eu anomaly. Moreover, it exhibits (87Sr/86Sr)i, ƐNd(t) and ƐHf(t) values of 0.70341, +5.0 and +8.4, respectively. Its zircon δ18O value is 4.8‰, lower than the mantle value. These characteristics suggest that it was derived from partial melting of altered oceanic crust. The oxygen fugacity obtained from zircon trace elements is ΔFMQ+1.3, consistent with a subduction setting.Other plutons have much younger ages ranging from 860 to 840 Ma and are mainly medium K, I-type granitoids. These granitoids show low MgO, Ni and Cr contents, low Sr/Y, (La/Yb)N, Nb/Ta and Zr/Sm ratios. They exhibit whole-rock (87Sr/86Sr)i values of 0.70236–0.70304, ƐNd(t) values of 4.2–5.2, ƐHf(t) values of 5.8–7.6 and zircon ƐHf(t) values of 5.5–10.4, slightly lower than coeval depleted mantle. Furthermore, they exhibit fractionated REE patterns, enrichments in LILE and depletion in HFSE. These geochemical features suggest that these granitoids were generated by remelting of arc crust. Compiled data show that the associated basaltic rocks are of arc affinity, which confirms the coeval development of arc magmatism in the southern ANS. Our results suggest that the growth of juvenile crust in the southern ANS started from the early Neoproterozoic and peaked at ca. 880 to 800 Ma, much earlier than those in the northern ANS. The prolonged history accounts for the growth of the vast juvenile crust in the ANS.

Settings Trace elements and garnet formation in a distal skarn zone: a case study of the Rudnik deposit, Central Serbia

The Rudnik Pb-Zn deposit is hosted in skarns and hornfels formed in the late Oligocene by contact metamorphism of limestones, sandstones and shales. Garnets, together with epidote, represent the main non-metallic minerals in the Rudnik skarn. In the distal skarn zone, the garnets are rare and their occurrence is related to the flow path of hydrothermal fluids. To constrain the hydrothermal and physicochemical conditions, in situ elemental SEM-WDS and LA-ICP-MS analyses, and fluid inclusion microthermometric measurements, were made. The Rudnik garnets from the distal skarn zone are predominantly of andradite-grossular composition (Adr39.3–88.9Grs2.9–53.9Alm0.5–10.0), with a small amount of spessartine. Generally, the Fe-rich garnets show a positive Eu anomaly with LREE enrichment and a HREE flat pattern, with homogenization temperatures and salinities of fluid inclusions ranging from 373 to 392°C and from 14.25 to 15.27% NaCl equivalent, respectively. The trace elements and microthermometric properties indicate that the garnets formed at moderately high temperatures, mildly acidic pH levels and increased oxygen fugacity

The fate of nitrogen during early silicate differentiation of rocky bodies constrained by experimental mineral-melt partitioning

Nitrogen (N) is an essential element for life. Yet the processes of planet formation and early planetary evolution through which rocky planets like Earth obtained their atmospheric and surface nitrogen inventory are poorly understood. In order to understand the effect of early silicate differentiation of the rocky bodies on N inventory, here we study the elemental partitioning of N between the silicate minerals and melts. We conducted laboratory experiments using tholeiitic basalts and Fe + Si alloy mixtures at 1.5 – 4.0 GPa and 1300 to 1550 °C under graphite saturation at an oxygen fugacity range of IW–1.1 to IW–3.0. The experiments yielded an assemblage of Fe-rich alloy melt (am) + silicate melt (sm) + clinopyroxene (cpx) ± garnet (grt) ± orthopyroxene (opx) ± plagioclase (plag). Using electron microprobe, we determine that under the experimental conditions, N act as an incompatible element with DNcpx/sm (0.11 – 0.47) >DNplag/sm (0.41) >DNopx/sm (0.25) >DNgrt/sm(0.06 – 0.21). The DNmineral/sm do not show any strong dependence on temperature, pressure, and melt composition. However, through comparison with previous estimates, it appears that with decreasing fO2, N becomes less incompatible. Under our experimental conditions of alloy melt-mineral equilibria, N behaves as a siderophile element (DNam/mineral ranging from 4.1 to 60.6) with fO2 playing the strongest control on DNam/mineral. Our data suggest that under reducing conditions, in the early stages of a magma ocean (MO) and/or deeper mantle, silicate minerals would hold a non-negligible fraction of N as N becomes less atmophile and siderophile. Therefore, reduced parent bodies could also retain substantial N in the residual mantle during partial melting. The extraction of N from an internal MO or a solid planetary mantle is thus enhanced only as the system becomes more oxidizing, enriching the surficial reservoirs in N. Thus, Earth’s N2-rich atmosphere may be intrinsically linked to its mantle oxidation, whereas other rocky planets of the Solar System, such as Mars and Mercury, may have retained a significant portion of their N inventory in nominally N-free mantle silicates through episodes of MO crystallization and mantle melting.

The Yadovitaya fumarole, Tolbachik volcano: A comprehensive mineralogical and geochemical study and driving factors for mineral diversity

Active volcanic fumaroles are one of the most spectacular natural objects in terms of mineral diversity. The Great Tolbachik Fissure Eruption (GTFE) (Kamchatka) fumaroles are renowned for its exceptional number of mineral species. The total number of minerals that have been reliably identified from this particular locality exceeds 400, which is approximately 6.5 % of all known minerals to date. In this study, we employ a comprehensive approach (bulk chemistry, microprobe analysis, powder X-ray diffraction, HR X-ray computed tomography, and 34S, 18O, and 65Cu isotope measurements) to study the distribution of primary exhalation and secondary mineral assemblages and to reveal the driving factors responsible for the unique mineral diversity in the Yadovitaya fumarole. High oxygen fugacity, the interaction of minerals with atmospheric oxygen and water from seasonal precipitation (leading to abundant hydrated mineral associations), temperature conditions controlling the spatial distribution of mineral-forming components, gas-rock interactions, and basaltic scoria morphology perfect for the crystallization of various minerals are some of the factors revealed. The combination of these factors caused a stepwise mineralization resulting in 12 zones of the Yadovitaya fumarole with characteristic mineral assemblages. The described mineralogy of the Yadovitaya fumarole demonstrates a consistent spatial evolution of fumarolic mineral assemblages that vary in complexity, chemistry, and interaction patterns with the surrounding environment. The examination of mineralogical and geochemical data yields novel insights into the active volcanic systems that are associated with the formation of distinct oxidation-type fumaroles.

Scheelite as a microtextural and geochemical tracer of multistage ore-forming processes in skarn mineralization: A case study from the giant Xintianling W deposit, South China

The Xintianling deposit is one of the largest skarn-type scheelite deposit in China. Recent discoveries of quartz-vein-type scheelite mineralization within the deposit have raised questions about its origin and the evolution of ore-forming fluids, hindering a comprehensive understanding of the ore-forming process. We investigate the microtextures, trace elements, and oxygen isotope compositions of scheelite from different stages in both skarn-type and quartz-vein-type W mineralizations. Combined with apatite geochemistry and U–Pb dating, we determine the timing of quartz-vein-type mineralization and the evolution of magmatic-hydrothermal system. Based on detailed petrological observation, three types (seven subtypes) of scheelite and two types of apatite are identified. The Mo contents and Eu/Eu* ratios of scheelite, along with the Ce/Ce* ratios of apatite indicate the oxygen fugacity of fluids during the skarn metallogenic episode is generally higher than that during the quartz-vein metallogenic episode. Furthermore, the Y/Ho ratios and REE patterns of scheelite indicate the presence of at least three significant stages of fluid influx and fluid-rock interactions throughout entire ore-forming process. The O isotope compositions of scheelite in the quartz-vein-type metallogenic episode reveal that the ore-forming fluids are originated from a magmatic source, and meteoric water was mixed into the system, leading to the precipitation of the latest stage of scheelite. The apatites closely coexist with scheelite, from the early and the late stages of quartz-vein metallogenic episode, yield consistent U–Pb ages within error of 160.4 ± 2.4 Ma and 158.4 ± 1.3 Ma, respectively, indicating a close genetic link between quartz-vein-type W mineralization and the fine-grained porphyritic biotite granite. Our study highlights the significance of pulsed fluid exsolution and the combined effects of multiple mechanisms, including fluid-rock interaction, fluid mixing, and physicochemical condition changes, in the formation of large W deposits.

The magma evolutional constrains on the genesis of proximal Zn skarn mineralization: A case study from the Yaojialing deposit in Tongling district, eastern China

The major factors especially the roles of the magma evolution controlling the Zn/Cu mineralization in skarn deposits are still controversial. Yaojialing is a large-sized skarn Zn polymetallic deposit (1.74 Mt Zn at 3.6 %, 30.4 t Au at 4.2 g/t and 24.8 t Cu at 0.83 %) located in the Tongling district of the Middle–Lower Yangtze belt (MLYB), both the proximal and distal areas of the deposit exhibit high Zn/Cu mineralization. The intrusions in Yaojialing primarily consist of quartz monzonite porphyry (QMP) and granodiorite porphyry (GDP), and the QMP is related to skarn mineralization. Both the QMP and GDP display relatively high (87Sr/86Sr)i values (0.707907 to 0.709390), low εNd(t) values (−9.05 to −8.17) and negative εHf(t) values (−8.51 to −11.72), suggesting that they originated from a mixed source of enriched mantle and lower crust. Both the QMP and GDP contain type I and type II amphiboles, while type III amphibole exists only in QMP. Type I amphibole is acicular crystals shape, type II amphibole is euhedral in shape and relatively large in size (0.6–2.0 mm), while type III amphibole crystallized around the margin of type II amphibole. The type I amphibole from QMP and GDP show similar calculated temperatures (948–1010 ℃), pressures (2.9–6.5 kbar, corresponding depths at 11.0 to 24.4 km), fO2 (ΔFMQ = 0.2–1.9) and H2O content (4.2–6.8 wt%). Type II amphibole crystallized at 815–941 ℃, 1.2–2.9 kbar (corresponding to depth of 4.6–11.1 km), ΔFMQ = 0.7–2.1, and 4.4–5.7 wt% H2O. Type III amphibole have a lower temperature (679–795 ℃), pressure (<0.5 kbar) and water content (2.5–4.3 wt%) but higher fO2 value (ΔFMQ = 3.1–3.8) compared to type I and type II amphiboles. Reverse zoning of plagioclase and higher Mg# (74 to 89) of type III amphibole in QMP are resulted from injection of mafic magma at shallow depths, which provide sufficient metal and favorable conditions for the formation of QMP parental magma. Modeling of magma H2O solubility indicates that QMP begins to exsolve fluid at depth of 6.2–11.1 km. Initial low oxygen fugacity and ore-forming element differential release during fluid exsolution process resulted in the high Zn/Cu mineralization at Yaojialing.

Geochronology and Geochemistry of Granodiorite Porphyry in the Baoshan Cu-Pb-Zn Deposit, South China: Insights into Petrogenesis and Metallogeny

The Baoshan Cu-Pb-Zn deposit is situated at the intersection of the Qin-Hang Cu polymetallic and Nanling W-Sn polymetallic metallogenic belts. The age, lithology, petrogenesis, and tectonic setting of granodiorite porphyry within the deposit remain subjects of debate. Additionally, there is a lack of comparative studies with the W-Sn-related granites in the region. This study conducted whole-rock major and trace element analysis, Sr-Nd isotope analysis, and zircon U-Pb dating on the Baoshan granodiorite porphyry. The zircon U-Pb age of the granodiorite porphyry is 162 ± 1 Ma. The whole-rock SiO2 and K2O contents range from 65.87 to 68.21 wt.% and 3.42 to 5.62 wt.%, respectively, indicating that the granodiorite porphyry belongs to high-potassium calc-alkaline I-type granite. The granodiorite porphyry is characterized by enrichment in LREE and depletion in HREE (LREE/HREE ratio = 6.2–21.2). The samples of granodiorite porphyry generally exhibit weak negative Eu anomalies or no Eu anomalies (δEu = 0.62–1.04, mean = 0.82). The (87Sr/86Sr)i and εNd(t) values are 0.707717–0.709506 and −7.54 to −4.87, respectively. The whole-rock geochemical composition and Sr-Nd isotopic values indicate that the magma originated from the partial melting of the Mesoproterozoic ancient crust and Neoproterozoic mafic juvenile lower crust, with the addition of high oxygen fugacity and water-rich lithospheric mantle melts. The source of the granodiorite porphyry in the Baoshan deposit is significantly different from the crust-derived metapelite source of the W-Sn-related granite in the area, indicating that different magma sources might be the main reason for the co-spatial and nearly contemporaneous development of Cu-Pb-Zn and W-Sn mineralization in the southern Hunan region.

The reduced alloy in Earth's upper mantle: Experimental constraints on Fe-Ni-S-C(-O) melt compositions and deep mantle oxygen fugacity (5–16 GPa)

High-pressure experiments conducted at upper mantle conditions reveal increased Fe3+ contents in majoritic garnet with increasing pressure. Consequently, at ∼8 GPa, Fe2+ disproportionation is expected to generate Fe0, leading to a higher metal/sulfur ratio of the initially present monosulfidic melt. This study experimentally investigates equilibrium systematics between the reduced Fe-Ni-S-C(-O) melt and mantle silicates at 5–16 GPa and near-adiabatic temperatures (1420–1590∘C), aiming to constrain the alloy melt composition in equilibrium with bulk silicate Earth-like (BSE) mantle silicates. As analysis of unquenchable liquid alloys requires large melt pools, experimental charges were designed towards a 50:50 ratio of alloy:silicates, with Fe/Ni ratios, sulfur and carbon scaled to correspond to a BSE with 200–250 ppm S and 100–150 ppm C.Observed phase assemblages consist of Fe-Ni-S-C(-O) melt (metal/(S+O): 0.9–3.5, Ni/(Fe+Ni): ∼0.3–0.6 and 0.2–1.6 wt.% oxygen) saturated with graphite/diamond and coexisting with olivine/wadsleyite (XMg: 0.76–0.91), garnet and cpx ± low-Ca pyroxene. Oxygen fugacities (fO2) range from -0.5 to +4.0 relative to the iron-wüstite (IW) buffer. In most runs, Fe0–Fe2+ redox equilibration affected silicate XMg's, resulting in values <0.90. Therefore, an empirical model was developed to predict KDNi-Fealloy-olivine, allowing to recalculate the experimental results for a primitive BSE mantle composition with XMg of 0.90.Modeling BSE, the alloy's metal/(S+O) increases from 1.1 to ∼7 while Ni/(Fe+Ni) decreases from 0.35 to 0.19 at 5–16 GPa. With BSE-like S concentrations, the abundance of the Fe-Ni-S-C(-O) melt increases from 600–750 ppm at 5 GPa to ∼3800 ppm at 16 GPa, 100–150 ppm bulk carbon lead to graphite/diamond saturation to ∼14 GPa. Finally, a method is presented to derive fO2 from modeled liquid alloy compositions, which act as a “redox-sensor”. For a BSE-like mantle with 250 ppm S, fO2 decreases from IW+2.6 at 5 GPa to IW at 8 GPa, further decreasing to IW-1.0 at 12–16 GPa.

The occurrence and enrichment of cobalt in skarn Pb-Zn deposits: A case study of the Niukutou Co-rich deposit, East Kunlun metallogenic belt, western China

The East Kunlun orogenic belt is one of the most important Co-rich polymetallic metallogenic belts in China. Niukutou, a typical Pb-Zn-(Fe) skarn deposit, is situated within the marble formations of the Ordovician-Silurian Qimantagh Group in this belt. Six distinct stages of mineralization have been identified: (1) prograde skarn stage, (2) hydrous mineral-oxide stage, (3) pyrrhotite stage, (4) chalcopyrite stage, (5) sphalerite-galena stage, and (6) carbonate stage. Co enrichment predominantly manifests at chalcopyrite stage, with two distinct Co minerals identified: glaucodot and cobaltite. Co is also present as isomorphous substitution in sulfides (mostly arsenopyrite) and as inclusions in chalcopyrite. Variations in As and S contents in arsenopyrite suggest a steady decrease in ore-forming fluid temperature from the pyrrhotite stage to sphalerite-galena stage. Variations in the Co, Ni, Se, As, Sb, Cu, Sn, Ag, and Zn contents in pyrite indicate fluctuations in temperature, oxygen fugacity, and fluid composition during ore formation. Sulfur isotope compositions (δ34S) through the pyrrhotite stage to the sphalerite-galena stages show a limited range from +3.4 to +7.0 ‰, suggesting a predominantly magmatic source. Whereas, the δ34S of pyrite and marcasite in carbonate stage exhibit significant variations from −22.5 to +22.7 ‰. We propose that this significant variation may be caused by mixing of sulfur from the surrounding rocks and the large fluctuations in oxygen fugacity due to the influx of meteoric water at the carbonate stage. Overall, Co in Pb-Zn skarn system may occur either as independent minerals or as lattice substitution in sulfides such as arsenopyrite. The deposition of Co-bearing minerals is related to decreases in temperature and fO2 during the chalcopyrite stage.

Chemical interdiffusion between Na-series tephritic and phonolitic melts with different H2O content, temperature, and oxygen fugacity values

Chemical interdiffusion between Na-series tephritic and phonolitic melts with different H₂O content, temperature, and oxygen fugacity values

Two-stage mineralization of the Jinkeng Sn-Cu deposit in Eastern Guangdong, Southeast China: Response to magmatic activities and tectonic transformation

The Jinkeng Sn-Cu polymetallic deposit in South China consists of two different types of orebodies: 1) NE-striking skarn- and vein-type Cu-Pb-Zn-Sn orebodies in volcanic rocks suffering subsequent ductile shear deformation, and 2) NW-striking quartz-cassiterite-sulfide veins filled in the faults at the porphyritic granodiorite outward from the fine-grained granite which does not exhibit deformation. The relationships among Sn-Cu polymetallic mineralization, regional magmatism, and deformation metamorphism are still controversial. To address it, the geochronological, whole-rock and mineral geochemical research along with the detailed field investigation were conducted in this study. Our zircon U-Pb dating results show that the volcanic rocks formed at 158–162 Ma, earlier than the porphyritic granodiorite which yields the emplacement age of 146–147 Ma. In-situ LA-ICP-MS U-Pb dating of cassiterite from the deformed skarn ores indicates the early-stage mineralization occurred at 146 ∼ 148 Ma, which is similar to the emplacement age of the porphyritic granodiorite, but earlier than the formation of quartz-cassiterite-sulfide veins and the fine-grained granite (141∼144 Ma). Further, the whole-rock and biotite geochemistry, and zircon Hf isotope compositions suggest that the porphyritic granodiorite exhibits a lower degree of magma differentiation, higher oxygen fugacity, higher Cl and lower F contents than the fine-grained granite. The porphyritic granodiorite might provide the most Cu-Pb-Zn budget accompanied by minor Sn for early-stage mineralization. Overall, our study suggests that the Jinkeng Sn-Cu polymetallic deposit formed in two scenarios where the early dominated Cu-Pb-Zn and minor Sn mineralization related to the emplacement of the porphyritic granodiorite is superimposed by the late vein-type Sn-dominated mineralization related to the emplacement of the fine-grained granite. The two isolated mineralizing events (∼147 Ma and ∼141 Ma, respectively) in Jinkeng were probably responded to the regional magmatic activities triggered by the tectonic transformation where two extensional tectonic events were separated by a short contractional event (147–144 Ma).

Vanadium isotope records of the transformation from carbonated melt to alkali basalt

Volcanic clasts from the International Ocean Discovery Program Site U1431 in the South China Sea (SCS) were analyzed for V isotopic compositions in this study. These volcanic clasts represent mantle-derived carbonated melts and record the transition from carbonated melts to alkali basalts. Based on the formation sequence, these clast samples were divided into early-stage (> 8.3 Ma) and late-stage (< 8.3 Ma) clasts. The early-stage volcanic clasts have δ51V values of −0.76‰ to −0.67‰, which provide an estimate for the V isotopic composition of primary carbonated melts. Their V isotopic compositions are slightly heavier than those of mid-ocean ridge basalts (−0.84‰ ± 0.10‰) and bulk silicate Earth (−0.86‰ to −0.91‰), reflecting the control of low-degree partial melting under conditions of high oxygen fugacity. The late-stage volcanic clasts have δ51V values ranging from −0.62‰ to 0.29‰, which are systematically heavier than those of early-stage volcanic clasts. The carbonated melts rose through and reacted with the lithospheric mantle and were transformed into alkali basalts by dissolving orthopyroxene and precipitating olivine and/or clinopyroxene. Because the reactants and reaction products do not lead to significant V isotope fractionation, the V isotopes show limited variations during transformation from carbonated melts to alkali basalts. The alkali basalts were emplaced into shallow crust by multiple pulses, in which the magma experienced variable degrees of magma differentiation, with δ51V values close to those of the initial alkali basalts or increasing due to fractional crystallization of FeTi oxides. The change in V isotopic compositions from early-stage volcanic clasts to late-stage volcanic clasts was driven by the varying magnitude of influence exerted by different magmatic processes en route from the deep mantle to the shallow crust.

The constant oxidation state of Earth’s mantle since the Hadean

Determining the evolutionary history of mantle oxygen fugacity (fo2) is crucial, as it controls the fo2 of mantle-derived melts and regulates atmospheric composition through volcanic outgassing. However, the evolution of mantle fo2 remains controversial. Here, we present a comprehensive dataset of plume-derived komatiites, picrites, and ambient mantle-derived (meta)basalts, spanning from ~3.8 Ga to the present, to investigate mantle thermal and redox states evolution. Our results indicate that fo2 of both mantle plume-derived and ambient mantle-derived melts was lower during the Archean compared to the post-Archean period. This increase in the fo2 of mantle-derived melts over time correlates with decreases in mantle potential temperature and melting depth. By normalizing fo2 to a constant reference pressure (potential oxygen fugacity), we show that the fo2 of both the mantle plume and ambient upper mantle has remained constant since the Hadean. These findings suggest that secular mantle cooling reduced melting depth, increasing the fo2 of mantle-derived melts and contributing to atmospheric oxygenation.

Mobilization of isotopically heavy sulfur during serpentinite subduction.

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.

Kyanite and Cordierite‐Andalusite occurrences in parts of Barrow's Staurolite zones – The effects of high ferric iron

AbstractGeorge Barrow's maps (1893, 1912) of the metamorphic zones named after him in the south‐eastern Scottish Highlands, show a prominent staurolite zone running from the west of Glen Clova to the North Sea coast near Stonehaven in the east. Pelitic mica schists throughout this zone commonly show principal mineral assemblages of staurolite+biotite+garnet+muscovite +quartz (St + Bt + Grt), with sodic plagioclase, ilmenite and sometimes magnetite as common accessories; these schists have bulk compositions corresponding with those of common Dalradian metasediments. However, the mineral assemblages on the low‐ and high‐grade margins of the staurolite zone show evidence of changes from west to east. Lower grade assemblages near Stonehaven include chloritoid+biotite, which has not been found further west in the classic ‘Barrovian’ sequence; whilst the higher grade assemblages near Stonehaven lack kyanite, which is widely seen further west. The Stonehaven area has been suggested to have under gone metamorphism at lower pressure (P) than the classic region of the ‘Glens’ inland to the west.This paper describes the occurrence at middle grade in the broad staurolite zone, of unusual bulk rock compositions showing high ratios of Fe2O3/(Fe2O3 + FeO) and MgO/(MgO + FeO) (abbreviated to M/FM). The high M/FM assemblages are distinct from those of the common St‐Bt‐Grt schists. The high ratios of ferric to ferrous iron are thought to result from original sedimentary protolith compositions, that led to metamorphism at relatively high conditions of oxygen fugacity (ƒo2), and resulted in the formation of haematite‐bearing assemblages, rather than ones carrying accessory ilmenite and magnetite as in the common St + Bt + Grt rocks.In the west (Glen Lethnot), the haematite‐bearing pelites show the occurrence of kyanite at a distinctly lower grade than the common (haematite‐free) pelites, and a transition from staurolite‐biotite (St + Bt) through staurolite–kyanite‐biotite (St + Ky + Bt) to kyanite‐biotite (Ky‐Bt) assemblages occurs with increasing abundance of haematite and higher bulk M/FM values. In all bulk compositions, the upgrade formation of kyanite may be associated with the movement of the St + Ky + Bt assemblage to lower M/FM bulk compositions with increasing temperature (T). The difference in the temperature of lowest‐grade kyanite formation in haematite‐rich schists, compared with that in common haematite‐free schists may approach 50°C.In the east (Stonehaven section), the haematite‐bearing assemblages are much rarer than in Glen Lethnot, but those found so far are very distinctive in showing large porphyroblasts of probable cordierite (typically altered to chlorite and sericite). Occasional assemblages of andalusite‐cordierite‐biotite (And‐Crd‐Bt) also occur in the haematite‐bearing rocks and confirm lower pressures of metamorphism near Stonehaven than those seen further west in Glens Clova, Lethnot and Esk.

Mineral chemistry, petrography and crystallization conditions of the Middle Eocene Kazıkbeli Pluton (Eastern Pontides, NE Türkiye)

The Eastern Pontides host a diverse suite of plutonic rocks spanning a wide range of ages and compositions. Among these, the Middle Eocene Kazıkbeli pluton, located in the Kürtün district of Gümüşhane, stands out due to its distinctive petrological characteristics. This study aims to unravel the petrological implications of petrographic and mineral chemical data to constrain the physicaydınçakırochemical conditions (temperature, pressure, oxygen fugacity) under which the Kazıkbeli magma crystallized and was emplaced. By integrating mineral chemical data, we seek to quantify emplacement pressure, crystallization temperature, and oxygen fugacity. A comprehensive understanding of the genetic relationships and physicochemical properties of the Kazıkbeli pluton rocks, as determined through geological, petrographic and mineral chemistry, is crucial for elucidating the geological evolution of the Eastern Pontides. The Kazıkbeli Pluton exhibits a predominant NE-SW orientation and encompasses an area of roughly 46 km². Modal mineralogical analysis reveals a compositional spectrum ranging from gabbroic diorite to monzogranite, with granodiorite and tonalite being the most prominent rock types. Textural variations encompass fine- to medium-grained, porphyritic, poikilitic, and occasionally graphic textures. The primary mineral assemblage of the pluton comprises plagioclase, orthoclase, quartz, amphibole, biotite, and Fe-Ti oxides. Accessory minerals include zircon, apatite, sphene, and allanite. Plagioclases are labradorite to oligoclase (An26 to An66) in composition. K-feldspar minerals exhibited an orthoclase composition (Or80 to Or97). All amphiboles belong to the calcic amphibole field and exhibit a magnesio-hornblende (Mg#=0.63-0.73) composition. Biotites crystallized as solidified melt products with compositions between annite and phlogopite endmembers, plotting close to the magnesium-rich (Mg#=0.52-0.58) end of the phlogopite solid solution series. Calculated crystallization temperatures derived from amphibole and biotite data range from 712°C to 824°C. Pressure estimations calculated using amphibole-plagioclase, amphibole and biotite suggest a range of 0.04 to 2.06 kbar. Oxygen fugacity (ƒO2) values calculated using amphibole and biotite fall between -12.5 and -16.1. Amphibole-based water content estimations indicate a range of 3.7% to 5.7% for the pluton. Biotite compositions within the studied Kazıkbeli pluton rocks exhibit characteristics suggestive of a potential mantle origin. Geobarometric calculations based on mineral chemistry data with geological and petrographic features indicate the emplacement of the Kazıkbeli Pluton at relatively shallow depths within the crust (~1 to 8 km).

Geochronology, Petrogenesis, and Metallogenic Implications of Quartz Monzonite Porphyry in the Shanlixu Copper–Gold Deposit in the Lujiang–Chuzhou Area, Middle–Lower Yangtze River Valley Metallogenic Belt, China

The Lujiang–Chuzhou Metallogenic Area is an important component of the Middle–Lower Yangtze River Valley Metallogenic Belt. Despite being an important copper–gold deposit in this area, the Shanlixu skarn Cu-Au deposit has not yet been systematically studied. According to LA-ICP-MS zircon U-Pb dating, the quartz monzonite porphyry from the Shanlixu deposit is aged 137.5 ± 1.7 Ma: while it differs from the timing of the magmatism and related mineralization in the Lujiang–Chuzhou Area, it is consistent with magmatic activity elsewhere in the Middle–Lower Yangtze River Valley Metallogenic Belt. The Ce4+/Ce3+ values of zircon in the quartz monzonite porphyry vary from 204.5 to 886.5, indicating that the intrusion might have formed in an environment with high oxygen fugacity. Additionally, the quartz monzonite porphyry exhibits high contents of Al2O3, Sr, Ba, and Mg# (Mg# = Mg2+/(Mg2+ + Fe2+)) and low ratios of Y, Nb, Ta, and K2O/Na2O, showing geochemical characteristics similar to those of adakitic rocks. Based on these characteristics, it is suggested that the intrusion might have been derived from the partial melting of subducted oceanic crust under a continental arc margin setting. Furthermore, it is strongly indicated that the quartz monzonite porphyry from the Shanlixu deposit, in the Lujiang–Chuzhou Area, is closely related to Cu-Au mineralization, as suggested by the age of the intrusion, which is approximately 137 Ma. These findings provide a new direction for research and exploration in this region.