Low fO2 Research Articles

Experimental constraints on the behaviour of sulphur in the 2021 Cumbre Vieja (La Palma) basanite

We performed experiments to constrain the effects of sulphur and oxygen fugacities on magma chamber and outgassing conditions of the La Palma 2021 eruption. Based on a series of controlled experiments on basanitic products carried out at 1040 °C and 200 MPa, we show that sulphur addition affects the stabilities of amphibole and olivine, in particular at high fO2 and elevated S contents which together inhibit amphibole crystallization. We also show that the overriding control on S systematics is oxygen fugacity, with melts capable of dissolving from 1000 up to 8000 ppm S, depending on fO2. Increasing the bulk S content increases the S content of the silicate melt up to ∼2000 ppm for fO2 < NNO + 2, and 7000–8000 ppm at higher fO2. Further increase in dissolved S is prevented by the buffering effects of either sulphide at low fO2 or anhydrite at high fO2. Modelling shows that the observed CO2/SO2 and H2O/SO2 ratios of volcanic gas emissions during the eruption imply a pre-existing >5 wt% exsolved fluid in the reservoir, with fS2 at ∼0.1 MPa at fO2 above NNO. Our work confirms that basaltic magmas may coexist with a significant amount of excess fluid which in turn holds an important part of the sulphur budget emitted to the atmosphere.

An estimate of chlorine fugacity in the low water fluid of the system С-О-(Н)-NaCl in the cumulus of ultrabasic-basic intrusions

At high PT parameters of the cumulates of ultramafic-mafic intrusions at low fO2 (below the QFM buffer), platinum dissolves in the fluid with CO as a carbonyl complex of the native metal. The high solubility of platinum as PtCl2 in brines with NaCl, which is associated with the formation of low-sulfide PGE deposits, is achieved at high oxygen fugacity (above the NNO buffer). It is assumed that at low oxygen fugacity in the low water CO–CO2 fluid, native Pt can also be converted into a cation-soluble form by chlorination. Experimental data (Р = 200 MPa, Т = 950oC, fO2 QFM and fluid CO–CO2) on the reaction of NaCl with magnetite and chromite, accessor minerals of mafic-ultramafic intrusions, with the formation of iron and chromium chlorides are presented. As shown by thermodynamic calculations, the equilibrium in the FeCl3–FeCl2 pair provides the high chlorine fugacity (fCl2). This fugacity is only 3–4 orders of magnitude lower than fCl2 in the Pt–PtCl2 equilibrium and 2.5–3 orders of magnitude higher than in the aqueous fluid 1 M HCl at the same P–T–fO2 parameters.

Evidence for isotopically light Fe mobility under oxidising conditions in subduction zone fluids: A record of Monviso meta-serpentinites, Western Alps

The isotopically light Fe signature of arc magmas relative to mid-oceanic ridge basalts (MORB) is expected to be related to the redox state of their source. This implies a link between Fe mobility and redox variations across subduction zones. Here we address slab chemical variations during prograde metamorphism through a comprehensive geochemical study, including major, trace elements and Fe stable isotope (δ56Fe) analyses, of meta-serpentinites composing the eclogitic meta-ophiolite of the Monviso massif (Western Alps, Italy). These rocks partly preserve mantle related geochemical heterogeneities, as supported by negative correlations between fluid immobile elements (High Field Strong Elements) and LREE/HREE (Light – Heavy Rare Earth Elements) ratios. They are however characterized by large Cs enrichments relative to U or alkali elements suggesting that abyssal fluid mobile elements signature was overprinted by subduction related processes. Meta-serpentinites display large δ56Fe variations, from -0.20 ± 0.05 ‰ to +0.09 ± 0.03 ‰. Mineral separate analyses of olivine bearing veins show low Δ56Fe between olivine and magnetite (∼ 0.4 ‰), which according to Fe isotope thermometry correspond to high temperature equilibration, estimated between 530 and 550 °C, compatible with Monviso metamorphic climax (520–570 °C and 2.6–2.7 GPa). These results, in combination with geochemical modelling, confirm a reset of δ56Fe signature of abyssal serpentinites during prograde metamorphism in subduction zones. The bulk rock δ56Fe values of Monviso meta-serpentinites are negatively correlated with their Fe3+/∑Fe and As concentrations (a redox-sensitive and fluid mobile element). These correlations can be attributed to a metasomatism by external fluids derived from slab serpentinites during subduction. It also concords with the oxygen fugacity (fO2) record in meta-serpentinites, with meta-serpentinites equilibrated at high fO2 displaying the lowest δ56Fe values while samples equilibrated at low fO2 display mantle like δ56Fe signatures. These results highlight that oxidising conditions during serpentinite dehydration are likely to boost isotopically light Fe mobility in slab derived fluids.

Cobalt remobilization during tectonic–hydrothermal overprinting: A case from the Tuolugou Co(–Au) deposit in East Kunlun Orogenic Belt, China

Stratiform Cu-Co deposits hosted in (meta-) sedimentary and volcaniclastic rocks contribute two-thirds of the global Co supply. However, the mechanisms driving Co remobilization during tectonic-hydrothermal overprinting events remain poorly understood. As a dominant Co repository, pyrite can provide valuable insights into mineralization history due to its refractory nature. Here, we present the first micro-analytical investigation of pyrite from the Tuolugou Co(–Au) deposit in East Kunlun Orogenic Belt. Ore textures indicate that Co mineralization is attributed to two distinct stages: primary enrichment and subsequent overprinting processes. The former is characterized by pyrite (PyI with up to 3.92 wt% Co) remnants exhibiting oscillatory zones, while the latter is marked by deformation of pyrite (PyII) ores. Three overprinting episodes, namely Da, Db, and Dc, are further distinguished according to varying extents of deformation and mineral assemblages. The Da is characterized by synkinematic PyIIa (up to 4.18 wt% Co) augens, which were most likely formed via pressure–solution mechanism. The Db is represented by polygonal PyIIb (up to 4.75 wt% Co) and siegenite with 120° triple–point junctions. The random orientation and rare intragrain misorientation of cobaltiferous sulfides at Db suggest their formation by recrystallization without plastic strains. The Dc resulted in the formation of Co ± As–rich PyIIc (up to 5.36 wt% Co) along with minor occurrence of cobaltite–gersdorffite, pyrrhotite (up to 1.25 wt% Co), and marcasite (up to 1.28 wt% Co). The PyIIc replacing PyI underscores the role of fluid-coupled dissolution and precipitation during fluid–rock interactions in the formation of these cobaltiferous sulfide assemblages at Dc. The presence of PyIIc infilling within the PyI fissures, in conjunction with the transition from siegenite to cobaltite–gersdorffite, suggests a shift towards low fO2 and low temperature conditions under relatively brittle setting. There is a discernible disparity in sulfur isotope compositions between the two mineralization stages. The PyI exhibits a narrow range of δ34SV–CDT values from –2.14 to 1.35 ‰, indicating a magmatic sulfur origin. In contrast, PyII displays a wide δ34SV–CDT range of –5.22 to 6.16 ‰, suggesting an involvement of strata sulfur during the overprinting stage. Monazite U-Pb dating has effectively constrained two mineralization events. The ca. 453 Ma age implies a potential correlation of the primary Co mineralization with the Late Ordovician to Early Silurian exhalative-syngenetic processes in a Proto–Tethyan-related post–collisional extension setting. Conversely, the ca. 190 Ma age indicates that Co remobilization was instigated by the early Mesozoic ductile–brittle deformation associated with the Paleo-Tethyan orogenesis. Finally, geochemical modeling was performed by simulating the interaction of a Co-rich acidic, reducing fluid with typical quartz-albitite rocks. The simulations demonstrate the appearance of independent Co minerals such as Co-pentlandite during the reaction progression, greatly supporting ore upgrading via tectonic-hydrothermal overprinting.

Pyrrhotites in asteroid 162173 Ryugu: Records of the initial changes on their surfaces with aqueous alteration

The surface chemistry of pyrrhotites from intact particles directly collected from asteroid (162173) Ryugu was investigated by micro-Raman spectroscopy. The Raman peak characteristic to pyrrhotite was observed at around 115 cm−1 in Ryugu pyrrhotites, similar to freshly cleaved surfaces of terrestrial pyrrhotites. Additional Raman bands centered at around 220, 275, and 313 cm−1 with broadened features were also detected from the Ryugu pyrrhotites. The set of Raman bands at 220 and 275 cm−1 was assigned to typical Fe-S stretching vibrations of ν2 (225 cm−1) and ν1 (275 cm−1). These bands are not clearly observed in bulk crystals of pyrrhotite but appear in its nanoparticulate phase. These bands are ordinarily seen in amorphous monosulfides that formed under low oxygen fugacity (fO2) conditions in nature, indicating that the structural alteration of pyrrhotite surfaces occurred heterogeneously on the nanoscale under low fO2 conditions. Further, the Raman band at 313 cm−1 was attributed to a characteristic tetrahedral bonding of Fe(III) in the lattice of FeII1-3xFeIII1-2xS, followed by the local breakdown of the crystal lattice structures from planar bonding with Fe(II). In addition, some areas of the Ryugu pyrrhotite grains showed corroded structures with iridescence. Furthermore, assemblages of magnetite particles were also preferentially observed on small areas of the likely-dissolved pyrrhotite crystals in phyllosilicate matrices. These characteristic features in the Raman spectra and in corroded structures of Ryugu pyrrhotites record changes in the local environmental conditions via aqueous alteration. The corrosion of pyrrhotite crystals followed by the preferential formation of magnetite particles by asteroidal water is the likely product of dissolution of Fe(II) from the pyrrhotite surface and its oxidative precipitation in microchemical environments on the Ryugu parent body.

Origin and thermal evolution of Cr-V-Ti magnetites (lodestones) from Coorg massif, southern India

This study deals with petrology, textural, thermometry, and geochemical characterization of naturally magnetized Cr-V-Ti magnetite deposits within the layered mafic-ultramafic intrusions in Coorg massif of southern India using ore petrography and mineral/whole rock geochemistry. These deposits, also known as ‘lodestones’, occur as rhythmic layers within the lateritized host rock, with the underlying basement distinguished by the presence of charnockites and layered gabbro-anorthosites and pyroxenites, delineating a stratified intrusive setting. Lodestones exhibit complex mineral assemblage involving magnetite, ilmenite, ulvöspinel, spinel, corundum, hematite, goethite, pyrite, pyrrhotite, and amphiboles. The bulk rock chemistry of the lodestone is analogues to Fe-Ti magnetite iron ore deposits with elevated vanadium and chromium contents. Their resemblance to tholeiitic magma-type suggests their formation in a layered intrusive setting, evolved through multiple fractional crystallization under oxidizing conditions. Thermometric and fugacity calculations using different textural associations estimate the magmatic fractional crystallization stage at elevated temperatures (601–704 °C) and low fO2 (−18.6 to −15.3), succeeded by the exsolution stage during subsolidus cooling at lower temperatures (379–540 °C) and high fO2 (−38.2 to −22.1). The whole sequence of formation and evolution of lodestone encompasses primary magmatic crystallization, subsolidus re-equilibration, metamorphism, and secondary weathering. The study also suggests a genetic linkage of lodestone with the associated mafic-ultramafic units, depicting two possible magmatic processes either through slab melting and fractional crystallization associated with subduction or due to plume magmatism and associated rifting.

Petrogenesis, geochronology, and tectonic setting of the Calymmian 1.45–1.50 Ga basic magmatism in the Southern Ribeira Belt, Brazil: evidence of intracontinental rifting and Columbia break-up

ABSTRACT We present new petrographic, whole-rock geochemistry, and SHRIMP U – Pb zircon geochronological data of metabasic rocks interlayered as sills in the metasedimentary units of the Perau and Betara formations, Votuverava Group, Southern Ribeira Belt, Brazil. These formations overlie ~ 1.8 Ga Paleoproterozoic metagranitoids that represent basement inliers from the Paranapanema Craton. Petrography and whole-rock geochemistry allow the recognition of four groups, ranging from primitive to evolved compositions: i) cumulatic metadolerites (G1), ii) isotropic metadolerites (G2), iii) ortho-amphibolites (G3); and iv) ferroan ortho-amphibolites (G4). They exhibit tholeiitic subalkali basaltic composition, near-flat REE patterns, and signatures between N- and E-MORB. Fractional crystallization under low fO2 conditions is the main petrogenetic process controlling the magmatic evolution, as observed by Ti/V and Cr/Y ratio and tholeiitic trends. Crustal contamination signatures are observed through negative Nb anomaly, Th/Nb-Ti/V proxies trends, LILE enrichment, and, also, assimilated xenocryst zircons aged ~ 2.2 Ga. REE and trace element systematics indicate that the basic magmas were generated by ~ 20–10% partial melting of a model asthenospheric mantle source within spinel facies. TiO2/Yb-Nb/Yb and Nb/Yb-Zr/Yb ratio proxies and P-MORB metabasic rocks, previously described in the literature within the Votuverava Group, suggest a plume-influenced melt. A new SHRIMP U – Pb zircon age of 1448 ± 11 Ma was determined for an ortho-amphibolite sample (G3 group). We propose an intracontinental tectonic setting for the genesis of the metadolerites whitin the Perau and Betara formations, suggesting that this extensional event is associated with the Paranapanema Craton rifting. Furthermore, the genesis of the studied metabasic rocks could be associated with a regional extensional event during Calymmian times (~1.5–1.45 Ga), which generated basic magmatism in several other cratons, such as the Congo, São Francisco, Siberian, Laurentian, and China cratons, linked to the break-up of the Columbia Supercontinent.

Optimization of transparent conductive properties of magnetron sputtered Sb-doped SnO2 films by RF power: Towards application in polymer-dispersed liquid crystal (PDLC) films

Sb-doped SnO2 (ATO) films were prepared with different RF powers (PRF) under two O2 flow rates (FO2) by magnetron sputtering, and then subjected to rapid thermal annealing (RTA) treatment. The effects of PRF, FO2, and RTA on the crystallinity, stress, surface morphology, conductive properties, transmittance in visible-light range (TVis), and energy gap (Eg) of the films were investigated. As the PRF increases, the film crystallinity improves or first improves and then slightly degrades, and the compressive stress decreases. With increasing PRF, the surface changes from textured to granular morphology and from granular to honeycomb-like morphology under two FO2, respectively. Meanwhile, the conductive properties first enhance and then degrade, and the TVis and Eg tend to decrease, especially at higher PRF. Basically, the films prepared with higher FO2 have lower compressive stress, inferior conductive properties, and larger TVis and Eg compared with the films prepared with lower FO2. After RTA, the film crystallinity obviously improves, the compressive stress transforms into tensile stress, and the surface morphology has not undergone significant changes. Meanwhile, the conductive properties significantly enhance and Eg obviously increases. The TVis of the films prepared with lower FO2 can be increased by RTA. The influence mechanisms of the above factors on the structure and optoelectronic properties of the ATO films were explored, and ultimately, the ATO films have the TVis of 76.35–80.86%, sheet resistance of 51.7–91.9 Ω/sq., and quality factor of 1.03–1.67 × 10−3 Ω−1 within the optimized PRF range. Polymer-dispersed liquid crystal (PDLC) films were fabricated using optimized performance ATO films as electrodes, and their on-state transmittance, off-state transmittance, threshold electric field, and saturation electric field were 2.08–4.61%, 61.69–68.56%, 0.656–0.796 V/μm, and 1.68–2.108 V/μm, respectively. The current results indicate the potential application of ATO films in PDLC films as electrode.

Partitioning of tin between mafic minerals, Fe-Ti oxides and silicate melts: Implications for tin enrichment in magmatic processes

The partition coefficients of Sn (tin) between minerals and silicate melts (DSnmin/melt) are vital for understanding the Sn enrichment during magmatic processes related to tin-granites. However, experimentally determined DSnmin/melt values remain scarce due to the difficulty in avoiding severe Sn loss to noble metal capsules. In this study, we performed mineral/melt Sn partitioning experiments at 0.5–1.0 GPa, 850–1000 °C, and fO2 of FMQ + 8 to ∼ FMQ − 1. The fO2s were imposed by solid buffers of Ru–RuO2, Re–ReO2, Ni–NiO, Co–CoO and graphite using three improved capsule designs: 1) a single sample capsule (Pt) for the Ru–RuO2 buffered runs, 2) double capsules with Pt95Rh05 as outer capsule and Re as inner sample capsule for the graphite and Re–ReO2 buffered runs, and 3) triple capsules for the Co–CoO and Ni–NiO buffered runs, with Pt95Rh05 (or Au) as outer capsule, Re lined Pt as inner sample capsule. These new capsule designs avoided significant Sn loss and enabled us to obtain accurate DSnmin/melt at a controlled fO2. The experimental results show that DSnmin/melt values are 0.08–12.66 for amphibole, 0.01–5.55 for biotite, 0.09–10.39 for clinopyroxene, 0.004–0.97 for orthopyroxene, < 0.01 for olivine, 1.34–108.43 for Ti-magnetite, 0.04–4.17 for spinel and 0.10–0.64 for ilmenite. The large variation of DSn for each mineral was mainly ascribed to the effect of fO2, which results in an arresting decrease of DSn with decreasing fO2. Under the reducing conditions (fO2 < FMQ), Sn is highly incompatible (DSn < 0.1) in almost all the minerals. Modeling results indicate that partial melting at low fO2 conditions results in Sn enrichment in the derived magma, while subsequent high degree of fractional crystallization is also important for the Sn enrichment in the residual melt. The experimental and modeling results thus explain why major primary tin deposits are always related to reducing and highly fractionated granites.

The gold-telluride connection: Evidence for multiple fluid pulses in the Jinqingding telluride-rich gold deposit of Jiaodong Peninsula, Eastern China

The mechanism of gold migration, enrichment, and precipitation in forming world-class gold deposits has been a topic of wide interest, particularly where these deposits are abundant in tellurides. The Jiaodong Peninsula in eastern China hosts some of the world-class gold deposits among which the Jinqingding deposit is one of the best examples with substantial telluride mineralization and thus provides opportunity to investigate the genetic connection between tellurium and gold mineralization. The orebody in this deposit is hosted in the NE-NNE-trending Jiangjunshi-Quhezhuang fault with the Jurassic Kunyushan granitic pluton as wall rock. The deposit involved three mineralization stages as inferred from assemblages and crosscutting relationships between veins. These stages are: (I) pre-ore gold-poor quartz-pyrite veins, (II) main ore auriferous quartz-pyrite-Te/Bi-minerals ± sphalerite ± chalcopyrite ± barite ± marcasite veins, and (III) post-ore quartz-calcite veins. We present here the textural, isotopic, and geochemical variations of different stages/generations of pyrite based on scanning electron microscopy-energy dispersive spectroscopy (SEM–EDS), electron probe microanalysis (EPMA), and laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS).Pyrite in the Jinqingding deposit displays distinct characteristics. Py1a shows a porous and dissolution-reprecipitation texture in the core, whereas Py1b exhibits a smooth and flat rim. Geochemical analysis reveals contrasting elemental compositions, with Py1a characterized by low Au (avg. 0.14 ppm), As (avg. 15.57 ppm), Ag (avg. 17.71 ppm), and Te (avg. 19.22 ppm) contents, but elevated Co (avg. 1068.10 ppm) and Ni (224.12 ppm) concentrations, and variable sulfur isotopic composition (δ34SV-CDT = 9.54‰–12.12‰). Conversely, Py1b displays increased concentrations of these elements and a more concentrated δ34SV-CDT value (11.99‰–12.23‰), possibly associated with weak coupled dissolution-reprecipitation (CDR) processes. In Stage II, pyrite can be further categorized into two generations: the porous core (Py2a) and the smooth periphery (Py2b). Notably, Stage II exhibits increased contents of Au (Py2a: avg. 0.47 ppm; Py2b: avg. 5.57 ppm), As (Py2a: avg. 1265.20 ppm; Py2b: 1049.46 ppm), Ag (Py2a: avg. 5.43 ppm; Py2b: avg. 65.23), and Te (Py2a: avg. 21.47 ppm; Py2b: avg. 51.66 ppm), δ34SV-CDT value exhibits minor changes (Py2a: 11.48‰–13.05‰; Py2b: 11.79‰–12.80‰). These changes potentially indicate the involvement of a fluid pulse characterized by low fO2: −34.9 to −30.2, medium fTe2: −14.7 to −10.9 and fS2: −11.4 to −6.9. Despite the dissolution-reprecipitation textures present in the ores, gold did not undergo remobilization, except for a possible weak contribution in Stage II. The presence of abundant Bi/Te-minerals underscores the significant role of low-melting point chalcophile elements in gold migration and enrichment. By compiling and analyzing sulfur isotopic composition of gold deposits across the entire Jiaodong Peninsula, which shows the reduction of marine sulfates as a crucial mechanism for sulfur enrichment. We conclude that the Jinqingding gold deposit, characterized by abundant tellurium, along with episodic pulses of ore-forming fluids, and exhibit subtle distinctions compared to other gold deposits within the Jiaodong Peninsula.

Geochronology and geochemistry of intrusion and multi-generation garnet at the Jia’erbasidao Fe skarn deposit: Implications for two-stage Fe mineralization in the Chinese Altay Orogen (NW China)

Over a hundred iron ore occurrences have been discovered in the Chinese Altay Orogenic Belt (AOB), which is a key Fe-ore belt in NW China. In the Jia’erbasidao ore district, Fe skarn mineralization was mainly developed along the contact zone between biotite granite and the marble of Altay Formation, which is different from most Fe mineralization (non-skarn contact zone) in the Chinese AOB. Two generations of garnet (Grt1and Grt2) have been identified to be related to the two stages of Fe-ore formation at Jia’erbasidao, and Grt1 and Grt2 can be further divided into Grt1a, 1b and Grt2a, 2b, respectively. Our U-Pb dating indicates that the biotite granite and garnet from prograde skarn stage 1 (Grt1a) were formed at 275.6 ± 3.1 Ma and 270.6 ± 4.4 Ma, respectively. The mineralized biotite granite is metaluminous to peraluminous, LREE-enriched and HREE-depleted. Meanwhile, two Grt2a samples from the prograde skarn stage 2 yielded lower intercept 206Pb/238U ages of 248.3 ± 2.9 Ma and 246.0 ± 6.0 Ma, respectively. Grt1 and Grt2 may have formed from different ore-forming fluids: Grt1a was precipitated from a LREE-depleted, near neutral and low fO2 fluid (δEu = 1.92–2.84); Grt1b and magnetite (Mag1) were precipitated from the same fluid with higher fO2 (δEu = mostly 1.22–2.63); Grt2a was precipitated from a fluid with relative LREE enrichment, relatively lower pH and higher fO2 (δEu = 0.98–1.69); Grt2b and magnetite (Mag2) was formed from a fluid that was HREE-enriched, near neutral, and higher fO2 (δEu = 0.76–1.09). Our study shows a two-stage Fe mineralization at Ja’erbasidao, including the Early Permian Fe skarn mineralization and the Early Triassic skarn mineralization.

Petrogenesis of the U-rich Permian Akkulen syenite intrusion, Tien Shan, Kyrgyzstan: insights into its magmatic evolution and geodynamic setting

ABSTRACT Permian alkaline granitoids are widely distributed throughout the Tien Shan Orogen and adjacent region of the southern Central Asian Orogenic Belt. However, their petrogenesis and related tectonic setting remain equivocal. A detailed mineralogical, U-Pb zircon dating, in situ elemental and Sr-Nd-Hf isotopic studies of the uranium-rich Akkulen syenite intrusion in the Northern Tien Shan of Kyrgyzstan were undertaken to better understand its magmatic processes and geodynamic evolution. Four independent oxygen barometers have shown that the oxygen fugacity of the Akkulen syenitic magma evolved from initial low fO2 (<NNO +1, where NNO is the nickel-nickel oxide buffer) to relatively high fO2 (>NNO +1) during magma ascent and cooling; Apatite geochemical characteristics also indicate that the magma is relatively high F (2.9–5.1 wt.%), with low Cl (0.053–0.13 wt.%) and anhydrous (<4 wt %) contents. According to whole-rock geochemical data, the syenite samples have abnormally high U (38.5–57.1 ppm) and Th (96.2–137 ppm) concentrations, we suggest that high F content and moderate oxygen fugacity are beneficial for uranium enrichment. Zircon grains from a syenite sample yielded a weighted 206Pb/238U age of 283.5 ± 2.6 Ma. The intrusion has an A-type granite affinity with high alkali (Na2O + K2O) contents and Fe/(Fe+Mg) ratios, high LREE/HREE (~5), and low Sr, Ba, and Eu contents. They have negative εNd(t) (−5.2 to −3.6) values with Mesoproterozoic two-stage model ages (T DM2 = 1.35–1.47 Ga), and variable εHf(t) values (−4.6 to +2.4) with Mesoproterozoic two-stage model ages (T DM2 = 1. 2–1.59 Ga), which suggest these rock derivations from the relatively old crustal with minor contribution from juvenile crustal melts. In comparison with regional available dataset, we propose that the alkaline Permian granitoids in Kyrgyz Northern Tien Shan may have been originated from large-scale partial melting of Mesoproterozoic metamorphic basement with minor juvenile crustal material in a post-extensional setting. In contrast, the Early Permian granitoid magmatism in the Tarim Craton may have been caused by the partial melting of Neoproterozoic basement rocks associated with Permian mantle plume activities.

Domestic cat larynges can produce purring frequencies without neural input

Most mammals produce vocal sounds according to the myoelastic-aerodynamic (MEAD) principle, through self-sustaining oscillation of laryngeal tissues.1,2 In contrast, cats have long been believed to produce their low-frequency purr vocalizations through a radically different mechanism involving active muscle contractions (AMC), where neurally driven electromyographic burst patterns (typically at 20-30Hz) cause the intrinsic laryngeal muscles to actively modulate the respiratory airflow. Direct empirical evidence for this AMC mechanism is sparse.3 Here, the fundamental frequency (fo) ranges of eight domestic cats (Felis silvestris catus) were investigated in an excised larynx setup, to test the prediction of the AMC hypothesis that vibration should be impossible without neuromuscular activity, and thus unattainable in excised larynx setups, which are based on MEAD principles. Surprisingly, all eight excised larynges produced self-sustained oscillations at typical cat purring rates. Histological analysis of cat larynges revealed the presence of connective tissue masses, up to 4mm in diameter, embedded in the vocal fold.4 This vocal fold specialization appears to allow the unusually low fo values observed in purring. While our data do not fully reject the AMC hypothesis for purring, they show that cat larynges can easily produce sounds in the purr regime with fundamental frequencies of 25 to 30Hz without neural input or muscular contraction. This strongly suggests that the physical and physiological basis of cat purring involves the same MEAD-based mechanisms as other cat vocalizations (e.g., meows) and most other vertebrate vocalizations but is potentially augmented by AMC.

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.

Carbonated eclogitic component beneath eastern China revealed by olivine phenocrysts in nephelinites

Carbonates subducted into the mantle alongside mafic material play a critical role in the deep cycling of carbon. This recycled oxidized carbon strongly affects the physical properties of the mantle, changes the local mantle oxidation state, and enhances its ability to melt. Olivine phenocrysts, which are the first to crystallize from mantle-derived magma, record the lithology of the mantle source and provide a new perspective on CO2-rich mantle domains. Here we present data for olivine phenocrysts from Cenozoic nephelinites from eastern China, which have extremely high Ca (1108–6575 ppm) and Mn (1595–5065 ppm) and low Fo (71–85) contents and differ from olivine crystallized from CO2-poor mantle-derived melts (e.g., peridotitic or pyroxenitic mantle-derived melts; Ca < 3000 ppm, Mn < 2500 ppm). This can be explained if the olivine phenocrysts are in equilibrium with melts derived from a carbonated eclogite source, because melts produced experimentally from carbonated eclogite have high Ca and Mn and low MgO contents. The nephelinites have lower δ26Mg (−0.46‰ to −0.37‰) and higher δ66Zn (0.40‰ to 0.56‰) values compared with normal (MORB-source) mantle, lending further support to the influence of carbonated components during the formation of the nephelinites. Decreases in the Ca and Mn contents of the olivine phenocrysts with increasing Fo contents are due to mixing between the initial melt and a reacted melt produced by melt–peridotite interaction during ascent. Our findings demonstrate that the signature of carbonated eclogite in the mantle can be recorded by olivine compositions. This highlights the importance of olivine phenocrysts for tracing CO2-rich lithologies in the mantle and that high Ca and Mn contents of olivine phenocrysts suggest a carbonated eclogite source.

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.

The effect of maternal position on placental blood flow and fetoplacental oxygenation in late gestation fetal growth restriction: a magnetic resonance imaging study.

Fetal growth restriction (FGR) and maternal supine going-to-sleep position are both risk factors for late stillbirth. This study aimed to use magnetic resonance imaging (MRI) to quantify the effect of maternal supine position on maternal-placental and fetoplacental blood flow, placental oxygen transfer and fetal oxygenation in FGR and healthy pregnancies. Twelve women with FGR and 27 women with healthy pregnancies at 34-38weeks' gestation underwent MRI in both left lateral and supine positions. Phase-contrast MRI and a functional MRI technique (DECIDE) were used to measure blood flow in the maternal internal iliac arteries (IIAs) and umbilical vein (UV), placental oxygen transfer (placental flux), fetal oxygen saturation (FO2 ), and fetal oxygen delivery (delivery flux). The presence of FGR, compared to healthy pregnancies, was associated with a 7.8% lower FO2 (P=0.02), reduced placental flux, and reduced delivery flux. Maternal supine positioning caused a 3.8% reduction in FO2 (P=0.001), and significant reductions in total IIA flow, placental flux, UV flow and delivery flux compared to maternal left lateral position. The effect of maternal supine position on fetal oxygen delivery was independent of FGR pregnancy, meaning that supine positioning has an additive effect of reducing fetal oxygenation further in women with FGR, compared to women with appropriately grown for age pregnancies. Meanwhile, the effect of maternal supine positioning on placental oxygen transfer was not independent of the effect of FGR. Therefore, growth-restricted fetuses, which are chronically hypoxaemic, experience a relatively greater decline in oxygen transfer when mothers lie supine in late gestation compared to appropriately growing fetuses. KEY POINTS: Fetal growth restriction (FGR) is the most common risk factor associated with stillbirth, and early recognition and timely delivery is vital to reduce this risk. Maternal supine going-to-sleep position is found to increase the risk of late stillbirth but when combined with having a FGR pregnancy, maternal supine position leads to 15 times greater odds of stillbirth compared to supine sleeping with appropriately grown for age (AGA) pregnancies. Using MRI, this study quantifies the chronic hypoxaemia experienced by growth-restricted fetuses due to 13.5% lower placental oxygen transfer and 26% lower fetal oxygen delivery compared to AGA fetuses. With maternal supine positioning, there is a 23% reduction in maternal-placental blood flow and a further 14% reduction in fetal oxygen delivery for both FGR and AGA pregnancies, but this effect is proportionally greater for growth-restricted fetuses. This knowledge emphasises the importance of avoiding supine positioning in late pregnancy, particularly for vulnerable FGR pregnancies.

LA-ICPMS trace elements and C-O isotopes constrain the origin of the Danaopo Cd-Ge-bearing Zn-Pb deposit, western Hunan, China

The Danaopo Zn-Pb deposit, hosted in algal limestone, is the second largest Zn-Pb deposit (150 Mt ores at an average grade of 3.06% Zn + Pb) in the western Hunan-eastern Guizhou metallogenic belt (WHEGMB). Here we investigate the trace elements of sphalerite and C-O isotopes and rare earth elements (REEs) of calcite in the Danaopo deposit, aiming to present insights into the mineralization potentiality of critical metals and origin of Zn-Pb deposits in the WHEGMB. In-situ trace element reveals the inhomogeneous distribution of critical metals within sphalerite, including Cd (1520 to 11570 ppm), Ge (0.73 to 236 ppm), Ga (0.04 to 26.90 ppm), and Tl (0.01 to 3.62 ppm). Cd and Ge exceed the Chinese comprehensive utilization standard. The LA-ICPMS elemental map and inter-element correlations suggest that Cd and Ge enter sphalerite lattice via the substitution of Zn2+ ↔ Cd2+ and 4Zn2+ ↔ Ge4+ + 2Fe2+ + □ (vacancy), respectively. The δ13CPDB (-3.93 to −0.12‰) values of the ore-stage calcite indicate that the carbon in hydrothermal fluids primarily originates from the dissolution of Cambrian algal limestone. Calculated δ18Ofluid (+5.23 to + 9.95‰) values on calcites lies between the oxygen isotopic compositions of the algal limestone (+18.76 to + 23.87‰) and the basinal hot brine (+4 to + 10‰), implying that the oxygen was sourced from a binary mixing of ore-host rocks and basin brine. Besides, the REE distribution pattern of Cal-Ⅰ falls within the field of ore-host rocks. In contrast, Cal-Ⅱ is plotted between the Cambrian ore-host and Proterozoic Banxi Group to Cambrian Niutitang Formation footwall. These findings suggest that REE of Cal-Ⅰ was mainly sourced from country carbonate rocks, while Cal-Ⅱ has mixed REE origins from ore-host rocks and footwall sedimentary and metamorphic basement rocks. Overall, based on detailed deposit geology, sphalerite trace elements, and calcite C-O and REE evidences, this study concludes that the Danaopo is a classic Mississippi Valley-type (MVT) Zn-Pb deposit with a low-temperature and low fO2 reductive ore-forming fluid.

The Redox State of Incipient Oceanic Subduction Zones: An Example From the Troodos Ophiolite (Cyprus)

AbstractTo understand the oxygen fugacity (fO2) during subduction initiation, we examined proto‐arc boninites and associated mantle peridotites from the Troodos ophiolite, Cyprus. The Troodos ophiolite represents an exhumed piece of oceanic lithosphere that formed during subduction initiation in Neo‐Tethys in Late Cretaceous. Dunites and surrounding harzburgites in the Kokkinorotsos podiform chromite deposit of the ophiolite were formed by reactions between peridotites and ascending boninitic magmas. The olivine‐chromite oxybarometers show that the fO2 values (∆QFM −0.41 ± 0.37) of the dunites are slightly higher than those (∆QFM −0.85 ± 0.52) of the harzburgites under mantle conditions, indicating that the mantle fO2 was raised limitedly by percolation of the boninitic magmas. Meanwhile, the boninitic upper pillow lavas in the Margi area also recorded relatively reduced fO2 values (∆QFM −0.52 ± 0.20) during olivine‐chromite crystallization, comparable to the fO2 of mid‐ocean ridge basalts. Shallow‐level processes (i.e., magma ascent, crystallization, crustal assimilation, and degassing) appear to have limited influence on the estimated fO2 values in Troodos. The similarly low fO2 values of the mantle peridotites and boninitic magmas suggest that the Troodos primary boninitic magmas were perhaps not as oxidized as the Izu‐Bonin‐Mariana (IBM) proto‐arc boninitic magmas, though both mantle sources have captured the slab fluids released during subduction inception. This difference might be attributed to the different nature of the slab components (i.e., a more reduced subduction input for Troodos). Our study thus suggests that subducted slabs might not always release oxidized fluids, and the oxidation processes might be different for each nascent subduction zones.

Re-evaluation of equilibrium relationships involving U6+/U4+ and Fe3+/Fe2+ in hydrothermal fluids and their implications for U mineralization

Uranium (U) and iron (Fe) are generally considered to have contrasting aqueous geochemical behavior, with U dissolution being favored in oxidizing fluids as oxidized U (U6+) and Fe in reducing fluids as reduced Fe (Fe2+) species. However, high concentrations of both U and Fe have been reported for the ore fluids of uranium deposits, suggesting that the two elements can be co-transported in the same fluid. In this study, geochemical modeling, based on recent thermodynamic and experimental data for U and Fe species and fluid inclusion compositions from two types of hydrothermal U deposits (volcanic-related and unconformity-related), was conducted to investigate the nature and conditions of UFe co-transportation. The results of the modeling indicate that high concentrations of U (>10, up to >100 ppm) and Fe (>1000 ppm) can be dissolved in acidic aqueous fluids (pH < ∼3.3) of moderate to high chlorinity (∼ 55 to 250 g/L Cl), for a wide range of logfO2 above and below the magnetite-hematite (MH) buffer (from ∼ MH-5 to MH + 30), at temperatures from 150 to 250 °C. There are four different combinations of dominant dissolved U and Fe species depending on the pH and redox conditions: U6+ and Fe3+ species (UO2Cl20 and FeCl30) at relatively high fO2, U4+ and Fe2+ species (UCl40 and FeCl42−) at relatively low fO2, and U6+ and Fe2+ species (UO2Cl20 and FeCl42−) or U4+ and Fe3+ species (UCl40 and FeCl30) at intermediate fO2 conditions. Because the most important U mineral in hydrothermal uranium deposits is uraninite (UO2), in which U is present as U4+, a necessary condition for U mineralization is that U is either transported as U4+ species or, if transported as U6+ species, precipitation of uraninite is induced by a reducing agent. The recognition that U6+ and Fe2+ species can be co-transported in the same fluid indicates that uraninite can be precipitated without the need to invoke a reducing agent external to the ore fluid. The driver of uranium mineralization in this case is an increase in pH due to fluid-rock interaction that leads to the alteration of the rocks by clay minerals and associated coupled sorption-reduction. These findings provide for a more extensive range of conditions for U transport and deposition than previously imagined and require that interpretation of the conditions of uranium mineralization consider both oxygen fugacity and pH. This study underscores the potential for uranium deposits to occur in geological settings where reducing agents are either absent or insufficiently abundant to account for the observed mineralization, and the possibility for the transport of U in environments that might otherwise be considered unfavorable.