Low Isotope Ratios Research Articles

Bio-mediated enhancement of supergene copper mineralization: Evidence from Cu isotope geochemistry

The relationship between microbial activity and the supergene modification of ore systems has been a major subject of debate. Here, we present isotopic evidence of microbial-driven secondary copper mineralization in the active cementation zone of the Las Cruces deposit, a volcanogenic massive sulfide deposit located in Iberian Pyrite Belt, Spain. Copper isotopic data show that the lower isotopic ratios (δ65Cu ≈ −9.2 ± 0.11 ‰, the lowest value measured worldwide in a supergene environment) are found in the upper part of the cementation zone, the same zone where the maximum copper grades are found and where there is direct evidence of extremophilic microbial activity. There is a tendency towards higher values downwards through the cementation zone (−9.2 ± 0.11 ‰ to + 1.67 ± 0.11 ‰ δ65Cu) and upwards into the former Cu-depleted gossan that originally capped the cementation zone (−7.79 ± 0.11 ‰ to −1.32 ± 0.11 ‰ δ65Cu). As microbes preferentially sequester the lighter isotope when incorporating intracellular Cu, this distribution indicates that microbes played a major role in the formation of the high-grade zones. Water arrives to the deposit enriched in isotopically heavy copper, likely because it has leached other ore bodies upstream. δ65Cu values of water currently flowing into the system are remarkably more positive than those in the ore, indicating that microbial activity is a major cause of copper isotope fractionation. At least half of the copper transported by the incoming waters remains within the ore body. Our best interpretation is that the large and high-grade cementation zone at Las Cruces is of biogenic origin, and that the primary mineralization acted as a trap for copper transported by groundwater, leading to the formation of an exotic mineralization distal to sub-eroded massive sulfides located upstream.

Benthic response to the strong Silurian climatic fluctuations—implications from Gotland (Sweden)

Climatically the Silurian was a most unstable period, as it is shows several strong δ13C excursions, with the Lau excursion being the strongest short-lived positive δ13C excursion of the entire Phanerozoic. The causes of these excursions remain a topic of debate. In order to determine how benthic communities responded to these climatic perturbations, a microfacies analysis of carbonate rocks from the Silurian period (Late Telychian to the uppermost Ludfordian) of Gotland was conducted. The development of reefs was significantly enhanced during periods characterized by carbon isotope excursions, compared to time intervals without. In periods of elevated δ13C values (≥ 3 ‰) the abundance of bryozoans and microbes increases, and in some areas, they form reefs (bryostromatolites), while corals and stromatoporoids were the main reef builders in periods of lower isotope ratios (0–3 ‰). Furthermore, a significant increase of phosphatic components, gypsum pseudomorphs and the microproblematicum Palaeomicrocodium is observed in times of increased isotope ratios. A model is proposed that explains the changes in the benthic communities over time. It is based on previously published models and explains the geochemical processes from coastal areas to the open ocean. Changes are assumed from a humid climate in times without isotope excursions to an arid climate in times of isotope excursions. It emphasizes processes that may have led to the strong δ13C shifts during the Silurian period, and includes the phosphorus cycle in sea water as an important factor in the development of the benthic communities.

The Carbon Isotopic Composition of Archean Kerogen and Its Resilience Through the Rock Cycle

The Archean rock record is limited and there is minimal organic matter available to understand the origin and evolution of life on early Earth. Low carbon isotope ratios have been measured in organic and reduced carbon phases in Archean rocks and have been invoked as biosignatures. However, it can be challenging to distinguish whether these low values reflect biotic formation, abiotic reactions, or post-depositional processes. To re-address this long-standing question, we compiled a comprehensive dataset of carbon isotope ratio measurements from organic carbon phases from Archean units that were analyzed using a variety of geochemical techniques. Our compilation also includes available descriptions and measurements of the stratigraphy, mineralogy, elemental ratios, and metamorphic grade for each data point. Our statistical analyses re-enforce a result that has been noted by prior compilations, that the carbon isotopic composition of Archean organic matter (OM) is broadly more 13C-deplete than the composition of Phanerozoic OM: The median δ13C values ( ±SD) of Archean total organic carbon and kerogen were −30.5±8‰ (n=2421) and −33.7±11.3‰ (n=556; Phanerozoic OM δ13C ±SD = −26.7±4.6‰ with n=449 from a prior compilation). Our study also identifies a previously unrecognized bimodality within the δ13C values of Archean OM that is observed even with subsampling of the data to account for geographic and stratigraphic sampling bias. We describe and model the isotopic and structural changes associated with the transformation of marine Type II kerogen from formation through diagenesis, catagenesis and metagenesis, and metamorphism, as described by trends on a van Krevelin diagram. Empirically, early maturation of organic matter during diagenesis results in shifts up to a few per-mille, which can occur in either direction depending on selective preservation and degradation of compounds. Thermal cracking that occurs during catagenesis can drive increases in δ13C of 5–12‰. At temperatures above greenschist metamorphism, carbon atoms exchange with other reactive carbon pools, driving increases in δ13C of up to 20‰. Together, our analyses suggest that the most metamorphosed graphitic samples from the earliest Archean are likely signatures of alteration, while low and multimodal ranges of δ13C values may preserve records of Archean ecology.

The Pristine Inner Galaxy Survey (PIGS) VII: a discovery of the first inner Galaxy CEMP-r/s star

ABSTRACT Well-studied very metal-poor (VMP, [Fe/H] <−2) stars in the inner Galaxy are few in number, and they are of special interest because they are expected to be among the oldest stars in the Milky Way. We present high-resolution spectroscopic follow-up of the carbon-enhanced metal-poor (CEMP) star Pristine_184237.56-260624.5 (hereafter Pr184237) identified in the Pristine Inner Galaxy Survey. This star has an apocentre of ∼2.6 kpc. Its atmospheric parameters (Teff = 5100 K, log g = 2.0, and [Fe/H] = −2.60) were derived based on the non-local thermodynamic equilibrium (NLTE) line formation. We determined abundances for 32 elements, including 15 heavy elements beyond the iron group. The NLTE abundances were calculated for 13 elements from Na to Pb. Pr184237 is strongly enhanced in C, N, and O, and both s- and r-process elements from Ba to Pb; it reveals a low carbon isotope ratio of 12C/13C = 7. The element abundance pattern in the Na–Zn range is typical of halo stars. With [Ba/Eu] = 0.32, Pr184237 is the first star of the CEMP-r/s subclass identified in the inner Galaxy. Variations in radial velocity suggest binarity. We tested whether a pollution by the s- or i-process material produced in the more massive and evolved companion can form the observed abundance pattern and find that an i-process in the asymptotic giant branch star with a progenitor mass of 1.0–2.0 $\, {\rm M}_{\odot }$ can be the solution.

Sulfur reduction distillation of sulfides and verification of the effect of sulfur isotopic fractionation during pretreatment

Toxic gases can be emitted when sulfides form compounds with heavy metals; thus, a series of pretreatments are required prior to the analysis of sulfur isotope ratios to remove unnecessary elements. In addition, it is necessary to verify the effect of sulfur isotope fractionation caused by the plurality of sulfides comprising different sulfide species during the pretreatment process. In this study, H2S(gas) was extracted from mixed sulfides comprising pyrite and galena and reacted with mixed acids (i.e., HCl + HI + H3PO2) at 200 °C, in sealed conditions filled with N2. Subsequently, CdS(s) was precipitated from the reaction with H2S(gas) in a trap filled with Cd(CH3COO)2(aq). CdS(s) was then ionized to SO42−(aq) after reacting with H2O2(l), followed by the addition of BaCl2(l) to precipitate BaSO4(s). The sulfur isotope values of the products (barite: av. 5.9‰) were lower than those of the reactants (sulfides: av. 6.9‰); this is attributed to the preferential fractionation of galena with a low isotope ratio when converting sulfide to H2S(gas). Therefore, in the pretreatment process for the sulfur isotope analysis of a sample composed of a sulfide mixture, the effect of isotope fractionation between sulfur species should be considered.

Multiple-Stage Neoproterozoic Magmatism Recorded in the Zhangbaling Uplift of the Northeastern Yangtze Block: Evidence from Zircon Ages and Geochemistry

The Yangtze Block records Neoproterozoic magmatism and sedimentation related to the breakup of Rodinia and is an important piece in the reconstruction of the supercontinent. However, the tectonic setting and position of this block in Rodinia remain a subject of debate. In the present study, we report the zircon U-Pb ages and Hf isotopic composition of zircon and geochemical and Nd-Pb isotopic compositions for meta-volcanic rocks exposed in the Zhangbaling uplift of the NE Yangtze Block. The volcanic rocks, dominated by rhyolite and dacite, belong to the calc-alkaline series and show geochemical characteristics of arc rocks. Zircon U-Pb isotopic ages show that volcanic rocks in the Xileng Formation formed at ca. 790 Ma and ca. 760–700 Ma peaking at ~740 Ma. The late-stage volcanism was widely exposed in the uplift, characterized by a temporal-spatial trend becoming younger southwards. The old volcanic rocks have low initial εNd (−11.0) and εHf (−19.7 to −8.2) values and low Pb isotopic ratios, likely indicating an origin from ancient basement rocks underneath the Yangtze Block. The younger ones, being similar to continental arc andesite in trace element compositions, have relatively high initial εNd (mostly −4.6 to 0.5) and εHf (−0.4 to 8.8) values and high Pb isotopic ratios. These isotopic features point to an origin from the partial melting of juvenile crustal rocks. Sedimentary rocks of the Xileng Formation and the overlying strata also contain numerous zircon grains of ~700 Ma to ~630 Ma. The volcanic rocks in the Zhangbaling uplift might demonstrate long-lasting subduction along the northeastern margin of the Yangtze Block, probably active until ca. 700 Ma.

Gold mineralized diorite beneath the Linglong ore field, North China craton: New insights into the origin of decratonization-related gold deposits

Gold deposits in Precambrian cratons were mostly generated during the formation and stabilization of the cratons, but the North China craton is unusual in that its gold deposits were mainly formed ∼1.7 b.y. after its stabilization. A magmatic-hydrothermal origin or mantle-derived fluid source has been proposed for the giant gold deposits of the Jiaodong District in the eastern North China craton, but direct evidence is sparse, and the mineralization processes remain controversial. Here, we present the results of a comprehensive geological, geochronological, and geochemical study of the gold mineralized Xiejia diorite beneath the Linglong ore field at Jiaodong to link the gold mineralization to underlying magmatism. Magmatic zircon and titanite grains from the Xiejia diorite have laser ablation−inductively coupled plasma−mass spectrometry (LA-ICP-MS) U-Pb ages of 121.3 ± 0.9 Ma to 120.8 ± 1.1 Ma and 121.7 ± 3.9 Ma, respectively, which are indistinguishable from the time of gold deposition throughout the Jiaodong District as constrained by previous studies. The diorite has a shoshonitic composition and is characterized by strong enrichment in large ion lithophile elements (LILEs) and light rare earth elements (LREEs) along with significant depletion in high field strength elements (HFSEs) and heavy rare earth elements (HREEs). Samples of the diorite have high initial 87Sr/86Sr ratios, but low εNd(t) and ɛHf(t) values and low Pb isotope ratios. These geochemical characteristics are akin to those of contemporaneous mafic dikes in most gold mines at Jiaodong, indicating that the Xiejia diorite was most likely derived from an enriched lithospheric mantle source. The upper part of the diorite intrusion is pervasively altered and mineralized, containing an average of 0.32 g/t Au, but locally up to 7.59 g/t. Hydrothermal titanite from the mineralized diorite has a LA-ICP-MS U-Pb age of 122.3 ± 4.3 Ma, which is consistent with the gold-bearing pyrite Re-Os isochron age of 122.5 ± 6.7 Ma. Ore-related sericite aggregates from the Dongfeng gold deposit above the Xiejia diorite have a 40Ar/39Ar plateau age of 122.6 ± 1.3 Ma. Pyrite from the mineralized diorite yielded δ34SCDT values of 2.1‰−9.7‰, which are comparable with those of pyrite (δ34SCDT = 5.8‰−8.1‰, where CDT indicates the Canyon Diablo troilite standard) from gold ores of Dongfeng. Pyrite grains from both groups also have similar Pb isotope compositions. The S and Pb isotope data are consistent with values of mafic dikes that are spatially and temporally associated with gold veins in the Linglong ore field. The results presented here thus indicate a possible genetic link between gold mineralization in the Xiejia diorite and underlying magma presumably represented by the Xiejia diorite. The auriferous fluids exsolved from that magma and migrated upward along the Potouqing fault to form the Dongfeng gold deposit above the Xiejia diorite. The mineralized diorite thus links shallow gold mineralization to deep-seated mantle-derived magmatism generated during the extensive destruction of the North China craton induced by the rollback of the subducted paleo-Pacific plate.

Characteristics and varieties of gases enclathrated in natural gas hydrates retrieved at Lake Baikal

Molecular and stable isotope compositions of hydrate-bound gases collected from 59 hydrate-bearing sites between 2005 to 2019 in the southern and central sub-basins of Lake Baikal are reported. The δ2H of the hydrate-bound methane is distributed between − 310‰ and − 270‰, approximately 120‰ lower than its value in the marine environment, due to the difference in δ2H between the lake water and seawater. Hydrate-bound gases originate from microbial (primary and secondary), thermogenic, and mixed gas sources. Gas hydrates with microbial ethane (δ13C: − 60‰, δ2H: between − 310‰ and − 250‰) were retrieved at approximately one-third of the total sites, and their stable isotope compositions were lower than those of thermogenic ethane (δ13C: − 25‰, δ2H: − 210‰). The low δ2H of ethane, which has rarely been reported, suggests for the first time that lake water with low hydrogen isotope ratios affects the formation process of microbial ethane as well as methane. Structure II hydrates containing enclathrated methane and ethane were collected from eight sites. In thermogenic gas, hydrocarbons heavier than ethane are biodegraded, resulting in a unique system of mixed methane-ethane gases. The decomposition and recrystallization of the hydrates that enclathrate methane and ethane resulted in the formation of structure II hydrates due to the enrichment of ethane.

Multi-scale isotopic heterogeneity reveals a complex magmatic evolution: An example from the wallundry suite granitoids of the lachlan fold belt, Australia

Open-system magmatic processes are expected to impart various sorts of isotopic heterogeneity upon the igneous rocks they produce. The range of processes under the “open-system” umbrella (e.g., simple two-component mixing, magma mingling, assimilation with fractional crystallization) cannot usually be uniquely identified using data from a single isotope system. The use of bulk-rock, mineral separate and in situ techniques and multiple isotope systems allows the characterization of isotopic variability at different sampling scales, illuminating details of the petrogenesis of a magmatic system. This approach has been applied to granitoids of the Wallundry Suite in the Lachlan Fold Belt, Australia. The Wallundry Suite exhibits variations in mineral assemblage, mineral composition and trends in bulk-rock major and trace element compositions consistent with the involvement of liquid-crystal sorting processes such as fractional crystallization. In situ paired O-Hf isotope data from zircon in six samples show an array indicating the isotopic evolution of the melt phase. Similarly, bulk-rock Sr-Nd-Hf isotope arrays support open-system magma evolution. These data combined with the petrographic observations and major and trace element geochemical variations suggest some form of assimilation-fractional crystallization process in the petrogenesis of the Wallundry Suite. Added complexity is revealed by two observations: 1) the isotopic variations are only weakly coupled to the lithology and major element compositions of the samples; and 2) there are distinguishable differences between the Hf isotope compositions of bulk-rock samples and those of the magmatic zircons they host. To varying degrees the rocks consistently show negative ΔεHfbulk-zrc values (i.e., the bulk-rock compositions have less radiogenic Hf isotope values than their coexisting zircons). The preservation of distinctly low Nd and Hf isotope ratios in an Fe-Ti oxide mineral separate suggests that the bulk-rock vs. zircon discrepancy is caused by the presence of unmelted components derived from a contaminant of continental origin (i.e., a rock with low Sm/Nd and Lu/Hf and thus unradiogenic Nd and Hf). Evidently, a complex interplay of assimilation, crystallization and melt segregation is required to account for the data. This investigation demonstrates that such complexity can, nevertheless, be disentangled through comparison of complementary isotope data at multiple sampling scales.

Pre-eruption magmatic processes and magma plumbing system at Hachijo-Nishiyama volcano, Izu–Bonin arc, Japan

Nishiyama volcano on Hachijojima Island is an active basaltic volcano located in the Izu–Bonin arc. In this study, petrological and geochemical analyses were conducted on mafic lavas and pyroclastics to understand the magma plumbing system and pre-eruption magmatic processes. Whole-rock major element compositions show significant variations (49.4–54.9 wt.% SiO2), and the samples contain variable amounts of plagioclase phenocrysts (1–40 vol.%). The whole-rock Sr, Nd, and Pb isotopic compositions of samples from the youngest volcanic stage (< 0.7 ka) are homogeneous, whereas some samples from the older stage (3–1 ka) have relatively low Pb isotopic ratios. This observation suggests that the younger magmas were derived from a single parental magma, but another parental magma with distinct geochemical features was involved in the magmatic system before 1 ka. The temporal variation in the FeO*/MgO ratios of the volcanic products is complex and is considered to reflect the intermittent injection of primitive magmas into the main magma chamber in which fractional crystallization occurred. Two-pyroxene geobarometry suggests that the main magma chamber was located at a depth of 9–12 km. The core region of some plagioclase phenocrysts consists of a glass inclusion-free inner core and an inclusion-rich outer mantle, suggesting that some plagioclase crystallized in the main magma chamber, which was followed by overgrowth during magma ascent because of increasing liquidus temperatures due to decompression-induced water exsolution from the melt. The whole-rock compositions of some eruption units with different Al2O3/MgO ratios exhibit distinct plagioclase-controlled trends, which negates the possibility that plagioclase accumulation occurred in a stable magma chamber. In addition, the density of plagioclase was higher than that of the melt during the magma ascent to the surface. From these observations, it is suggested that the accumulation of plagioclase phenocrysts occurred in ascending magmas as the plagioclase settled relative to the surrounding melt. The estimated depth of 9–12 km for the main magma chamber coincides with the depth range over which earthquake swarms occurred in 2002, suggesting that the magma chamber is still active, and that the earthquake swarms may reflect the injection of primitive magma into the magma chamber.Graphical

Genesis and Evolution of Hydrothermal Fluids in the Formation of the High-Grade Hishikari Gold Deposit: Carbon, Oxygen, and Sulfur Isotopic Evidence

The Hishikari low-sulfidation epithermal gold (Au) deposit in Kyushu, Japan, is world-famous for its premium ore. It has been hypothesized that magmatic contributions to the hydrothermal fluid during early stages of mineralization is possible, even if the hydrothermal fluids for many Au occurrences near the Hishikari deposit are of meteoric origin and are influenced by basement sedimentary rocks. The purpose of this study is to obtain constraints on the genesis and evolution of hydrothermal fluids in the formation of the high-grade Hishikari Au deposit by carbon and oxygen isotope ratios of calcite-bearing samples. Since the microanalysis of carbon and oxygen isotope ratios in every 12 μm of the calcite-bearing sample along the growth direction (corresponding to 10 years of the Hishikari mineralization) scatter in a particular range, the fluid evolution might not be a gradual change from a magmatic to a meteoric origin. Alternatively, a rapid turnover of two fluids might be happening locally. The average sulfur isotope ratio of hydrothermal pyrite is similar to that of the adjacent magma. However, according to the secondary ion mass spectrometry (SIMS) microanalysis, local pyrite with extremely low sulfur isotope ratios may interact with basement sedimentary rocks. Unlike other epithermal Au deposits in the vicinity, rapid local mixing of the magmatic-origin deep fluid and meteoric-origin fluid reacted with organic matter containing basement sedimentary rocks might cause gold precipitation at the Hishikari deposit.

The Mal’dzhangarka Carbonatite Massif (Anabar Shield): The Age of Magmatism and Mineralization (U–Pb and Re–Os Isotope Systems)

Abstract—We present the first results of a comprehensive isotope-geochemical study of dolomitic carbonatites of the Mal’dzhangarka massif located in the southeast of the Billyakh melange zone (southeastern periphery of the Anabar Shield). Zircon grains separated from core samples from a depth of 6–30 m have a three-phase structure. All of them were trapped from the host metamorphic rocks and mark the age of the main stage of high-gradient metamorphism in the region, 2027 ± 9 Ma. Pyrochlore containing 38–705 ppm U and 5–21 ppm radiogenic Pb, with weak metamictization of the crystal lattice and an undisturbed U–Pb system, made it possible to estimate the concordant age of rare-metal mineralization in the massif, 167 ± 4 Ma, which is probably close to the crystallization age of the host carbonatites. The estimated age corresponds to one of the stages of kimberlite–carbonatite magmatism on the eastern slope of the Anabar dome. The Re–Os isotope system of pyrite from superposed late carbonate–sulfide veinlets in the carbonatites testifies to a close (within the error of determination) age, 179 ± 14 Ma, and a low initial Os isotope ratio, which indicates the contribution of mantle material to the formation of this isotope system.

Asthenospheric mantle metasomatized by subducted marine sediments: Li isotopic evidence from Dagze mafic rocks, southern Tibet

Lithium (Li) isotopes show large isotopic fractionation during low temperature processes and have been widely used to trace subduction components at convergent margins. To identify recycled subducting components in the asthenospheric mantle, we report the lithium concentrations and isotopic compositions of the ca. 90 Ma Dagze mafic rocks from the eastern Gangdese Arc, southern Tibet, along with their corresponding whole-rock analyses and Sr-Nd-Pb isotope data. They mainly comprise basalts and diabases with high MgO (7.2–8.3 wt%) and low K 2 O (0.02–0.68 wt%) contents. These rocks show slightly variable initial 87 Sr/ 86 Sr ratios (0.7048 to 0.7057), relatively low and homogeneous Pb isotope ratios ( 206 Pb/ 204 Pb = 18.2948–18.6462, 207 Pb/ 204 Pb = 15.5587–15.6132, 208 Pb/ 204 Pb = 38.3843–38.8352) and positive ε Nd (t) values (3.0–4.9), similar to ophiolites from the Indus-Yarlung Tsangpo suture (IYTS). However, they are remarkably depleted in high field strength elements (HFSE; such as Nb and Ta) and slightly enriched in light rare earth elements (LREE) [(La/Yb) N = 2.8–4.4], both of which imply their mantle affinities with distinctive arc signatures. The δ 7 Li values of these rocks range from −2.0 to +2.0‰ (average = −0.7‰), with the majority of samples falling outside the depleted mantle range (+3.4 ± 1.4‰). They exhibit high Li contents (13.2 to 34.1 ppm) and Li/Y ratios (0.8 to 2.2), which are comparable with marine sediments. The negative correlation between Li/Y ratios and δ 7 Li values also suggests the addition of subducted marine sediments. The modeling of δ 7 Li values in combination with Pb-Sr-Nd isotopic ratios suggests that ~1 to 5% of marine sediments have been added into the mantle source of the Dagze mafic rocks. Combined with a previous study, we suggest that the Dagze mafic rocks were derived from the upwelling asthenospheric mantle metasomatized by subducted marine sediments. • Reporting the negative δ 7 Li values of the Dagze mafic rocks. • Demonstrating the lithium isotopic heterogeneities in the asthenospheric mantle. • Modeling ~1 to 5% of marine sediments to the mantle source of the Dagze mafic rocks.

Application of optically stimulated luminescence in volcanic hydrothermal uranium deposits in the Guyuan Basin, North China

Volcanic basins in North China have great potential for the discovery of volcanic-related uranium deposits. However, most of the traditional geochemical exploration that have the inadequacies of the unexpected errors, weak anti-interference ability and exception information have become untenable in exploring uranium deposits overlain by volcanic rocks and sediments. To identify and track the abnormal geochemical source, feldspar infrared stimulated luminescence (IRSL) and quartz optically stimulated luminescence (OSL) were utilized for the first time to explore deeply concealed volcanic-related uranium deposits in North China. Our results confirm that feldspar IRSL-based drill-core samples are oversaturated and therefore fail to trace the deep uranium orebodies. In contrast, quartz OSL in sedimentary covers over the drill holes hosting economic and subeconomic uranium mineralization yields older apparent ages than their actual depositional ages. The high apparent ages of quartz OSL in the sediments and low helium isotope ratios (3He/4He) of the drill core indicated that the soil radon gas (Rn) anomaly was caused by Rn migration from deeply buried uranium ore decay.

New CA-ID-TIMS U–Pb zircon ages for the Altenberg–Teplice Volcanic Complex (ATVC) document discrete and coeval pulses of Variscan magmatic activity in the Eastern Erzgebirge (Eastern Variscan Belt)

The Altenberg–Teplice Volcanic Complex (ATVC) is a large ~ NNW–SSE trending volcano-plutonic system in the southern part of the Eastern Erzgebirge (northern Bohemian Massif, south-eastern Germany and northern Czech Republic). This study presents high precision U–Pb CA-ID-TIMS zircon ages for the pre-caldera volcano-sedimentary Schönfeld–Altenberg Complex and various rocks of the caldera stage: the Teplice rhyolite, the microgranite ring dyke, and the Sayda-Berggießhübel dyke swarm. These data revealed a prolonged time gap of ca. 7–8 Myr between the pre-caldera stage (Schönfeld–Altenberg Complex) and the climactic caldera stage. The volcanic rocks of the Schönfeld–Altenberg Complex represent the earliest volcanic activity in the Erzgebirge and central Europe at ca. 322 Ma. The subsequent Teplice rhyolite was formed during a relatively short time interval of only 1–2 Myr (314–313 Ma). During the same time interval (314–313 Ma), the microgranite ring dyke intruded at the rim of the caldera structure. In addition, one dyke of the Sayda-Berggiesshübel dyke swarm was dated at ca. 314 Ma, while another yielded a younger age (ca. 311 Ma). These data confirm the close genetic and temporal relationship of the Teplice rhyolite, the microgranite ring dyke, and (at least part of) the Sayda-Berggießhübel dyke swarm. Remarkably, the caldera formation in the south of the Eastern Erzgebirge (caldera stage of ATVC: 314–313 Ma) and that in the north (Tharandt Forest caldera: 314–312 Ma) occurred during the same time. These data document a large ~ 60 km NNW–SSE trending magmatic system in the whole Eastern Erzgebirge. For the first time, Hf-O-isotope zircon data was acquired on the ring dyke from the ATVC rocks to better characterize its possible sources. The homogeneous Hf-O-isotope zircon data from the microgranite ring dyke require preceding homogenization of basement rocks. Some small-scale melts that were produced during Variscan amphibolite-facies metamorphism show similar Hf-O-isotope characteristics and can therefore be considered as the most probable source for the microgranite ring dyke melt. In addition, a second source with low oxygen isotope ratios (e.g. basic rocks) probably contributed to the melt and possibly triggered the climactic eruption of the Teplice rhyolite as well as the crystal-rich intrusion of the ring dyke.

Sulphur-rich cold gas around the hot core precursor G328.2551-0.5321

Context.During the process of star formation, the dense gas undergoes significant chemical evolution leading to the emergence of a rich variety of molecules associated with hot cores and hot corinos. However, the physical conditions and the chemical processes involved in this evolution are poorly constrained; the early phases of emerging hot cores in particular represent an unexplored territory.Aims.We provide here a full molecular inventory of a massive protostellar core that is proposed to represent a precursor of a hot core. We investigate the conditions for the molecular richness of hot cores.Methods.We performed an unbiased spectral survey towards the hot core precursor associated with clump G328.2551-0.5321 between 159 GHz and 374 GHz, covering the entire atmospheric windows at 2 mm, 1.2 mm, and 0.8 mm. To identify the spectral lines, we used rotational diagrams and radiative transfer modelling assuming local thermodynamical equilibrium.Results.We detected 39 species plus 26 isotopologues, and were able to distinguish a compact (~2″), warm inner region with a temperature, T, of ~100 K, a colder, more extended envelope withT ~20 K, and the kinematic signatures of the accretion shocks that have previously been observed with ALMA. We associate most of the emission of the small molecules with the cold component of the envelope, while the molecular emission of the warm gas is enriched by complex organic molecules (COMs). We find a high abundance of S-bearing molecules in the cold gas phase, including the molecular ions HCS+and SO+. The abundance of sulphur-bearing species suggests a low sulphur depletion, with a factor of ≥1%, in contrast to low-mass protostars, where the sulphur depletion is found to be stronger. Similarly to other hot cores, the deuterium fractionation of small molecules is low, showing a significant difference compared to low-mass protostars. We find a low isotopic ratio in particular for12C/13C of ~30, and32S/34S of ~12, which are about two times lower than the values expected at the galactocentric distance of G328.2551-0.5321. We identify nine COMs (CH3OH, CH3OCH3, CH3OCHO, CH3CHO, HC(O)NH2, CH3CN, C2H5CN, C2H3CN, and CH3SH) in the warm component of the envelope, four in the cold gas, and four towards the accretion shocks.Conclusions.The presence of numerous molecular ions and high abundance of sulphur-bearing species originating from the undisturbed gas may suggest a contribution from shocked gas at the outflow cavity walls. The molecular composition of the cold component of the envelope is rich in small molecules, while a high abundance in numerous species of COMs suggests an increasing molecular complexity towards the warmer regions. The molecular composition of the warm gas is similar to that of both hot cores and hot corinos, but the molecular abundances are closer to the values found towards hot corinos than to values found towards hot cores. Considering the compactness of the warm region and its moderate temperature, we suggest that thermal desorption has not been completed towards this object yet, representing an early phase of the emergence of hot cores.

Genesis of orogenic gold systems in the Daduhe belt: Evidence of long-lived fertile mantle lithosphere as a source of diverse metallogeny on the western margin of the Yangtze Craton, China

The poorly documented Daduhe gold belt on the western margin of the Yangtze Craton, an important metallogenic belt in southwest China, is characterized by typical orogenic gold systems against a highly anomalous geodynamic setting. A synthesis of regional and deposit geology, mineralization ages, and S-O isotopic compositions of 33 gold deposits from the Danba-Kangding-Shimian-Mianning area of the belt reveals regional metallogenic patterns, establishes a consistent genetic model, and demonstrates a source equivalent to other diverse mineral systems on the western margin of the Yangtze Craton. The Daduhe orogenic gold deposits are controlled by the lithosphere-scale Xianshuihe and Anninghe strike-slip faults in the northern and southern segments of the belt, respectively. The alteration and ore mineral assemblages of the Daduhe orogenic gold deposits define a wide range of hypozonal, mesozonal, and epizonal sub-types. They formed during two episodes: 1) Early Jurassic gold mineralization related to closure of the Paleo-Tethys Ocean, with a large hypozonal gold deposit on the margin of the Danba dome in the northern segment; 2) Cenozoic gold mineralization associated with continental collision on the Tibetan Plateau, with small mesozonal and epizonal gold deposits in shear zones in migmatite basement and at contacts with cover sequences in both the northern and southern segments. At the belt and deposit scales, the ore-controlling structures for both mineralization episodes are NNE-trending second-order extensional faults or their intersections with the dominant NW-trending compressional faults. The three deposit sub-types have overlapping δ34S of 0 ∼ 10‰, δ18Ofluid of 6 ∼ 11‰, and low He-Ar isotope ratios, all consistent with derivation of ore fluids from metasomatized mantle lithosphere. Importantly, the Daduhe orogenic gold deposits have similar S-O-He-Ar isotope compositions to the giant IOCG, Cu-Ni-PGE, Fe-V-Ti, anomalous porphyry Cu-Mo-Au, and carbonatite-related REE deposits in the Panxi region on the shared margin of the western Yangtze Craton. This suggests that these diverse mineral systems have a common source of ore fluids and metals derived from fertile mantle lithosphere during different geodynamic and metallogenic events. Such a widespread hydrous metal-rich deep source with lithosphere-scale faults as ore fluid pathways, and a depth continuum of orogenic gold deposits in the Daduhe belt suggest a high prospectivity and a higher future gold endowment for the belt. This study adds to an increasing awareness of the diversity of mineral systems on specific craton margins globally.

Palaeoceanography of the Japan Sea Across the Mid‐Pleistocene Transition: Insights From IODP Exp. 346, Site U1427

AbstractLarge‐scale atmospheric circulation patterns, such as the East Asian monsoon, have been proposed as possible feedbacks of the mid‐Pleistocene transition (MPT). Marine sediments of the Japan Sea (JS) record variations in the East Asian monsoon over long timescales and may be crucial for understanding of the MPT. To interpret these sediments correctly an understanding of the JS palaeoceanography is necessary. So far, the JS palaeoceanography has been extrapolated across the MPT from studies of the most recent glacial‐interglacial cycles. These suggest a good connection and unrestricted water‐mass exchange with the open ocean during interglacial sea‐level highstands, while during glacial sea‐level lowstands the JS is nearly isolated. Glacial isolation often results in poor carbonate preservation and unusually low oxygen isotope (δ18O) ratios from low‐saline/low‐δ18O waters accumulating in the basin. Using the sediments of Integrated Ocean Drilling Program (IODP) Site U1427, a shallow‐water site in the southern JS, we present a continuous foraminiferal δ18O record encompassing the MPT. This record shows the JS‐typical low glacial δ18O values in the late phase of the MPT, across Marine Isotope Stages (MIS) 24‐17, while earlier MPT glacials, across MIS 39‐25, are characterized by high δ18O values. We propose that high glacial δ18O values are the result of an improved connection between the shallow, southern JS and adjacent ocean during early MPT glacials. The impact of this palaeoceanographic mode, if continued to deep‐water sites, would make the interpretation of dark/light sediment layers as glacial/interglacial deposits uncertain.

Detailed investigation of two high‐speed evolved Galactic stars

AbstractThe study of metal poor stars provides clarification and knowledge about the primordial Universe. Specially, halo stars provide explanations of the nature of the first generations of stars and the nucleosynthesis in the metal‐poor regime. We present a detailed chemical analysis and determination of the kinematic and orbital properties of two stars characterized by high speed with respect to the Sun. We analyzed two high‐resolution Subaru spectra employing the MyGIsFOS code, which allows to derive the detailed chemical abundances for 28 elements (C, N, O, Na, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr, Ba, La, Ce, Pr, Nd, Sm, and Eu), and abundance from two ionization states in the case of four elements (Ti, Cr, Fe, and Zr). TYC 622–742–1 and TYC 1193–1918–1 are metal‐poor stars ([Fe/H] of −2.37 and −1.60), they are similar in the chemical pattern with respect to Fe, they are enhanced and show a slight excess in Eu abundance. Both giant stars are poor in C and rich in N, as expected for evolved stars, and this fact is supported by the low isotopic ratio in TYC 1193–1918–1. Nevertheless, the C abundance of TYC 622–742–1 is particularly low. TYC 622–742–1 and TYC 1193–1918–1 have a similar chemical composition to the other Galactic halo stars of comparable metallicity. According to their kinematics, both stars belong to the Galactic halo, but they are not a part of the Gaia‐Sausage‐Enceladus structure.

Magmatism and related metamorphism as a response to mountain-root collapse of the Dabie orogen: Constraints from geochronology and petrogeochemistry of metadiorites

ABSTRACTPost-collisional mountain-root collapse and subsequent massive partial melting occurred in the high-temperature (HT) ultrahigh-pressure (UHP) metamorphic terrane of the North Dabie complex zone (NDZ), central China. The NDZ was deeply subducted in the Triassic, producing widespread migmatites and various magmatic intrusions in the Cretaceous. Post-collisional metadiorites with distinctive large K-feldspar augen porphyroblasts, locally reported but rarely exposed in the NDZ, underwent a complex evolutional history. In this contribution, integrated studies including field investigation, petrographic observation and mineral analysis, zircon U-Pb geochronological and Hf isotopic analyses, and whole-rock elemental and Sr-Nd-Pb isotopic analyses of the metadiorites were carried out. Our results provide new constraints on the mountain-root collapse in the Dabie orogen. The metadiorites are enriched in large ion lithophile elements and light rare earth elements, whereas they are depleted in high field strength elements and heavy rare earth elements with significant Ba positive anomalies, a composition consistent with the lower continental crust. All the studied samples have moderately enriched initial 87Sr/86Sr ratios (0.707582–0.708099), low εNd(t) values (−15.3 to −20.4), and low initial Pb isotopic ratios (16.0978–16.8452, 15.3167–15.4544, and 37.1778–37.8397 for 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb, respectively). However, they have highly negative εHf(t) values and Paleoproterozoic two-stage Hf model ages, which are only partially consistent with data from the associated UHP metamorphic rocks. Such features suggest the metadiorites resulted from a magma produced by mixing of Triassic UHP mafic lithologies and minor amounts of mantle-derived materials. Zircon morphological analysis and U-Pb sensitive high-resolution ion microprobe dating combined with conventional thermobarometry indicate that these upwelling melts crystallized at pressure-temperature (P-T) conditions of 5.4–5.7 kbar and 750–768 °C at ca. 130 Ma and subsequently suffered HT metamorphism at ca. 125 Ma. We conclude that the metadiorites’ precursors were derived from partial melting of the Triassic subducted Neoproterozoic mafic lower-crustal rocks, with addition of minor amounts of mantle-derived materials in the Early Cretaceous, in response to mountain-root collapse of the orogen. Based on petrographic textures and mineral compositions, it is moreover inferred that formation of the distinctive K-feldspar porphyroblasts is likely related to a two-stage process, i.e., crystallization derived from biotite breakdown after the formation of the metadiorite at T = 640–703 °C and P &amp;lt; 4.5 kbar and coarsening related to shear deformation.