Os Isotope Research Articles

Spatial Distribution of Critical Metals and Chemostratigraphy in Co‐Rich Ferromanganese Nodules in the Northwestern Pacific Ocean

AbstractFerromanganese nodules are important marine storehouses for critical metals and windows for changing oceans. Although advanced in situ analytical techniques have been applied to visualize the elemental distribution in the nodule cross‐sections, their spatial distribution remains largely uncertain. This study addresses this gap by employing micro X‐ray fluorescence mapping of parallel nodule cross‐sections to delineate the spatial distributions of critical metals (Mn, Fe, Co, Ti, Ni, and Cu) in three Co‐rich ferromanganese nodules from the northwestern Pacific Ocean. The 10‐layer Os isotopic compositions of one nodule closely align with the well‐documented marine Os isotope evolution of seawater, providing a chronological framework and a maximum age of ∼36 Ma for these nodules. Three concentric chemostratigraphic layers, labeled L1, L2, and L3, were identified from the inside out, based on microscopic structures and the distributions of critical metals. The early growth stage was marked by Mn‐rich, Si‐rich, and high Mn/Fe ratios, suggesting a diagenetic‐driven process attributed to high paleoproductivity conditions because of the low latitude of the study area at that time. The subsequent growth stages are all hydrogenetic in origin to be rich in Fe, Co, and Ti with low Mn/Fe ratios. The apparent detritus present during the second growth stage of the nodules may correspond to the stronger bottom currents in the early Miocene. The final mineralization stage indicates a more stable environment with diminished bottom current activity, leading to the formation of a dense, laminar hydrogenetic layer.

Deep marine records of Deccan Trap volcanism before the Cretaceous–Paleogene (K–Pg) mass extinction

The Cretaceous−Paleogene boundary is marked by a large impact and coeval mass extinction event that occurred 66 m.y. ago. Contemporaneous emplacement of the volcanic Deccan Traps also affected global climate before, during, and after the mass extinction. Many questions remain about the timing and eruption rates of Deccan volcanism, its precise forcing of climatic changes, and its signature in the marine geochemical sedimentary proxy record. Here, we compile new and existing mercury (Hg) concentration and osmium isotope (187Os/188Os) records for various stratigraphic sections worldwide. Both geochemical proxies have been suggested to reflect past variations in Deccan volcanic activity. New data from deep marine pelagic carbonate records are compared to contemporaneous records from shallower marine sites correlated through high-resolution cyclostratigraphic age models. The robustness of the proxy records is evaluated on a common timeline and compared to two different Deccan eruption history scenarios. Results show that the global 187Os/188Os signal is clearly reproducible, while the global Hg record does not form a consistent pattern. Moreover, the deep marine sections investigated do not record clear variations in the Hg cycle, particularly in the latest Cretaceous, prior to the extinction event. A detailed reevaluation of the precise depth of the redistribution of impactor-sourced platinum group elements does not exclude the possibility of a minor drop in 187Os/188Os corresponding with a pulse of Deccan volcanism ∼50,000 years before the Cretaceous−Paleogene boundary. Simple Os isotope mass balance modeling indicates that the latest Cretaceous was marked by significant levels of basalt weathering. CO2 sequestration during this weathering likely overwhelmed the emission of Deccan volatiles, thereby contributing to the end of the late Maastrichtian warming.

Rhenium-platinum group elements reveal seawater incursion induced massive lacustrine organic carbon burial

Organic carbon burial in ancient lacustrine settings is a crucial source of petroleum resources. Unlike the marine environment, the dynamics of organic carbon burial in the terrestrial realm are more complex due to the interplay of global and regional climate-tectonic factors. There appears to be a potential linkage between seawater incursion events (SWIEs) and the generation of lacustrine source rocks. However, reliable proxies to reconstruct the frequency and extent of SWIEs are currently lacking. Here, we explore the potential of rhenium-platinum group elements (Re-PGE) system as a novel proxy for determining SWIEs in the Nenjiang Formation of the lacustrine Songliao Basin in China that is noted for its high-quality source rock. By comparing marine and non-marine intervals, we validate the utility of Re-PGE fractionation patterns and osmium (Os) isotope compositions. Moreover, the Re/Ir ratios demonstrate two main episodes of quantitative seawater-lake water exchange. The comparison of variable indicators shows that the Re-PGE system is more sensitive to the changes in water sources, thus providing detailed information of frequency and exchange amount. The inverse variation between seawater contribution and total organic carbon content further implies that the massive sulfate influx from SWIEs facilitated bacterial sulfate reduction in the sediment pile, which had the effect of recycling nutrients (e.g., phosphorous) back into the water column. The SWIEs-triggered eutrophication induced a positive feedback loop between productivity and hypoxia, creating ideal conditions for the preservation of organic carbon. Our data reveals the detailed mechanism of SWIEs-triggered organic carbon burial and emphasizes the significant role of SWIEs in generating economically important hydrocarbon reservoirs.

A novel approach for the anomalous collectivity in the neutron-deficient Os isotopes

Abstract An algebraic model with three-body boson interactions is proposed to incorporate the different quadrupole modes in nuclear collectivity. It is shown that the recently observed anomalous collective structure characterized by $B_{4/2}=B(E2;4_1\rightarrow2_1)/B(E2;2_1\rightarrow0_1)<1.0$ and $R_{4/2}= E(4_1)/E(2_1)\geq2.0$, which cannot yet be explained by any other microscopic nuclear models, naturally emerge in the present model due to the inclusion of triaxial rotor modes.
This description is further extended to describe the odd-$A$ nuclei by including the coupling to the Fermion degree of freedom. That allows us to give a unified explanation of the anomalous $B(E2)$ strengths in both even-even and even-odd systems which seemed to indicate different behaviors. As examples, the model is applied to describe the spectroscopy and $E2$ transition properties of $^{168,169,170,171}$Os. All recent measurements of those isotopes can be well reproduced on the same footing which suggests that the anomalous collectivity persists even in the odd-$A$ systems.

Intrasample osmium isotope disequilibrium in young volcanic rocks: Insights from a new progressive digestion procedure

Some young volcanic rocks have been found to possess intrasample Os-isotope heterogeneity. This has important implications for source tracing and dating. Here, we use a new procedure through which it is possible to sequentially extract, from a single aliquot, the 187Os/188Os ratio of: i) the surface contaminant(s) (hydrobromic acid leachate); ii) the residual bulk rock powder (Step I) and iii) the Os-bearing phases entrapped within silicates (Step II). We applied this technique to two young basaltic reference materials (RMs), USGS BHVO-2 and EN026 10D-3. The former samples the 1919 lava from the Kīlauea summit crater (Hawaii) and the latter is a basalt sample dredged from Mohns Ridge (Greenland Sea). Both rock standards have previously been shown to display large intrasample Os isotope heterogeneity. In addition to analyzing these RMs, we also analyzed the RM USGS BHVO-1 for comparison, as well as another sample from the Kīlauea 1919 summit eruption (Kil 1919-6) along with a picritic tholeiite from the Kīlauea Iki 1959 eruption.Our leaching results show that BHVO-2 is contaminated with a highly radiogenic and labile contaminant with 187Os/188Os ratio of 0.525 ± 0.021. Without leaching, the Step I 187Os/188Os ratios varied from 0.1399 ± 0.0013 to 0.1568 ± 0.0014 while those for Step II were uniform (average = 0.1286 ± 0.0006, N = 5). A comparison of Re, Mo concentrations and 187Os/188Os ratio of the leachates of BHVO-2 and its predecessor (BHVO-1) indicates that BHVO-2 was contaminated during preparation. After leaching, the Step I and Step II 187Os/188Os ratios of BHVO-1 and another sample (Kīlauea 1919-6) from the same lava flow are identical within error to that of the Step II ratio of BHVO-2. A picrite from the 1959 Kīlauea Iki eruption also analyzed using the new technique gives homogenous results for both the steps with an average 187Os/188Os ratio of 0.1302 ± 0.0005. The 187Os/188Os ratio of recent Kīlauea lavas is identical within error to that of the primitive upper mantle (=0.1296). The Kīlauea Os-isotope composition could represent a “common component” that occurs globally in many plumes. The Step I 187Os/188Os ratio of EN026 10D-3 is 0.136 with Step II ratio being 0.131 (N = 2). The Step II 187Os/188Os ratios are more radiogenic than the nearby Jan Mayen lavas (187Os/188Os = 0.124–0.129) that have been argued to influence the chemistry of the Western section of the Mohns Ridge basalt but fall within the range of the Primitive Upper Mantle. We also discovered that BHVO-1, KIL 1919-6, 1959 Kīlauea Iki picrite, and EN026 10D-3 show Os-isotope disequilibrium between the leachate and Step I, suggesting wall rock assimilation during magma ascent. The data set presented here indicates a need for re-evaluating the extent to which mantle heterogeneities influence the Os isotope composition of ocean basalts.

Carboniferous–Permian interglacial warming and volcanism temporally linked to the world's oldest alkaline lake deposit of the Fengcheng Formation, NW China

In addition to being an important lacustrine hydrocarbon source rock, the Fengcheng Formation possesses well-preserved sodium‑carbonate evaporite units and tuff beds. Known ancient alkaline salt-lake deposits bearing sodium‑carbonate evaporite minerals like the Late Paleozoic Fengcheng Formation are limited beyond the modern day. However, hitherto the absolute age of the alkaline lacustrine Fengcheng Formation of the Junggar Basin (China) is debated (Late Carboniferous and/or Early Permian), and therefore its temporal link to a specific stage of the Late Paleozoic Ice Age (LPIA) remains unclear. Here, new ReOs geochronology demonstrates that the Fengcheng Formation is predominately of Late Carboniferous-age (304.4 to 297.3 Ma), and therefore its deposition coincides with the interglacial climate warming interval between glaciation C4 and P1 of the LPIA and not the younger interglacial stages as previously proposed. The ReOs isotope systematics indicate that the lake water column during the deposition of the Fengcheng Formation had a relatively unradiogenic Os (187Os/188Os, Osi) isotope composition (0.32 to 0.36), which is in contrast to the typical radiogenic Osi recorded for lacustrine deposits throughout geological time. The unradiogenic Osi for the Fengcheng Formation ties the source of the Os in the lake to the weathering of adjacent mafic volcanic rocks and/or hydrothermal input (∼0.13). As a result, the penecontemporaneous relationship to the Late Paleozoic interglacial climate warming (causing enhanced evaporation) coupled with weathering of volcanic rocks and/or hydrothermal fluid input into the lake is considered to have been mechanistic in the formation of an alkaline salt lake dominated by sodium and carbonate.

Solid bitumen Rhenium-Osmium (Re–Os) isotope geochronology and existing problems: Sampled of Sinian-Cambrian gas reservoir in Sichuan Basin, China

Understanding the key timings related to petroleum evolution is crucial for optimizing exploration targets and assessing oil/gas resources, attract petroleum geologists’ attention worldwide. Recently, hydrocarbon (oil and bitumen) Re–Os isotope dating has been innovatively applied to constrain the timing related to oil/gas generation, however, the resulting Re–Os isochron ages can be complex and challenging to interpret. This study utilizes various geochemical and geochronological data from Sinian to Cambrian natural gas reservoirs in the Sichuan Basin to reconstruct the hydrocarbon evolution process and discuss the significance of different bitumen Re–Os dating results. The gas accumulation in the Sinian-Cambrian reservoirs experienced four stages of evolution: (1) initial oil generation during the Ordovician to Silurian periods, (2) secondary oil generation during the Triassic period, (3) gas generation through thermal cracking of liquid oil from the Jurassic to Cretaceous periods, and (4) gas reservoir redistribution since the late Cretaceous. The Re–Os dates (ca. 485 Ma) of low maturity and biodegraded bitumen from the western Sichuan Basin record the oil generation during the Ordovician before the Caledonian tectonic event. The Re–Os dates (ca.184–128 Ma) of highly mature bitumen associated with MVT Pb–Zn deposits in northern Sichuan Basin provide insights into both liquid oil-cracking and thermochemical sulfate reduction (TSR) processes. The complex Re–Os dates (ca.414 Ma, ca.154 Ma) of highly mature bitumen from the central Sichuan Basin may represent different periods related to either oil or gas generation. Future studies should explore the genetic type, maturity, thermal cracking, or TSR degrees of bitumen to better understand the significance of Re–Os dates.

Deep crustal assimilation during the 2021 Fagradalsfjall Fires, Iceland.

Active basaltic eruptions enable time-series analysis of geochemical and geophysical properties, providing constraints on mantle composition and eruption processes1-4. The continuing Fagradalsfjall and Sundhnúkur fires on Iceland's Reykjanes Peninsula, beginning in 2021, enable such an approach5,6. Earliest lavas of this volcanic episode have been interpreted to exclusively reflect a change from shallow to deeper mantle source processes7. Here we show using osmium (Os) isotopes that the 2021 Fagradalsfjall lavas are both fractionally crystallized and strongly crustally contaminated, probably by mid-ocean-ridge gabbros and older basalts underlying the Reykjanes Peninsula. Earliest eruptive products (187Os/188Os ≤ 0.188, platinum (Pt)/iridium (Ir) ≤ 76) are highly anomalous for Icelandic lavas or global oceanic basalts and Os isotope ratios remain elevated throughout the 2021 eruption, indicating a continued but diluted presence of contaminants. The 2022 lavas show no evidence for contamination (187Os/188Os = 0.131, Pt/Ir = 30), being typical of Icelandic basalts (0.132 ± 0.007). Initiation of the Fagradalsfjall Fires in 2021 involved pre-eruptive stalling, fractional crystallization and crustal assimilation of earliest lavas. An established magmatic conduit system in 2022 enabled efficient magma transit to the surface without crustal assimilation.

Re−Os Isotope and PGE Abundance Systematics of Coast Range Ophiolite Peridotites and Chromitite, California: Insights into Fore-Arc Magmatic Processes

Abstract We report platinum-group element (PGE) and Re concentrations, and Re−Os isotopic data for peridotites and podiform chromitite from the mid-Jurassic Coast Range ophiolite (CRO), California. Our aim is to provide insights into the formation and evolution of the CRO in a fore-arc tectonic setting. The CRO peridotites are divided into two groups: abyssal and supra-subduction zone (SSZ). They have Ir-group PGE concentrations similar to estimates for the primitive mantle and nearly chondritic relative abundances [(Os/Ir)N ≈ 1.1]. Abyssal-type peridotites have slightly subchondritic Pd-group PGE (PPGE)−Re abundances and flat chondrite-normalized patterns, whereas the SSZ-type ones are depleted overall with highly fractionated PPGE−Re patterns. The CRO peridotites have 187Os/188Os values of 0.1188 to 0.1315 (γOs = −8.3 to 1.4) and 187Re/188Os ranging from 0.022 to 0.413. The oxygen fugacity based on the V/Yb ratios of the CRO peridotites is equivalent to the fayalite−magnetite−quartz buffer. The abyssal-type peridotites are residues after ≤5% melting of the primitive upper mantle and represent a remnant of oceanic lithosphere trapped in an SSZ setting but before it was re-melted or modified by subduction processes. The abyssal-type peridotites yield an aluminachron model age of ~1.5 Ga, implying that the CRO mantle had experienced episode(s) of melt extraction before the CRO crust was formed. The SSZ-type peridotites are refractory residues after ~5% to 15% melting. Extraction of fore-arc basalts generated mainly by decompression melting resulted in the SSZ-type peridotites. The chromitite has 187Os/188Os value of 0.1250 (γOs = −3.5) and PGE−Re patterns complementary to that of boninite, indicating a genetic link to fore-arc magmatism.

Evidence for large-scale, long-term highly siderophile element heterogeneities in the Atlantic mantle from Leg 153 and 209 peridotites

Seafloor abyssal peridotites are products after partial melting and melt-rock interaction, providing constraints on upper mantle processes and heterogeneity. Despite extensive studies of ophiolitic peridotites and a burgeoning dataset for dredged abyssal peridotites, limited studies have been undertaken on abyssal peridotite drill core samples. This omission means a lack of comparison between modern ocean mantle lithosphere and that of ophiolites, where field context is possible in the latter, but not the former. Ocean Drilling Program (ODP) Leg 153 near the Kane fracture zone, and ODP Leg 209, near the Fifteen-Twenty fracture zone, both on the mid-Atlantic Ridge but ∼1000 km distant from one another, recovered serpentinized mantle peridotites. We report whole-rock major-, trace- and highly siderophile-element (HSE: Re, Pd, Pt, Ru, Ir, Os) abundances and 187Os/188Os ratios of peridotites from three cores (maximum depth of 200.8 m) from the two Legs to explore mantle heterogeneity within the Atlantic Ocean basin. Peridotites from ODP Leg 153 are relatively fertile, with Al2O3 contents ranging from 1.1 to 2.7 wt%. They are characterized by relatively radiogenic 187Os/188Os (0.1259 ± 0.0017; 2 S.D.) and uniform HSE abundances. The ODP Leg 209 peridotites are highly refractory, with Al2O3 contents ranging from 0.1 to 0.8 wt%, and imply that they record an extensively depleted mantle. They have 187Os/188Os of 0.1207 ± 0.0023 (2 S.D.) and fractionated HSE abundances, indicative of depletion occurring > 1 billion years ago. Marked heterogeneity both in the extent and timing of depletion are therefore evident along a large segment of the mid-Atlantic ridge that produces zero-age basalts. Measurement of Os isotopes in spatially associated mid-ocean ridge basalts (MORB) is challenging due to their sub ng/g Os contents. Instead, Nd isotopes of MORB are used to show that they are unlikely to have formed directly from abyssal peridotite-like sources. Abyssal peridotites therefore represent long-lived refractory residues during mantle upwelling with the sources of MORB being more enriched. Comparison between drilled abyssal peridotites and ophiolitic mantle reveals larger compositional variations in the latter. The overall higher melting extent in ophiolite mantle is likely reflective of a more complex life cycle than the modern oceanic lithosphere.

A heterogeneous mantle and crustal structure formed during the early differentiation of Mars.

Highly siderophile element abundances and Os isotopes of nakhlite and chassignite meteorites demonstrate that they represent a comagmatic suite from Mars. Nakhlites experienced variable assimilation of >2-billion-year-old altered high Re/Os basaltic crust. This basaltic crust is distinct from the ancient crust represented by meteorites Allan Hills 84001 or impact-contaminated Northwest Africa 7034/7533. Nakhlites and chassignites that did not experience crustal assimilation reveal that they were extracted from a depleted lithospheric mantle distinct from the deep plume source of depleted shergottites. The comagmatic origin for nakhlites and chassignites demonstrates a layered martian interior comprising ancient enriched basaltic crust derived from trace element-rich shallow magma ocean cumulates, a variably metasomatized mantle lithosphere, and a trace element-depleted deep mantle sampled by plume magmatism.

Accretion of “young” Phanerozoic subcontinental lithospheric mantle triggered by back-arc extension—the case of the Ivrea-Verbano Zone

The subcontinental lithospheric mantle (SCLM) beneath Phanerozoic regions is mostly constituted by fertile lherzolites, which sharply contrast with cratonic mantle made of highly-depleted peridotites. The question of whether this chemical difference results from lower degrees of melting associated with the formation of Phanerozoic SCLM or from the refertilization of ancient depleted SCLM remains a subject of debate. Additionally, the timing and geodynamic environment of accretion of the fertile SCLM in many Phanerozoic regions are poorly constrained. We here document new geochemical and Nd-Hf isotopic data for orogenic lherzolite massifs from the Ivrea-Verbano Zone (IVZ), Southern Alps. Even though a few Proterozoic Re depletion ages are locally preserved in these mantle bodies, our data reveal that the IVZ lherzolitic massifs were “recently” accreted to the SCLM in the Upper Devonian (ca. 370 Ma) during Pangea amalgamation, with a petrochemical evolution characterized by low-degree (~ 5–12%) depletion and nearly contemporaneous pervasive to focused melt migration. The lithospheric accretion putatively took place through asthenospheric upwelling triggered by Variscan intra-continental extension in a back-arc setting related to the subduction of the Rheic Ocean. We thus conclude that the fertile sections of Phanerozoic SCLM can be accreted during “recent” events of back-arc continental extension, even where Os isotopes preserve memories of melting events in much older times.

Petrogenesis of volcanic rocks from the Quaternary Eifel volcanic fields, Germany: detailed insights from combined trace-element and Sr–Nd–Hf–Pb–Os isotope data

Quaternary rocks from the East and West Eifel volcanic fields in western Germany are a key suite of intraplate volcanic rocks that can provide insights into volcanism of the Central European Volcanic Province (CEVP) and into continental intraplate volcanism in general. We present a comprehensive dataset for Eifel lavas including isotope as well as major and trace element data for 59 samples covering representative compositions of the different volcanic fields. In line with previous studies, the lavas are all SiO2-undersaturated, alkaline-rich and mainly comprise primitive basanites, melilitites, and nephelinites (Mg# ≥ 57). Geochemical compositions of samples from both volcanic subfields display distinct differences in their trace-element as well as radiogenic isotope compositions, largely confirming previous subdivisions. Coupled trace-element and radiogenic Sr–Nd–Hf–Pb–Os isotope compositions can now provide firm evidence for spatially heterogeneous mantle sources and compositionally distinct magmatic pulses. Within the West Eifel Field, Sr–Nd–Pb isotope compositions of the younger (≤80 ka), ONB-suite (olivine-nephelinite-basanite) are similar to FOZO (FOcal ZOne) or the EAR (European Asthenospheric Reservoir) and resemble compositions that have been previously reported from plume-sourced ocean island basalts (OIB). In marked difference, older (700 Ma to 80 ka) volcanic rocks from the F-suite (Foidite) in the West Eifel field and from the entire east Eifel Field tap a more enriched mantle component, as illustrated by more radiogenic Sr isotope (86Sr/87Sr up to 0.705408) and variable Pb isotope compositions (206Pb/204Pb = 18.61–19.70, 207Pb/204Pb = 15.62–15.67 and 208Pb/204Pb = 38.89–39.76). Combined trace-element compositions of ONB-suite samples are in good agreement with results from batch melting models suggesting a hybrid composition of Eifel magmas formed through mixing 10% of a FOZO-like melt with 90% of a DMM-like melt, similar to melts from the Tertiary HEVF. However, radiogenic Sr–Nd–Pb isotope compositions of F-suite and EEVF and some ONB lavas require the admixture of melts from lithospheric mantle sources. Elevated Nb/Ta and Lu/Hf ratios in combination with variable 187Os/188Os ratios can now demonstrate the presence of residual carbonated eclogite components, either in the lithosphere or in the asthenospheric mantle. Finally, by combining geochemical and temporal constraints of Tertiary and Quaternary volcanism it becomes evident that CEVP volcanism in central and western Germany has resulted from compositionally distinct magmatic pulses that tap separate mantle sources. Although the presence of a mantle plume can neither be fully confirmed nor excluded, plume-like melt pulses which partially tap carbonated eclogite domains that interact to variable extents with the lithosphere provide a viable explanation for the temporal and compositional cyclicity of CEVP volcanism.

Geochemical Evidence of Plume Sources for High-MgO Lavas in the Western Kunlun Orogenic Belt

Abstract Plume-derived high-MgO lavas provide important information on the lithological, thermal and chemical variations of Earth’s deep mantle. Here we present results from detailed field, mineralogical and geochemical studies of Late Permian–Late Triassic high-MgO lavas near the Chalukou area in the Western Kunlun (WK) orogenic belt, NW China. The major element compositions of the lavas show extremely high MgO contents (26.6–33.8 wt %) in accordance with olivine accumulation. The parental magma is inferred to be picritic in composition with MgO of 17.2 ± 0.9 wt %. Olivine Zn/Fe and Mn/Zn ratios suggest a peridotite-dominated source with a minor fraction of pyroxenite. The temperature and oxygen fugacity estimates based on multi-methods including olivine-melt Mg–Fe equilibria, Al-in-olivine and olivine–spinel thermometry and oxybarometer yield a mantle potential temperature of 1522–1556 °C and high oxygen fugacity of FMQ (fayalite-magnetite-quartz) + 0.93. The H2O contents in the picrite flows are estimated as 3.67 ± 1.0 wt %, indicating the volatile-rich nature of parental magma and its mantle source. The immobile trace element features show that the WK picrites are OIB (oceanic island basalt)-like, with the enrichment in light rare earth elements and positive Nb, Ta, Zr and Hf anomalies. Furthermore, the Nd–O–Os isotopes display typical mantle values without involvement of recycled materials. Our results suggest the high-MgO volcanism in the WK orogenic belt originated from a volatile-rich plume source.

Sources of Ore Material in the Platinum-Group Element Deposits of Polar Siberia and the Middle Urals Based on the Data from Radiogenic (Re–Os, Pt–Os) and Stable (Cu, S) Isotopes

Abstract —Understanding the main events of platinum-group element (PGE) ore formation is impossible without analysis of the sources and behavior of major ore-forming components, namely, platinum, osmium, sulfur, and copper, which are important indicators of magmatic and hydrothermal processes. In contrast to the Re–Os isotope system, the radiogenic Pt–Os isotope system, as well as stable isotopes of Cu and S in PGE deposits, are still relatively understudied. Our comprehensive research is aimed at filling this gap. The paper presents data for the Guli massif of ultramafic and alkaline rocks and carbonatites in Polar Siberia and on the zonal Nizhny Tagil and Svetly Bor clinopyroxenite–dunite massifs in the Middle Urals, which include: (1) the contents of the highly siderophile elements (HSE) in whole rocks and platinum-group minerals (PGM), (2) the Re–Os and Pt–Os isotope systematics of chromitite, Os–Ir alloys, and Ru–Os sulfides, (3) the sulfur isotope composition in Ru–Os and Ir–Rh sulfides in primary and secondary PGM assemblages, and (4) the copper isotope composition in Pt–Fe minerals from chromitites and placers. The research was performed using scanning electron microscopy, electron probe microanalysis, and high-precision isotope-geochemical analysis. The high-precision Re–Os and Pt–Os isotope data show that the HSE contents in chromitites and PGM of the Guli massif were controlled by the composition of the mantle source that evolved with near-chondritic time-integrated Re/Os and Pt/Os ratios, which are also typical of the sources of most komatiites and abyssal peridotites. The δ65Cu values of the studied samples of ferroan platinum and isoferroplatinum are identical within the analytical uncertainty and are close to 0‰, which is typical of high-temperature Cu-containing minerals. The sulfur isotope compositions of the Ir–Rh sulfides of the kashinite–bowieite series and of the Ru–Os sulfides of the laurite–erlichmanite series in the primary PGM assemblages indicate that the source of sulfur has a chondritic isotope composition, which is in agreement with the osmium isotope composition of the Ru–Os sulfides and Os–Ir alloys. The heavy sulfur isotope composition (δ34S = 5.6 ± 1.5‰) of As-containing erlichmanite is consistent with its secondary origin. The new data on the isotope compositions of osmium, copper, and sulfur can be used as new important parameters that characterize the sources of PGE mineralization.

Significance of highly siderophile element and Re–Os isotope systematics in global carbonatites

The systematics of highly siderophile elements (HSE) in carbonatites have rarely been investigated although carbonatite melts are among key metasomatic agents in the Earth's mantle. Thus, establishing the Os isotope systematics of carbonatites is of prime importance because carbonatite metasomatism might play a determining role in driving 187Os/188Os signature of the Earth's mantle as a consequence of extreme mobility of carbonatite liquids. In this study, a suite of carbonatites from continental settings was analyzed for HSE abundances and Re–Os isotope systematics, combined with detailed petrography of sulfide phases, to provide constraints on the HSE behavior during the formation of carbonatite melts, the role of sulfides in distribution of HSE and the reliability of Re–Os isotope compositions. All investigated carbonatites display low ΣHSE <1 ppb whereby calciocarbonatites exhibit supra-chondritic OsN/IrN ratios from ∼1.4 to 15, in contrast to magnesiocarbonatites and Mg/Fe-rich carbonatites showing exclusively sub-chondritic OsN/IrN. We posit that preferential removal of Os over Ir during the segregation of calcite-normative melts from the co-existing S-rich silicate melts is the main driver of Os/Ir elemental fractionation. The present-day 187Os/188Os ratios in carbonatites range from mildly unradiogenic (∼0.124) to extremely radiogenic values (∼115–152), with 187Os/188Os(i) ratios spanning from negative to highly radiogenic (∼17) values, paralleled by highly variable 187Re/188Os ratios between 0.096 and ∼ 26,000, and without any clear relationship to the carbonatite type or emplacement age. The Re–Os systematics of carbonatites appear to be significantly modified by hydrothermal processes resulting in either removal of both Re and Os, or Re addition and, consequently, commonly negative calculated γOs values, which may indicate a rather limited potential of the Re–Os systematics to evaluate the nature of carbonatite melts. Conversely, limited Re–Os data for the samples that were likely not affected by late-stage perturbation indicate a largely radiogenic 187Os/188Os nature of carbonatite melts. Nevertheless, carbonatite melts may, in part, be responsible for the radiogenic γOs values commonly observed in mantle-derived silicate melts influenced by carbonatite-like metasomatism.

Integrated cyclostratigraphy of the Cau core (SE Spain) - A timescale for climate change during the early Aptian Anoxic Event (OAE 1a) and the late Aptian

We report a cyclostratigraphic study performed on the Cau core (Spain), which is considered an Aptian stratigraphic reference for global correlation and paleoenvironmental reconstruction. This investigation presents an astronomical timescale for the Aptian from the Ap2a to Ap14 carbon-isotope stages. Based on the evaluation of a multiproxy dataset from the Cau core, we recalibrate the age and duration of different biozones, bioevents, chemostratigraphic substages and horizons from the early and late Aptian, with special focus on the Selli Event, providing a new astronomical framework for Aptian climate. From the recognition of 14 long-eccentricity cycles, we propose a time span of 5.67 Ma from C-isotope segments Ap2a to the top of Ap14, and ages of 120.82 Ma for the onset of the nannoconid crisis, and 120.20 Ma for the onset of oceanic anoxic event (OAE) 1a. Calculations yield a duration of 1.47 Ma for OAE 1a. We estimate the age for the onset of the main non-radiogenic phase of the Os isotopes at 120.08 Ma, 120 ka after the onset of OAE 1a. The high-resolution data from the Cau core provide further insights in the temporal constraints of the OAE 1a and other Aptian paleoclimatic events. The onset of the main non-radiogenic excursion in Os isotopes occurring 120 ka after the onset of OAE 1a reinforces the theory of rapid destabilization of methane hydrates as the trigger of the anoxic event, that preceded the onset of large-scale volcanism.

Re–Os isotopes and geochemistry of pyrite from the Dongguashan Cu(-Au) deposit, Eastern China: Implications for porphyry-skarn-stratabound mineralization systems

Stratabound deposits are widely distributed along the Middle-Lower Yangtze River metallogenic belt (Eastern China). The stratabound mineralization system in these stratabound deposits remains enigmatic as to whether it is associated with late Mesozoic intrusions or late Carboniferous sedimentary exhalative processes. Dongguashan is a typical stratabound deposit and is characterized by pyrite that formed in porphyry-skarn-stratabound orebodies, which makes it ideal for comparing porphyry, skarn, and stratabound mineralization systems by pyrite study. We classify pyrite types according to occurrence and generation. Specifically, the pyrite in the porphyry orebodies is composed of Py-p1 (potassic zone) and Py-p2 (propylitic and phyllic zone). Py-s, among garnet grains, occurs in the skarn orebodies. From top to bottom, the pyrite in the stratabound orebodies is composed of macrocrystalline pyrite (Py-m) in the massive mineralization zone, Py-l in the laminated mineralization zone, and coarse-grained pyrite (Py-v1) and microcrystalline pyrite (Py-v2) in the vein-like mineralization zone. Co, Ni, Se, As, and Au are most likely to occur as solid solutions in the Dongguashan pyrite. Pb and Bi are likely distributed in Dongguashan pyrite homogeneously as nanoinclusions. The Zn, Cu, and Mo in Dongguashan pyrite indicate that these elements occur as micromineral inclusions. The positive correlation between S and Fe, high Co/Ni ratios (mostly > 2), and coexistence with hydrothermal minerals imply a magmatic-hydrothermal origin for the Dongguashan pyrite. Py-m yields a Re–Os isochron age of 135.8 ± 2.8 Ma (MSWD = 1.8), which is interpreted as the stratabound ore-forming age. Combined with previous results, the porphyry-skarn-stratabound mineralization is the product of the same hydrothermal fluid system related to Early Cretaceous magmatic activity.

Probing the 186Os/188Os Precision Barrier: New Recommended Values for the DROsS Reference Material and an Assessment of Mixed 1011 and 1012 Ω Amplifier Arrays

We present high precision negative ion thermal ionisation mass spectrometry (N‐TIMS) Os isotope measurement results for the DROsS isotope reference material (iCRM), to investigate the limits on the precision of TIMS‐based 186Os/188Os results. We used analytical conditions previously highlighted to optimise precision, present a new flexible data processing protocol, and measured 184Os intensities on a Faraday Cup equipped with an amplifier using a 1012 Ω resistor. Despite a measurement procedure that minimised uncertainty contributions from counting statistics and Johnson‐Nyquist noise, the intermediate measurement precision of our approach does not significantly improve on previous high precision Os isotope measurements, with the exception of 184Os/188Os. This is probably due to uncertainties in measured amplifier gain factors, which are greater when using mixed arrays of 1011 and 1012 Ω resistors than when using 1011 Ω resistors alone, though Faraday Cup deterioration could also contribute. We propose that multi‐dynamic Os isotope measurements could largely eliminate both of these uncertainties. Our 184Os/188Os measurement results are the most precise yet, yielding 184Os/188Os = 0.0013036 ± 0.0000007 (2s, n = 38). Additionally, we average our data with published data to recommend the following isotope ratios for DROsS: 186Os/188Os = 0.1199319 ± 0.0000024, 187Os/188Os = 0.1609227 ± 0.0000022, 189Os/188Os = 1.219709 ± 0.000010, 190Os/188Os = 1.983793 ± 0.000011.

Fine-grained interplanetary dust input during the Turonian (Late Cretaceous): evidence from osmium isotope and platinum group elements

The Turonian age (~ 90–94 Ma) was the hottest geological interval in the Cretaceous and also marked by the K3 event, a pronounced enrichment of 3He in pelagic sediments (i.e., massive input of extraterrestrial materials). Here, we present Os isotopic (187Os/188Os) and platinum group element (PGE) data from Turonian sedimentary records. After a sharp unradiogenic shift during the end-Cenomanian oceanic anoxic event 2, the 187Os/188Os ratios declined continuously throughout the Turonian, which could be ascribed to the formations of several large igneous provinces (LIPs). Because the interval with the most unradiogenic 187Os/188Os ratios (i.e., enhanced LIP volcanism) does not correspond to the warmest interval during the mid-Cretaceous, additional sources of CO2, such as subduction zone volcanism or the kimberlite formation, may explain the Cretaceous Thermal Maximum. As Os isotope ratios do not show any sharp unradiogenic shifts and PGE concentrations do not exhibit a pronounced enrichment, an influx of fine-grained cosmic dust to the Earth’s surface, possibly from the long-period comet showers, can be inferred at the time of the 3He enrichment during the mid-Turonian K3 event. Our findings highlight the different behaviors of 3He and PGE information in the sedimentary rocks during the input of fined-grained extraterrestrial materials.