Oxygen Isotope Signatures Research Articles

Matrix Corrected SIMS In Situ Oxygen Isotope Analyses of Marine Shell Aragonite for High Resolution Seawater Temperature Reconstructions

AbstractMarine shells incorporate oxygen isotope signatures during growth, creating valuable records of seawater temperature and marine oxygen isotopic compositions. Secondary ion mass spectrometry (SIMS) measures these compositions in situ at finer length‐scales than traditional stable isotope analyses. However, determining oxygen isotope ratios in aragonite, the most common shell mineral, is hampered by a lack of ideal reference materials, limiting the accuracy of SIMS‐based seawater temperature reconstructions. Here, we tested the capability of SIMS to produce seawater temperature reconstructions despite the matrix calibration challenges associated with aragonite. We cultured Anadara trapezia bivalves at four controlled seawater temperatures (13–28°C) and used strontium labeling to mark the start of the temperature‐controlled shell increment, allowing for more spatially precise SIMS analysis. An improved matrix calibration was developed to ensure more accurate bio‐aragonite analyses that addressed matrix differences between the pure abiotic reference materials and the bio‐aragonite samples with intricate mineral‐organic architectures and distinct minor and trace element compositions. We regressed SIMS‐IRMS biases of abiotic and biogenic aragonites that account for their systematic differences in major, minor, and trace elements, allowing for more accurate SIMS analyses of the temperature‐controlled shell increment. The thorough matrix calibration allowed us to provide a SIMS‐based seawater‐corrected oxygen isotope thermometer of T(°C) = 23.05 ± 0.36 − 4.48 · (δ18Oaragonite [‰ VPDB] − δ18Oseawater [‰ VSMOW] ± 0.25) and 103lnαaragonite‐seawater = (17.78 ± 0.88) · 103/T (K) − (29.44 ± 2.40) that agrees with existing aragonitic IRMS‐based thermometer relationships and improves the applicability of SIMS‐based paleo‐environmental reconstructions of marine bio‐aragonites.

The Isotopic Composition of Selected Phosphate Sources (δ18O-PO4) from the Area of the Vistula and Bug Interfluve (Poland)

Phosphorus belongs to the crucial bioelements that cause eutrophication, and phosphates, easily assimilated by organisms, are widespread in the environment. Phosphates can be of natural or anthropogenic origin and can derive from various point or non-point sources. Knowledge about the origin of nutrients is necessary to effectively manage, protect, and revitalize water resources. To recognize various phosphate sources in the study area of our research, i.e., the Vistula and Bug interfluve (SE Poland), we used the oxygen isotopic signature of phosphate ions (δ18O-PO4), which has been successfully used in recent decades as a tracer of phosphorus cycling in water studies. We measured the δ18O-PO4 of dissolved inorganic phosphates (DIPs) extracted from various phosphate sources. The obtained results are as follows: For springs, the δ18O-PO4 value varied from +14.8‰ to +18.5‰; for riverine samples, from +10.3‰ to +18.6‰, which were significantly location-dependent; while waste water treatment plant effluents ranged from +12.4‰ to +15.6‰. Two tested drainage water samples had similar isotopic compositions (+16.7‰ and +17.3‰). In the case of two analyzed bedrock samples, the δ18O-PO4 values, which were similar (+20.5‰ and +21.7‰), are close to the existing data on sedimentary bedrocks derived from similar geological periods. The obtained results can be helpful in future research aimed at identifying phosphate sources and P cycling in the studied area.

Characteristics and geological significance of carbon and oxygen isotopes of the Permian Lucaogou Formation dolomite in the southern Junggar Basin, northwestern China

Anomalously positive δ13C values in ancient dolomites are very rare. Dark gray argillaceous rocks of the lacustrine sediments of the Permian Lucaogou Formation are important source rocks in the Junggar Basin, and dolomites of varying thicknesses from 10 cm to 150 cm are often interspersed in argillaceous rocks. Based on the study of petrographic sections, this paper systematically analyzes the carbon and oxygen isotopes of dolomite and discusses the causes of abnormally high carbon isotope values and their significance in reconstructing paleoenvironment and paleoclimate. The results show that carbon isotope values are abnormally high in the dolomite of Lucaogou Formation, and the δ13C value is between +3.2 ‰ PDB and +19.6‰ PDB, with an average of +9.7‰ PDB. The δ18O values range from -17.4‰ PDB to -1.7‰ PDB, with an average of -8.1‰ PDB. From the lower part to the upper part of the Lucaogou Formation, the carbon isotope value gradually increases and becomes increasingly positive, and the carbon isotope of the dolomite deposited near the shore is more positive than that of the dolomite deposited far from the shore. The anomalously positive δ13C of the dolomite is mainly caused by microbial methanogenesis, with some contribution from evaporation. Microorganisms are mainly distributed at the redox interface. Evaporation controls the salinity and fluctuation of the redox interface in sedimentary water. The positive deviation difference in carbon isotopes between nearshore and offshore sedimentary dolomites may be related to the location of the redox interface during deposition. Together, the petrographic features and carbon and oxygen isotope signatures of the sections reflect the gradual evolution of the paleolake from a hydrologically open environment to a hydrologically closed one and the possible transition of the paleoclimate from a relatively warm to an arid condition, which is possibly a geochemical response to global climate change in the Permian period.

Absolute 230Th/U chronologies and Δ47 thermometry paleoclimate reconstruction from soil carbonates in Central Asian loess over the past 1 million years

Pleistocene loess records of the Khovaling Loess Plateau (KLP) in Tajikistan provide rich collections of lithic artifacts demonstrating past human presence in the region. To understand the timing of human activity and environmental conditions prevailing at that time U–Th dating and clumped/stable C/O isotope measurements have been applied to modern and Pleistocene soil carbonates (SCs) collected at several sites on the KLP and surroundings. U–Th ages were corrected by two methods: 1) assuming an initial [230Th/232Th] activity ratio of 0.85 ± 0.25 based on gamma spectrometry of loess/paleosol samples, and 2) the isochron technique using leachates and fully dissolved subsamples. Diagenetic alteration and potential U/Th mobilization and related isotope fractionation due to alpha-recoil was also modelled and found to be minor in the studied soil carbonates. Compared to model ages as references, uncorrected 230Th ages are only acceptable if measured [230Th/232Th] activity ratios of leachates are high (>30), while 230Th ages derived using method 1 are mostly overcorrected. It appears that SCs can be reliably dated by the U-series disequilibrium method in this sedimentary setting, but isochron dating cannot be spared. Application of the isochron method is required to derive 230Thmodel ages, which ensures that the non-zero initial 230Th and possible U–Th gain/loss due to alpha-recoil can be simultaneously corrected and reliable U–Th ages obtained. U–Th ages of Pleistocene SCs clearly demonstrate post-pedogenic ingrowth of multiple, non-contemporaneous populations of SCs within loess/paleosol units, and that SC formation happened in many cases under cold, presumably dry glacial climate conditions. Considering that U–Th ages of SCs provide minimum ages of the sediment in which they form, these ages can be useful in developing loess stratigraphic models and for correlation of paleosols with marine isotope stages. This implies that the age of a given paleosol and any lithic artifacts it may contain, indicating human activity, cannot be younger than the age of SCs formed in that paleosol. This is due to the nature of soil carbonates, which can be the product of both syn- and post-depositional processes.Clumped isotope thermometry of SCs collected from modern soils at three sites in Tajikistan provide evidence for SCs dominantly recording summer season soil temperatures, while the calculated soil water oxygen isotope signatures reflect annual signals and carbonate precipitation from source waters incorporating rainfall from prior to and during SC formation. In contrast, some Pleistocene SCs record soil temperatures and stable isotope compositions more appropriate to glacial conditions, confirming the findings of U–Th ages, and highlighting the primary role of aridity-driven soil moisture changes in SC precipitation in this setting. Considering the interpretative complexities of SC stable isotope compositions, involving issues such as SC formation depth within a soil/paleosol profile, seasonality of SC growth and violation of the law of superposition, SC stable isotope proxy records of past climates cannot be considered as a set of clearly sequential data through time. This implies that such SC-based stable isotope records must be accompanied by U–Th dating of carbonates to be meaningful.

Footwall refrigeration versus footwall hydration: Reassessing steep thermal gradients below detachment faults with in situ SIMS oxygen isotope analysis

The extensional detachment systems of metamorphic core complexes (MCC) have the potential to facilitate significant fluid movement between Earth's surface and the warm, ductile middle crust. One long-standing and influential detachment fault-fluid interaction model called the “footwall refrigeration hypothesis” (Morrison and Anderson, 1998) postulates that cool meteoric fluids circulating downward along a detachment can facilitate large-scale heat loss at depth before rocks are exhumed by faulting. Stable isotopes of oxygen and hydrogen have long been recognized as potentially useful tracers of surface-to-depth fluid flow in core complexes; however, typical sampling methods and the competing effects between temperature and fluid composition have made oxygen isotope signatures of meteoric fluid infiltration difficult to detect and/or interpret in the rock record.Here, we use in situ δ18O measurements by secondary ion mass spectrometry (SIMS) to address the rock record of meteoric fluid interactions and temperature variation within the Whipple Mountains MCC footwall beneath the Whipple detachment fault (WDF). The micro-scale sampling of SIMS (10 µm diameter x 1–2 µm deep pits) allows investigation of isotope variability as a function of mineral geochemistry and microstructure and enables more accurate interpretation of the causes of isotope variability. In the Whipple footwall mylonites, quartz and epidote show grain-to-grain oxygen-isotope variability within samples and as a function of distance from the main detachment. Approaching the WDF, both quartz and epidote show increasing spread toward low δ18O values. The lowest SIMS-measured δ18O epidote values require exchange with a low δ18O, meteoric fluid at high temperature. However, SIMS data also reveal that meteoric fluid-rock interactions were spatially heterogeneous at the scale of individual grains, resulting in local preservation of metamorphic quartz-epidote oxygen isotope equilibrium unaffected by infiltrating meteoric fluid. Within preserved metamorphic domains at all investigated structural levels of the WDF footwall, quartz and epidote δ18O values are tightly clustered and yield similar fractionations (∆18Oqz-ep). For samples from the longest footwall traverse, these ∆18Oqz-ep values are 4.0 ± 0.4‰, consistent with δ18O equilibrium at 521+43/-37 °C. We conclude that there is no evidence of a large paleo-thermal gradient associated with the Whipple Detachment Fault (i.e., no evidence for footwall refrigeration).

A review of benthic foraminiferal oxygen and carbon isotopes

Stable isotopes in the calcium carbonate of benthic foraminifera provide important paleoenvironmental information about seawater/sedimentary porewaters that these foraminifera live in. Oxygen isotopes provide essential insights about variations in deep water temperatures and sea-level/ice volume changes, while carbon isotopes provide information about sea-water carbon/nutrient cycling. In this review we look into detail at the direct and indirect mechanisms that contribute to stable oxygen and carbon isotope signals in Rotaliid benthic foraminifera. This includes effects from ontogenetic- and calcification mechanisms, and the impact of methane seeps and post-depositional diagenesis. We conclude our review with an overview of current challenges and provide recommendations for future research endeavors aimed at outstanding knowledge gaps in understanding how these biomineralizers control their stable isotopes.

Stable Water Isotope Signals and Their Relation to Stratiform and Convective Precipitation in the Tropical Andes

AbstractStratiform and convective precipitation are known to be associated with distinct isotopic fingerprints in the tropics. Such rain type specific isotope signals are of key importance for climate reconstructions derived from climate proxies (e.g., stable isotopes in tree rings). Recently, the relation between rain type and isotope signal in present‐day climate has been intensively discussed. While some studies point out the importance of deep convection, other studies emphasize the role of stratiform precipitation for strongly depleted isotope signals in precipitation. Uncertainties arise from observational studies due to data scarcity while modeling approaches with global climate models cannot explicitly resolve convective processes and rely on parameterizations. High‐resolution climate models are particularly important for studies over complex topography and for the simulation of convective cloud formation and organization. Therefore, we applied the isotope‐enabled version of the high‐resolution climate model from the Consortium for Small‐Scale Modeling (COSMOiso) over the Andes of tropical south Ecuador, South America, to investigate the influence of stratiform and convective rain on the stable oxygen isotope signal of precipitation (δ18OP). Our results highlight the importance of deep convection for depleting the isotopic signal of precipitation and increasing its deuterium excess. Due to the opposing effect of shallow and deep convection on the δ18OP signal, the use of a stratiform fraction might be misleading. We therefore propose to use a shallow and deep convective fraction to analyze the effect of rain types on δ18OP.

Temperatures of Vein Formation Associated With Plate Interface Deformation Constrained by Oxygen and Clumped Isotope Thermometry

AbstractTectonic mélanges, characterized by conditions reflective of modern subduction fault zones, preserve mineral veins formed through mass transfer, a mechanism influencing the slip behavior of subduction megathrusts. In this study, we apply secondary ion mass spectrometry quartz‐calcite oxygen isotope thermometry and clumped isotope thermometry to examine the temperatures of vein formations in six mélange units in the Cretaceous Shimanto belt and one mélange in the Kodiak accretionary prism. Calcite in the veins exhibits δ13CPDB values ranging from −17.2‰ to −6.8‰, indicative of a carbon source mixing with sedimentary carbonate and organic matter. δ18OSMOW values of calcite range from +11.1‰ to +17.2‰; quartz yields δ18OSMOW values of +14.9‰ to +21.7‰. Oxygen isotopic signatures in minerals reveal that most vein‐forming fluids are significantly affected by rock buffering, while some retain isotopic compositions of seawater and meteoric water. Temperature estimates, derived from both thermometers, fall within the range of 100–250°C. Notably, vein temperatures remain constant across diverse vein types and mélange units with distinct maximum temperatures. The combined temperature records and fluid isotopic compositions imply vein formations at shallower depths linked to the incorporation of seawater, meteoric water, and fluid released from early dehydration reactions. At greater depths, vein formations are associated with fluid released from clay dehydration and long‐distance fluid flow. Reduced vein formations between 250 and 350°C may correlate with a shift to fluid‐unsaturated conditions resulting from clay hydration reactions. Our study highlights potential mechanical and hydraulic variations within the thermal conditions of 100–350°C along the plate boundary driven by fluid‐mineral interactions.

Deciphering ore genesis with oxygen and sulfur isotope signatures: A case study from the Singhbhum Shear Zone, Eastern India

The importance of light-stable isotopes and their mass-dependent fractionations in understanding past geological processes is enormous. The present research delivers precise, high-resolution, in-situ oxygen (18/16O) and triple sulfur (32/33/34S) isotope ratios from quartz and sulfide minerals found in the CuAu Kendadih deposit located along the Mesoproterozoic (∼1.6 Ga) Singhbhum Shear Zone (SSZ) in eastern India. Oxygen and sulfur isotope analyses were carried out on quartz and pyrite-chalcopyrite pairs that are in textural equilibrium, using the most advanced Large Geometry-Secondary Ion Mass Spectrometer (LG-SIMS; CAMECA IMS-1300HR3). The results show restricted ranges for δ18Oquartz (+6 to +7.7‰; average: 6.9 ± 0.9‰, n = 50) and δ34Schalcopyrite-pyrite (+11.4 to +11.9‰; average: 11.79 ± 0.2‰, n = 62). This isotopic homogeneity suggests a single, uniform fluid source for the ore-forming metals. The combined oxygen, sulfur isotope ratios, and fluid inclusion data are consistent with a hydrothermal fluid derived from an “I-type” granitic melt. This study incorporates existing fluid inclusion, stable, and radiogenic isotope data from temporally similar deposits within the shear zone, reevaluating their implications in light of the new findings. It proposes that, around 1.6 billion years ago, underplating the Singhbhum Craton by the Dalma Plume resulted in the remelting of the lower crust. This remelting is attributed to the plume's introduction of a significantly elevated thermal perturbation. The process is hypothesized to have led to the generation of second-order granitic melts. Upon emplacement in the lower crust, these granitic melts became the potential source for essential metals, ligands, and hydrothermal fluids, contributing to mineralization within the deep-seated Singhbhum Shear Zone. This research attempts to comprehensively describe the “source-to-sink” ore genesis model by proposing potential magma chamber processes that concentrate metals and ligands at the roof zone, followed by the separation of metal-rich hydrothermal fluids, fluid-rock interaction, and the physicochemical conditions governing the deposition of the extensive polymetallic deposit. This work offers novel insights into the Mesoproterozoic metallogenesis along the Singhbhum Shear Zone, challenging existing paradigms that favored evaporite or seawater brine sources. Furthermore, it sheds light on the Mesoproterozoic sub-crustal processes beneath the Indian Craton in this region.

Hydrological dynamics and manganese mineralization in the wake of the Sturtian glaciation

The Cryogenian Sturtian and Marinoan glaciations stand as the most extreme climate events in Earth history. Intriguingly, large-scale Mn carbonates characterize the nonglacial interlude of this period in South China. The formation mechanism of Mn carbonates and the potential correlation underlying this temporal association remain elusive. Here, we present an integrated petrographic and geochemical study of drill core materials intercepting the Mn-bearing Datangpo Formation. Rare earth element patterns of these Mn carbonates exhibit positive Ce anomalies and a lack of Y anomalies, which differ from those of modern seawater but resemble marine Mn-Fe oxides. These features, combined with negative carbonate carbon isotope compositions (δ13Ccarb as light as −9.9 ‰ VPDB), indicate the presence of oxide precursors and the incorporation of light carbon during Mn-carbonate precipitation. Phosphate oxygen isotope ratios (δ18Op) of HCl-extractable apatite reveal a ∼4 ‰ difference in the average δ18Op between Mn-rich and Mn-poor rocks. We propose that the more positive δ18Op of Mn-rich samples may result from the dominance of phosphate released by reductive dissolution of metal oxides or a heavier oxygen isotope signal of surrounding waters with which isotopic equilibrium has been reached. We further illustrate how marine invasions into coastal anoxic basins could have triggered the formation of Mn oxides and highlight the role of glaciation–deglaciation in the development of giant Mn deposits.

Rapid oxygen isotopic exchange between bicarbonate and water during photosynthesis

Whether rapid oxygen isotopic exchange between bicarbonate and water occurs in photosynthesis is the key to determine the source of oxygen by classic 18O-labeled photosynthetic oxygen evolution experiments. Here we show that both Microcystis aeruginosa and Chlamydomonas reinhardtii utilize a significant proportion (>16%) of added bicarbonate as a carbon source for photosynthesis. However, oxygen isotopic signal in added bicarbonate cannot be traced in the oxygen in organic matter synthesized by these photosynthetic organisms. This contradicts the current photosynthesis theory, which states that photosynthetic oxygen evolution comes only from water, and oxygen in photosynthetic organic matter comes only from carbon dioxide. We conclude that the photosynthetic organisms undergo rapid exchange of oxygen isotope between bicarbonate and water during photosynthesis. At the same time, this study also provides isotopic evidence for a new mechanism that half of the oxygen in photosynthetic oxygen evolution comes from bicarbonate photolysis and half comes from water photolysis, which provides a new explanation for the bicarbonate effect, and suggests that the Kok-Joliot cycle of photosynthetic oxygen evolution, must be modified to include a molecule of bicarbonate in addition to one molecule of water which in turn must be incorporated into the cycle instead of two water molecules. Furthermore, this study provides a theoretical basis for constructing a newer artificial photosynthetic reactor coupling light reactions with the dark reactions.

Formational stages of natural fractures revealed by U-Pb dating and C-O-Sr-Nd isotopes of dolomites in the Ediacaran Dengying Formation, Sichuan Basin, southwest China

Deep core (>4.9 km) from Ediacaran Deng IV Member algal dolomites in the Gaoshiti-Moxi block in the Sichuan Basin, southwest China, reveals multiple generations of dolomite-lined and dolomite-filled opening-mode fractures. Three progressive stages of fracture formation are marked by crosscutting relations visible in the core, by acoustic emission experiments revealing evidence of past stress directions, and by fluid inclusions, U-Pb ages, C-O-Sr-Nd isotope patterns, and rare earth element data for dolomite cements in fractures, which document ages and differing thermal conditions and fluid compositions during fracture. In calcite-filled fractures, U-Pb ages and carbon and oxygen isotope signatures vary greatly, indicating that fractures developed with intensified tectonic activity marked by regional structures and with enhanced diagenetic alteration. In stage I, WNW-striking opening-mode fractures formed that contain dolomite deposits precipitated from basinal fluids between ca. 549 Ma and ca. 532 Ma. At this time, the Sichuan Basin experienced Xingkai taphrogenesis (rifting) from the late Neoproterozoic to early Cambrian. The central Sichuan paleo-uplift was undergoing ENE extension, and preexisting ESE- and nearly E-W−striking faults were oblique to the ENE principal stress orientation. This led to a local stress field favoring dextral shear near fault zones accommodated by the fractures. In stage II, ENE-striking fractures that are younger based on crosscutting relations contain dolomite deposits from basinal fluids with ages from ca. 423 Ma to ca. 411 Ma. Contemporaneous with Xuefeng thrusting, the central Sichuan paleo-uplift was in a NNE-striking transpressional stress field, which likely further generated ENE-striking fractures. In stage III, nearly N-S−striking fractures formed in the Gaoshiti-Moxi block. High-temperature fluids related to the Permian Emeishan large igneous province invaded these fractures from ca. 260 Ma to ca. 256 Ma. At this time, the Sichuan Basin was uplifted under the influence of the Emei taphrogenesis in the late Permian, and the central Sichuan paleo-uplift was subjected to E-W−striking extension. In fractures in these carbonate rocks, micro-computed tomography imaging reveals that macropores (>10 μm, 12.1%−21.8%) and small pores (2−10 μm, 76.6%−86.1%) dominate the dolomite mineral deposits, and that there are few (1.6%−1.8%) micropores or nanopores (<2 μm). Medium-sized throats (1−3 μm) are the main connecting channels. We infer that fractures served as conduits for fluid migration, leading to the dissolution of matrix pores adjacent to the fractures. This secondary porosity not only enhances reservoir storage capacity but also augments reservoir connectivity. Our study shows that in situ U-Pb dating and full-diameter rock acoustic emission data can effectively constrain the timing of fractures. By integrating this information with regional tectonic sequences and fracture diagenetic sequences from combined relative timing, geochemistry, and rock mechanics evidence, we clarify the factors controlling fracture formation.

Using stable isotopes in deciphering climate changes from travertine deposits: the case of the Lapis Tiburtinus succession (Acque Albule Basin, Tivoli, Central Italy)

Quaternary stable isotope records of marine and lacustrine carbonate deposits as well as speleothems were extensively studied to reconstruct global and regional climatic evolution. This study demonstrates how stable isotope records of travertine provide fundamental information about climate and the consequences of its evolution on groundwater level fluctuations. The deposition of the Lapis Tiburtinus travertine succession occurred during the Late Pleistocene (150–30 ka), coeval with the last activity of the Colli Albani volcanic complex. Two boreholes (Sn1 and Sn2) were drilled into the Acque Albule Basin (23 km E of Rome), crossing the entire Lapis Tiburtinus succession. The Sn1 borehole in the central part of the basin crosscuts a travertine succession of 62.1 m in thickness, while the Sn2 borehole in the southern part of the basin is characterized by a travertine succession 36.3 m in thickness. Carbon and oxygen stable isotope ratios were analysed on 118 samples (59 samples both for Sn1 and Sn2 boreholes) representative of the entire Lapis Tiburtinus travertine succession crossed by the boreholes. Values, measured and correlated in the two drilled boreholes, permitted determination of the sensitivity of the travertine depositional system to glacial and interglacial cycles, unravelling the complex oxygen and carbon cycle dynamic recorded in such sedimentary succession. Moreover, the results obtained correlated with available pollen curves of the Mediterranean area (from the Castiglione crater, 25 km E of Rome). Regional and global oxygen isotope continental and marine curves, calibrated with the stratigraphy of the Acque Albule Basin, and available U/Th dating allow the identification of at least three phases of the last interglacial (Marine Isotope Stage 5-MIS5). The carbon isotope record, compared with CO2 flux reconstructed and associated with the volcanic activity of the Colli Albani volcanic complex, instead shows an influence from groundwater level changes. In particular, positive shifts that occurred during arid phases are associated with a lower groundwater level and increased CO2 degassing, inducing a major fractionation effect on carbon isotopes. Instead, the negative shifts occurring during more humid periods indicate the inhibition of CO2 degassing and increase in pressure, attesting to a rise in groundwater level. In this view, travertine deposits, frequently studied to define the tectonic setting and activity of the area where they develop, can thus also be used as a tool to understand climate changes and groundwater variations apparent in their stable oxygen and carbon isotope signature.

Upper Visean (Mississippian) coral biostromes during onset of the late Palaeozoic Ice Age: A record from the equatorial eastern Palaeotethys

The late Visean-Serpukhovian is a critical time in reef evolution and climate history, characterized by the gradual collapse of coral reef systems during the onset of the main glaciation phase of the late Palaeozoic Ice Age (LPIA). However, detailed palaeoecological variations of coral reefs during the collapse phase are not well understood. In this study, about one-meter thick coral biostromes are reported from the upper Visean Shangsi Formation in the Yashui section, central Guizhou Province, South China. Coral colonies are primarily in growth position resulting in the classification of autobiostrome and autoparabiostrome. Dominant colonial rugose coral species are Stylostrotion petalaxoidea and Siphonodendron pauciradiale, respectively. The biostromal framework is simple and primarily constructed by bafflestones with slightly positive relief. Diversified dwellers are found between coral skeletons, including abundant foraminifers, crinoids, calcareous algae and brachiopods with less bryozoans, tabulate and solitary rugose corals, gastropods and ostracods. Relative sea-level fluctuations control the growth and demise of the Yashui biostromes, evidenced from changes in both microfacies and biotic assemblages from their underlying to overlying strata. The petalaxoidea biostrome developed in relative deeper water depth than that of the pauciradiale biostrome, between storm wave-base and fair-weather wave-base on a shallow photic open-marine shelf. The pauciradiale biostrome in South China (eastern Palaeotethys) has similar biotic composition, colony preservation and depositional environments to coeval coral biostromes in Ireland (western Palaeotethys). The Yashui coral biostromes formed shortly after the LPIA onset, evidenced in small-scaled eustatic fluctuations and a positive shift in brachiopod oxygen isotopic signatures.

Oxygen Isotope and Fluorine Impurity Signatures during the Conversion of Uranium Ore Concentrates to Nuclear Fuel.

Within the front end of the nuclear fuel cycle, many processes impart forensic signatures. Oxygen-stable isotopes (δ18O values) of uranium-bearing materials have been theorized to provide the processing and geolocational signatures of interdicted materials. However, this signature has been minimally utilized due to a limited understanding of how oxygen isotopes are influenced during uranium processing. This study explores oxygen isotope exchange and fractionation between magnesium diuranate (MDU), ammonium diuranate (ADU), and uranyl fluoride (UO2F2) with steam (water vapor) during their reduction to UOx. The MDU was precipitated from two water sources, one enriched and one depleted in 18O. The UO2F2 was precipitated from a single water source and either directly reduced or converted to ADU prior to reduction. All MDU, ADU, and UO2F2 were reduced to UOx in a 10% hydrogen/90% nitrogen atmosphere that was dry or included steam. Powder X-ray diffraction (p-XRD) was used to verify the composition of materials after reduction as mixtures of primarily U3O8, U4O9, and UO2 with trace magnesium and fluorine phases in UOx from MDU and UO2F2, respectively. The bulk oxygen isotope composition of UOx from MDU was analyzed using fluorination to remove the lattice-bound oxygen, and then O2 was subsequently analyzed with isotope ratio mass spectrometry (IRMS). The oxygen isotope compositions of the ADU, UO2F2, and the resulting UOx were analyzed by large geometry secondary ion mass spectrometry (LG-SIMS). When reduced with steam, the MDU, ADU, and UO2F2 experienced significant oxygen isotope exchange, and the resulting δ18O values of UOx approached the values of the steam. When reduced without steam, the δ18O values of converted ADU, U3O8, and UOx products remained similar to those of the UO2F2 starting material. LG-SIMS isotope mapping of F impurity abundances and distributions showed that direct steam-assisted reduction from UO2F2 significantly removed F impurities while dry reduction from UO2F2 led to the formation of UOx that was enhanced in F impurities. In addition, when UO2F2 was processed via precipitation to ADU and calcination to U3O8, F impurities were largely removed, and reductions to UOx with and without steam each had low F impurities. Overall, these findings show promise for combining multiple signatures to predict the process history during the conversion of uranium ore concentrates to nuclear fuel.

Rainfall-runoff partitioning in small watersheds of different vegetation types in the loess area based on hydrogen and oxygen isotope tracing.

Recognizing watershed runoff process and its component sources is a prerequisite for the rational use of water resources. To elucidate the effects and quantitative contributions of various vegetation types on the components of watershed runoff, we centered on the Caijiachuan main channel watershed in Jixian, Shanxi and five sub-watersheds with distinct vegetation types. By tracking the hydrological responses to two representative rainfall events and assessing the spatiotemporal variations in hydrogen and oxygen isotope signatures, we aimed to discern disparities in the runoff processes across these sub-watersheds and pinpoint their constituent origins. The results showed that under medium rainfall condition, the contribution rates of event water to the river flow of each watershed were in an order of protected forest (94.3%) > Caijiachuan main channel (83.1%) > agro-pastoral composite (64.3%) > plantation-secondary forest (52.4%) > cropland (0.3%) > secondary forest (0.0%); under light rainfall condition, plantation-secondary forest (52.4%) > protected forest (58.5%) > cropland (40.6%) > secondary forest (15.8%) > agro-pastoral composite (12.5%) > Caijiachuan main channel (9.3%). The event water contribution rate of secondary forest and protected forest watersheds to runoff was higher than that of plantation watersheds. The secondary forests watersheds had a stronger runoff storage capacity. The event water contribution rate of protected forest and agro-pastoral composite watersheds under medium rainfall intensity condition was greater than that under light rainfall intensity condition, while the event water contribution rate of cropland, plantation-secondary forest, and secondary forest watersheds was in adverse. The event water contribution to the runoff of forested watersheds was greater than that of cropland watersheds, which may be related to the presence of silt dams at the mouth of agricultural watershed channels. This study can provide a scientific basis for the analysis of water conservation and runoff change attribution in the loess area of west Shanxi.

Holocene climatic and tectonic forcing of decadal hydroclimate variation on the north-eastern Tibetan Plateau

A better understanding of past climate and landscape variability in high resolution on the Tibetan Plateau is of critical importance for the understanding of fundamental mechanisms and interactions in the global climate system. However, due to relatively few datasets in decadal-resolution available for analyzing possible seasonal effects and seismic activity on the northeastern Tibetan Plateau, further high-resolution lake records as an integration need to be explored to test the significance of the seasonal variations of surface processes and climatic phenomena as well as tectonic impact on a decadal scale. The rhomb-shaped pull-apart Lake Donggi Cona along the modern monsoon marginal zone on the north-eastern TP is considered an excellent archive that monitors neotectonic and climatic changes through time. We obtained new high-resolution (mean 20 yr) proxy records from a 488 cm-long sediment core from the lake and compare them directly with paleoclimate records from nearby lakes. A decadal-resolution oxygen stable isotope (δ18O) record co-varies positively with carbonate content and demonstrates the profound and varying contribution of glacier/snow melt (winter/spring moisture) to lake hydrology at different lake evolution stages. This is also indicated by the grain size composition and related endmember modelling (EMMA) results. During 11.8–9.4 cal Ka BP, the lake experienced a swamp status, apart from the major lake body followed by water rise towards the littoral zone until 7.5 cal Ka BP. Glacier melt water supply started to be active since the late Younger Dryas and led to the strong excursions of carbonate contents and δ18O values according to insolation increase. This phase was dominated by the westerlies and characterized as low seasonality with long winter duration. Water rose to its highest level during 7.5–6.5 cal Ka BP and fluctuated with deep water phases until 4.7 cal Ka BP, due to glacier melt maxima and potential increase of summer (convective) moisture preserved in the oxygen isotopic signals. Water cover dropped and remained low until 2.9 cal Ka BP due to the reduced glacier melt and colder climate. However, the low δ18O values at a reduced water budget points to the still active contribution of spring glacier/snow melt that kept the lake not dry-up unlike other lakes with no glacier melt water supply. After 2.9 cal Ka BP water level dropped towards a pond/lagoon situation until 2.0 cal Ka BP, albeit temperature rise after a long cold climatic interlude. It might be caused by another phase of lake deepening triggered by subsidence and related sediment relocation from the shore, rather than by climatic factors. However, water level increased again afterwards and fluctuated towards the present level due to non-summer moisture supply in long freezing winters. We assume profound signatures of high seasonality in climate after 7.5 cal Ka BP and the lake became open since1.3 cal Ka BP. We suggest that combined thermal forcing by glacier/snow melt and tectonics play a significant role together with solar forcing, governing hydroclimate changes on the north-eastern Tibetan Plateau with decadal to millennial cycles.

Climate change is rapidly deteriorating the climatic signal in Svalbard glaciers

Abstract. The Svalbard archipelago is particularly sensitive to climate change due to the relatively low altitude of its main ice fields and its geographical location in the higher North Atlantic, where the effect of Arctic amplification is more significant. The largest temperature increases have been observed during winter, but increasing summer temperatures, above the melting point, have led to increased glacier melt. Here, we evaluate the impact of this increased melt on the preservation of the oxygen isotope (δ18O) signal in firn records. δ18O is commonly used as a proxy for past atmospheric temperature reconstructions, and, when preserved, it is a crucial parameter to date and align ice cores. By comparing four different firn cores collected in 2012, 2015, 2017 and 2019 at the top of the Holtedahlfonna ice field (1100 m a.s.l.), we show a progressive deterioration of the isotope signal, and we link its degradation to the increased occurrence and intensity of melt events. Our findings indicate that, starting from 2015, there has been an escalation in melting and percolation resulting from changes in the overall atmospheric conditions. This has led to the deterioration of the climate signal preserved within the firn or ice. Our observations correspond with the model's calculations, demonstrating an increase in water percolation since 2014, potentially reaching deeper layers of the firn. Although the δ18O signal still reflects the interannual temperature trend, more frequent melting events may in the future affect the interpretation of the isotopic signal, compromising the use of Svalbard ice cores. Our findings highlight the impact and the speed at which Arctic amplification is affecting Svalbard's cryosphere.

The triple oxygen isotope signature of uranium oxides in the nuclear fuel cycle

Uranium oxides, in the form of U3O8 and UO2, are principal compounds in the uranium nuclear fuel cycle and attract significant interest in the general field of nuclear forensics, for the development of new and credible signatures to support attribution. This study presents, for the first time, the analytical method and high-precision measurements of the triple oxygen isotope composition of U3O8 and UO2. We show that Δ’17O can be measured at the accuracy and reproducibility needed for nuclear forensics. Δ’17O exhibits a wide range, from -450 to -120 ppm, for both commercial and synthetic uranium oxides. The presentation of the data in Δ’17O-δ’18O space provides a two-dimension identification of uranium oxides for nuclear forensic characterization of samples. The relation between Δ’17O and the process from which the oxide was formed or manipulated, has the potential to trace the chemical history of the material. We determined the change in Δ’17O of the system U3O8 – atmospheric O2 resulting from isotope exchange at the temperature range of 298 K to 973 K. The dependency of the triple isotope exponent, θ, on temperature was calculated for this exchange reaction, concluding that the phase transition from pseudo-hexagonal to hexagonal structure plays a major role in determining Δ17O and θ. A set of reduction reactions of U3O8 to UO2 indicate that Δ’17O undergoes minimal change during this process.

Oxygen Isotopes of Iron Oxides as a Diagnostic Tool for Iron Formation-Hosted High-Grade Magnetite-Hematite Deposits

Coarse-grained granoblastic magnetite-hematite and sheared platy hematite iron orebodies comprise several small deposits (5 to 30 Mt each) on the eastern margin of the São Francisco Craton, bordering the Ediacaran–Cambrian Brasiliano Orogenic belt. Three main mineralization stages are associated with the Brasiliano Orogeny: (1) syn- to the late-collisional stage (ca. 580–560 Ma) with development of lens-shaped schistose orebodies along thrust planes. (2) late- to the post-collisional stage (ca. 560–530 Ma) with the formation of massive magnetite bodies by contact metamorphic-metasomatism with pegmatite. (3) Post-tectonic stage with crystallization of granular hematite associated with late pegmatite (ca. 530–490 Ma). In order to better evaluate the fluid oxygen signature of each mineralization stage, new oxygen isotopes measurements were performed on ore bodies associated with the three stages. These stages are followed by changes in the oxygen isotope signature, with a progressive decrease of the δ18O from the iron formation (1.7 to 8.1‰) to high-grade ore (-1.6 to 2.6‰) that appears to be a common aspect of the mineralization of iron formations. In the present cases, magmatic fluids (δ18O from 4.6 to 13.1‰) have imprinted a relatively “heavier” signature than the most hypogene iron formation high-grade ores worldwide that was progressively modified by meteoric water percolated along extensional fractures. The iron oxides from the contact zones of pegmatitic yielded intermediate δ18O values (1.8 to 5.0‰), indicating a higher magmatic fluid/rock ratio.