Stable Isotope Geochemistry Research Articles

INDIVIDUAL FORAMINIFERAL ANALYSES: A REVIEW OF CURRENT AND EMERGING GEOCHEMICAL TECHNIQUES

Abstract The trace element (TE) and isotopic composition of calcareous foraminifera has been invaluable in advancing our understanding of environmental change throughout the geological record. Whereas “bulk” geochemical techniques, typically requiring the dissolution of tens to hundreds of foraminiferal tests for a single analysis, have been used for decades to reconstruct past ocean-climate conditions, recent technological advances have increased our ability to investigate foraminiferal geochemistry from an individual test to a micron-scale domain level. Here we review current and emerging techniques and approaches to studying the trace element and stable isotope geochemistry of individual foraminifera (i.e., individual foraminiferal analyses or “IFA”), covering spatial scales including whole-test analysis, intratest spot analysis, and cross-sectional chemical mapping techniques. Our discussion of each technique provides an overview of how the specific analytical tool works, the history of its usage in foraminiferal studies, its applications, considerations, and limitations, and potential directions for future study. Lastly, we describe potential applications of combining multiple IFA techniques to resolve key questions related to paleoceanography, (paleo)ecology, and biomineralization, and provide recommendations for the storage, dissemination, and transparency of the vast amounts of data produced through these methods. This review serves as a resource for budding and experienced foraminiferal geochemists to explore the wide array of cutting-edge approaches being used to study the geochemical composition of modern and fossil foraminifera.

Effect of CO2 and H2SO4 on the dissolution of a carbonate basement and alteration of silicates in a volcano-sedimentary system in central Mexico

This study explores the hydrogeochemical and isotopic characteristics of groundwater in the Irapuato Valley and Celaya Valley Aquifers in central Mexico, specifically focusing on the role of CO2 in mineral alteration during water-rock interaction. The study is grounded in the principles of hydrogeochemistry and stable isotope geochemistry, analyzing the impact of CO2 and H2SO4 on the weathering of carbonates and silicates. Hydrogeochemical analysis, including Piper diagrams, and isotopic measurements (δ13C, δ18O, δ2H), were conducted on water samples from wells in four municipalities (Irapuato, Salamanca, Villagrán, and Juventino Rosas). The data was statistically evaluated using Shapiro-Wilk tests to assess normality, skewness, and kurtosis, ensuring the reliability of the findings. The results indicate that HCO3− dominates the groundwater composition, with CO2 and H2SO4 significantly influencing mineral alteration processes. The isotopic data suggest that CO2 is primarily released from carbonate rock degassing, with slight isotopic enrichment in δ13C due to water-carbonate interaction. Hydrothermal fluids contribute to the geochemical evolution of the aquifer, leading to the formation of minerals such as tridymite, alunite, and kaolinite. Additionally, some groundwater samples exhibit evidence of thermalism and water-rock interactions, influencing their isotopic signatures and temperatures. These findings underscore the importance of CO2 in groundwater chemistry and highlight the need for further studies to understand regional flow dynamics and the potential impact of geothermal systems on water quality.

Metallogenic model of the Lykling ophiolite-hosted lode Au deposit, Scandinavian Caledonides: Insight from fluid inclusions, mineral chemistry and stable isotope geochemistry

The Lykling lode Au deposit represents a unique example of gold mineralization in the Upper Allochthone of the Scandinavian Caledonides. The mineralization is hosted by the Early Ordovician Lykling Ophiolite Complex and the intruding trondhjemite unit and spatially associated with two generations of mafic dykes that crosscut both the ophiolitic complex and trondhjemite. Field observations indicate that the mafic dykes did not play an active role in the emplacement of Au at Lykling, however their contacts with the immediate host rocks (i.e., gabbro and trondhjemite) may have focused ore-forming fluids.Three main stages in the evolution of the hydrothermal system in the Lykling area are documented by two generations of auriferous quartz veins: 1) older quartz-carbonate veins hosted by moderately angled brittle-ductile shear zones and 2) younger quartz-sulfide veins that fill steeply dipping brittle faults. Stage 1 resulted in deposition of barren quartz and gold-free pyrite from moderately saline NaCl-CaCl2-H2O ± CO2 fluids at temperatures between ∼310–330 °C and pressures in the range from 2.7 to 3.5 kbars. Under the given physicochemical conditions Au was mobile in the form of its chloride complexes. Stage 2 is associated with multiple episodes of ductile deformation punctuated by concomitant brecciation reflecting brittle-ductile transition processes. Fluid inclusion data reveals a decrease in temperature and pressure that may result in the formation of stable Au-bisulfide complexes and making the hydrothermal mobility of Au sensitive to changes in pressure. Consequently, the fluctuation in pressure controlled by the development of brittle-ductile structures likely resulted in the precipitation of native gold in quartz veins. Stage 3 represents a pure brittle event which is accompanied by a significant decrease in the fCO2/fS2 ratio. Mixing of higher-temperature and moderate-salinity fluids with cooler fluids has been recognized as the principal trigger for deposition of sulfides and a paragenetically late phase of native gold in the Lykling hydrothermal system.The Lykling ophiolite-hosted lode Au deposit shows numerous similarities with orogenic gold deposits elsewhere, including structural controls during mineralizing events, deposition from moderately to low salinity CO2-bearing aqueous solutions, deposition from a focused fluid flow along trans-crustal fault zones with a mixed brittle-ductile character and the spatial association with regionally metamorphosed terranes. In contrast to the great majority of the known orogenic gold deposits, the Lykling ophiolite-hosted lode Au deposit records a magmatic origin of volatiles. Therefore, taking into consideration field relationships and the regional setting of the Lykling deposit, we argue that its formation is concomitant with emplacement of the Sunnhordland Batholith during post-collisional thinning of the crust and associated localized uplift within the Lykling Ophiolite Complex.

Cathodoluminescence Petrography and Stable Isotope Geochemistry of Carbonate Rocks to Evaluate Diagenetic Evolution of the Middle Jurassic Samana Suk Formation (SSF), Kahi Section, Nizampur Basin, NW Himalayas, Pakistan

Cathodoluminescence Petrography and Stable Isotope Geochemistry of Carbonate Rocks to Evaluate Diagenetic Evolution of the Middle Jurassic Samana Suk Formation (SSF), Kahi Section, Nizampur Basin, NW Himalayas, Pakistan

On accurate calculations of equilibrium H/D fractionations at super-cold conditions (≤200 K) I: Full Partition Function Ratio (FPFR) vs. Path Integral Monte Carlo (PIMC)

Accurate estimations of Hydrogen/Deuterium (H/D) isotope effects have been a long-standing problem since the beginning of stable isotope geochemistry, primarily due to their strong nuclear quantum effects (NQEs). Currently, the D/H ratio plays a key role in deciphering the origin and evolution of water ice and organics in the solar system. Additionally, the Big-bang origin of Deuterium necessitates that the observed D/H variations be linked to isotope exchange reactions, such as HD + H2O ↔ H2 + HDO. Therefore, an accurate benchmark dataset describing the equilibrium H/D isotope fractionations at low temperatures (≤ 200 K) is essential for interpreting rapidly accumulating astrochemical observation data. In this study, we implemented and compared two methods developed for evaluating the NQEs of H/D isotopes: 1) the Full Partition Function Ratio (FPFR) method and 2) the Path Integral Monte Carlo (PIMC) method. Both were assessed for their accuracy and efficiency in estimating equilibrium isotope effects (EIEs) using 10 common interstellar small molecules (H2, HF, HCl, HCN, HNC, H2O, H2S, NH3, HCHO, and CH4) as examples. Most of them are calculated at high precision for the first time. For the FPFR method, several higher-order corrections to the Urey-Bigeleisen-Mayer model were considered, including anharmonicity, quantum mechanical rotation with nuclear-spin statistics, and corrections to the Born-Oppenheimer approximation. For the PIMC method, four different actions related to the thermal density matrix are used. These include the primitive and three fourth-order actions (Takahashi and Imada, Suzuki-Chin and Chin approximations), based on the direct scaled-coordinates transformation. Three main conclusions are obtained: 1) Under the framework of Born-Oppenheimer approximation, the PIMC method holds the same and even slightly better accuracy (more comprehensive descriptions of quantum anharmonicities) in estimating EIEs for H/D isotopes as the FPFR method. However, both methods suffer from the neglection of the DBOC when using the Born-Oppenheimer potential energy surfaces. For the PIMC method, additional corrections for particle distinguishability must be considered when nuclear spin statistics exhibit its effects at low temperatures (e.g., < 160 K for H2). 2) Among the four actions, three fourth-order actions show better convergence and efficiency (2.2 to 26.5 times speedups at 50 K) than the primitive action, making them superior candidates for PIMC simulations at super-cold (≤ 200 K) conditions. 3) A combination of accurate potential energy surface with the PIMC method serves as an alternative way for theoretical estimations of H/D isotope effects.

Paleozoic Equatorial Records of Melting Ice Ages (PERMIA): calibrating the pace of paleotropical environmental and ecological change during Earth's previous icehouse

Abstract. The upper Paleozoic Cutler Group of southern Utah, USA, is a key sedimentary archive for understanding the Earth-life effects of the planet's last pre-Quaternary icehouse–hothouse state change: the Carboniferous–Permian (C–P) transition, between 304 and 290 million years ago. Within the near-paleoequatorial Cutler Group, this transition corresponds to a large-scale aridification trend, loss of aquatic habitats, and ecological shifts toward more terrestrial biota as recorded by its fossil assemblages. However, fundamental questions persist. (1) Did continental drift or shorter-term changes in glacio-eustasy, potentially driven by orbital (Milankovitch) cycles, influence environmental change at near-equatorial latitudes during the C–P climatic transition? (2) What influence did the C–P climatic transition have on the evolution of terrestrial ecosystems and on the diversity and trophic structures of terrestrial vertebrate communities? The Paleozoic Equatorial Records of Melting Ice Ages (PERMIA) project seeks to resolve these issues in part by studying the Elk Ridge no. 1 (ER-1) core, complemented by outcrop studies. This legacy core, collected in 1981 within what is now Bears Ears National Monument, recovered a significant portion of the Hermosa Group and the overlying lower Cutler Group, making it an ideal archive for studying paleoenvironmental change during the C–P transition. As part of this project, the uppermost ∼ 450 m of the core were temporarily transferred from the Austin Core Repository Center to the Continental Scientific Drilling Facility at the University of Minnesota for splitting, imaging, and scanning for geophysical properties and spectrophotometry. Here we (1) review the history of this legacy core, (2) introduce recently obtained geophysical and lithologic datasets based on newly split and imaged core segments to provide a sedimentological and stratigraphic overview of the Elk Ridge no. 1 core that aligns more accurately with the currently recognized regional lithostratigraphic framework, (3) establish the position of the boundary between the lower Cutler beds and the overlying Cedar Mesa Sandstone in the core, and (4) outline our ongoing research goals for the core. In-progress work on the core aims to refine biostratigraphic and chemostratigraphic age constraints, retrieve the polarity stratigraphy, interrogate preserved cyclostratigraphy, analyze sedimentary structures and paleosol facies, investigate stable isotope geochemistry, and evaluate elemental abundance data from X-ray fluorescence (XRF) scanning. Together with outcrop studies throughout Bears Ears National Monument and its vicinity, these cores will allow the rich paleontological and paleoenvironmental archives recorded in the continental Carboniferous–Permian transition of western North America to be confidently placed in a robust chronologic context that will help test hypotheses relating ecosystem evolution to the Carboniferous rainforest collapse, initial decline of the Late Paleozoic Ice Age, and long-wavelength astronomical cycles pacing global environmental change.

Paleoenvironment in the circum-arctic region from the Middle Jurassic to Early Cretaceous: Trace element and stable isotope geochemistry of the Agardhfjellet Formation, Svalbard

From the Middle Jurassic to Early Cretaceous, the mudstone-dominated Agardhfjellet Formation was deposited during the prolonged shelf dysoxic-anoxic event (SDAE) recorded predominantly in the circum-arctic polar regions. Commonly, oceanic anoxic events (OAEs) throughout Earth's history are linked to the emplacement of large igneous provinces (LIPs). OAEs and LIPs, alone or jointly, are inferred to be triggers for severe biotic crises in Earth's history. However, the causes for SDAEs remain uncertain. To elucidate these causes, we document the geochemical features of the Agardhfjellet Formation using trace element concentrations and stable isotope ratios. The Agardhfjellet Formation, which consists of the Oppdalen, Lardyfjellet, Oppdalssåta, and Slottsmøya members in ascending order, formed during ∼13 Myr of prolonged dysoxic, anoxic, and euxinic conditions. The onset of shelf anoxia took place between deposition of the Oppdalen and Lardyfjellet Members. The extent of sea floor anoxia in the basin varied within the Lardyfjellet Member but likely persisted throughout most of the Slottsmøya Member. Mo/TOC and MoEF/UEF ratios in the sedimentary rocks are consistent with the anoxic events. Enhanced continental runoff marked the Oppdalen, Oppdalssåta, and Slottsmøya members, contrasting with most of the Lardyfjellet Member, in which authigenic phases were widespread under anoxic conditions. Our results show that, compared to other OAEs, such as the Toarcian OAE (∼183 Ma) or the OAE2 (∼94 Ma), the Late Jurassic – Early Cretaceous SDAE recorded in the Agardhfjellet Formation is characterized by prolonged suboxic–anoxic condition, substantial water-mass stratification, and increased continental runoff.

Volatile light hydrocarbons as thermal and alteration indicators in oil and gas fields

Volatile light hydrocarbons (VLH) are an essential component of reservoir petroleum fluids. Understanding of their origin and fate is crucial not only in exploration but increasingly also in petroleum engineering, as this greatly impacts fluid typing, proper mapping, recoverability and economic value. Due to their sensitivity to subsurface thermal stress and geological alteration processes, their proper characterisation holds promise to understanding the thermal conditions under which petroleum fluids were generated and subsequent fluid modifications during migration and within the reservoir. To study the behaviour of these hydrocarbons under different geological conditions we selected oil and gas fields from two giant conventional petroleum systems in the Arabian Peninsula collectively spanning the entire petroleum spectrum from heavy oil to dry and sour gas. In situ representative bottomhole or recombined pressure–volume–temperature (PVT) fluid composition data were constrained with molecular and stable carbon isotope geochemistry in key wells. Systematic covariance among the slope factor (SF) of propane to pentane and the isomer ratios of butane and pentane with reservoir engineering and geochemical variables in well-constrained black oil to gas condensate petroleum systems allowed the derivation of three formulas to calculate thermal maturity in terms of vitrinite reflectance equivalent from VLH fluid composition: (1) %VRe(SF) = 0.38 SF + 0.41, (2) %VRe(i4) = 1.70 (iC4/nC4) + 0.61, and (3) %VRe(i5) = 0.89 (iC5/nC5) + 0.56. The slope factor, iC4/nC4, and iC5/nC5 ratios all increase monotonically with the thermal evolution of unaltered fluids, allowing for effective application of their derived %VRe formulas across the entire unaltered fluid spectrum, from heavy oil to dry gas. Deviations from indigenous-fluid trends do occur for fluids altered by phase separation, biodegradation, thermal cracking, and thermochemical sulfate reduction (TSR), but corrections can be made to minimize uncertainty in assessing true thermal maturity of altered fluids while respecting other reservoir fluid properties such as gas-to-oil ratio (GOR) and saturation pressure relationships. For instance, although a single charge that has been phase fractionated yields fluids with variable GORs, saturation pressures and slope factors, their butane and pentane isomer ratios remain reflective of the original fluid maturity. In contrast, biodegradation-induced overestimation of maturity based on the isomer ratios of butane and pentane can be corrected by the less affected SF-derived maturity parameter. Reversal to lower apparent SF-derived maturity in thermally and TSR cracked fluids can, on the other hand, be corrected by considering the less affected butane and pentane isomer ratios. Overall, maturities calculated using VLH composition correspond well with fluid type defined based on phase behaviour and source-rock kinetics, thereby putting forward new tools to quantify thermal maturity of reservoir fluids that may be applicable in other petroleum systems.

Multi-stage micrite diagenesis in the late Jurassic of the Eastern Paris Basin: petrophysical and mechanical properties for engineering purposes

Abstract The Calcaires du Barrois Formation is a succession of dominantly micritic limestone of Kimmeridgian to Tithonian age, outcropping in the eastern part of the Paris Basin. This is an active karstic aquifer of interest to Andra (French National Agency for Radioactive Waste Management), who are studying the feasibility of a deep geological repository of radioactive waste in an underground research laboratory located approximately 450 m below the surface. Surface installations of the Industrial Centre for Geological Disposal project are planned in the upstream recharge zone of the aquifer. It is of primary interest to characterize the Calcaires du Barrois Formation to provide guidelines for the planning and sizing of these facilities, to minimize the impact on the aquifer system. An integrated study was designed for this purpose, linking petrography (thin section and scanning electron microscopy), carbon and oxygen stable isotope geochemistry, X-ray diffraction, petrophysics and geomechanics. It is based on the analysis of three key cored wells penetrating the formation at different relative depths. The Calcaires du Barrois have undergone several stages of diagenesis that have defined the current properties. Unconformities associated with the Jurassic–Cretaceous transition led to prolonged early subaerial exposures during which freshwater flowed efficiently through the upper half of the formation. Through mineralogical stabilization, among other processes, microporosity was preserved in micrites in this interval consisting of clean limestone with thin marl layers. The lower half of the formation, more argillaceous, was not or was only slightly affected by this early meteoric diagenesis, and recrystallization and cementation of micrites occurred during burial diagenesis, involving chemical compaction. Later, during the return to the surface associated to the Cenozoic orogens, another phase of meteoric diagenesis affected the uppermost few metres below the outcropping portions of the formation, but without modifying significantly the previously acquired petrophysical properties. Consequently, an intra-formational boundary was progressively developed at around 75 m (from the top reference). This boundary separates (1) a lower half of the Calcaires du Barrois with dense and tight micrites, showing high Young's modulus values, and a moderate intensity of fractures, from (2) an upper half with microporous micrites showing low Young's modulus values, and almost devoid of fractures. A transitional zone of about 30 m thick, with intermediate properties, sitting above this boundary and below the only thin metre-scale macroporous grainstone level of the formation, accommodated most of the deformation linked to the Cenozoic Western European orogens and is intensively fractured. The current hydrogeological model considers a purely sedimentological boundary to delimit two sub-aquifers within the Calcaires du Barrois Formation. This will have to be reappraised since it is here demonstrated that the real boundary is located significantly higher in the formation and is inherited from a multi-stage diagenetic history. These findings will complement and influence planning for the Industrial Centre's project.

Stable hydrogen and oxygen isotope geochemistry of Fe3+-rich, interstratified clay minerals from seafloor hydrothermal sites

Chemical and structural complexities in interstratified clay minerals arising from mineral transformations and evolving formation conditions should be recorded in their stable isotope signatures. This paper examines the controls on the stable hydrogen and oxygen isotope compositions of Fe3+-rich, glauconite-nontronite, talc-nontronite and talc-saponite from submarine hydrothermal sites, with a focus on the Red Sea Atlantis II Deep. Values of δ18O became less positive in the order nontronite > glauconite-nontronite > talc-nontronite > talc-saponite, yielding oxygen isotope temperatures ranging from ∼40 °C for nontronite to ∼135–300 °C for talc-saponite. These clay minerals have low δ2H, ranging from −145 to −127‰ for talc-nontronite, −135‰ for nontronite, −129 to −85‰ for glauconite-nontronite, and −95 to −59‰ for talc-saponite. The clay mineral-water hydrogen isotope fractionation is strongly affected by Fe3+ content, with increasing structural Fe3+ causing progressive weakening of O-H bonds. The large ionic radius and high charge of Fe3+ cause it to be more poorly shielded by surrounding oxygen from hydroxyl hydrogen relative to other octahedral or tetrahedral cations. The resulting lengthening of O-H bonds favours 1H over 2H. Our results confirm that Fe-rich phases, such as nontronite-glauconite, are produced at the lowest temperatures and Mg-rich phases, such as talc-saponite, are formed at the highest temperatures in seafloor hydrothermal environments. Evolving fluid chemistry and fluid pathways during clay mineral formation are also important. Glauconite layer formation from precursor nontronite likely occurred during diagenesis; redox changes causing Fe-reduction and an increase in layer charge facilitated interlayer K-fixation. Talc-saponite compositions vary with temperature and fluid chemistry, forming at variable sediment depths depending on access to the hottest hydrothermal fluids.

Stable isotope geochemistry evidences from fossil carbonate and sulfur minerals on the origin of geothermal water, Kızıldere Geothermal Field, Western Turkey

The Kızıldere geothermal field, located at the eastern part of the Büyük Menderes graben in Western Turkey, is the most important geothermal reservoir suitable for electricity generation. Current and fossil fumaroles and alteration zones are directly related to the tectonic zones influenced by N-S directional extension since Miocene period. Associated to fossil geothermal activities carbonate (calcite, dolomite) and sulfate (gypsum, anhydrite) minerals were occurred in the form of void/crack fill and bands/lenses parallel to bedding of Neogene clastic and carbonate rocks. The carbon (δ13CPDB ‰) and oxygen (δ18OPDB ‰) isotope compositions of hydrothermal calcites and dolomites and sulfur (δ34SCDT) and oxygen (δ18OSMOW) isotope compositions of gypsum and anhydrites are analyzed first time and correlated current geothermal water composition. The carbon and oxygen isotope data of calcites and dolomites have similar carbon but different oxygen isotope composition which increases in the direction of surface calcite – drill cuttings calcite – drill cuttings dolomite – surface dolomite. The isotope compositions of calcite and dolomite minerals range between limestone and marble host rock compositions and indicate the carbonate mineral-forming fluids originated from dissolution of carbonate rocks during the circulation of hot geothermal waters. According to the calcite-CO2 and dolomite-CO2 isotopic fractionation data for the 0–300 °C temperature range, the fossil isotope composition is higher than the composition of current CO2 and reflects relatively lower temperature conditions. The isotope compositions of gypsum and anhydrite minerals indicate that hot thermal waters dissolved terrestrial evaporites and formed a sulfur-rich geothermal solution, and hydrothermal gypsum and anhydrite precipitated from this solution. The δ34SCDT compositions of hydrothermal gypsum and anhydrites are similar to the current geothermal water compositions. Stable isotope geochemistry data of hydrothermal carbonate and sulfate minerals in the Kızıldere geothermal field have shown that the fluids forming these minerals were originated from host rocks instead of magmatic volatiles.

Determining of an oceanic anoxic event and paleoenvironmental conditions of the Gulneri Formation Kirkuk Oilfield, Northern Iraq

Stable isotopic geochemistry in relation to major and trace elements geochemistry of core samples from the Gulneri Formation at Kirkuk Oilfield Northern Iraq has been conducted to determine the occurrence of the oceanic anoxic event (OAE2) and reconstruct the paleoenvironmental conditions during this event. Positive values of the stable carbon isotopic data have revealed that temperature is high during deposition accompanied with higher organic productivity and a high rate of organic carbon burial with a decrease in dissolved oxygen in marine environments, whereas, negative oxygen isotopic values indicate deposition in hot, dry, semi-arid environments with salty marine waters and high organic productivity. These results were also supported by geochemical evidence of paleoclimate through C-value and ratios of Sr/Cu, Rb/Sr, and Ga/Rb, paleosalinity using proxies from Ca/Ca+Fe and Sr/Ba ratios, and paleoproductivity using P/Ti, P/Al and barium ratios. The paleoredox proxies from V/(V+Ni), V/Ni, and U/Th ratios and Uδ indicate dominant anoxic conditions. The recorded oceanic anoxic event (OAE2) has been determined through significant excursion in carbon and oxygen isotopic values as well as geochemical proxies within the sequences of the upper part of the formation marking the final stage of the OAE event.

Metal Organic Complexation in Seawater: Historical Background and Future Directions.

The speciation of most biologically active trace metals in seawater is dominated by complexation by organic ligands. This review traces the history of work in this area, from the early observations that showed surprisingly poor recoveries using metal preconcentration protocols to the present day, where advances in mass spectroscopy and stable isotope geochemistry are providing new insights into the structure, origin, fate, and biogeochemical impact of organic ligands. Many long-standing hypotheses about the specific biological origin of ligands such as siderophores in seawater are finally being validated. This work has revealed the complexity of organic complexation, with multiple ligands and, in some cases, timescales of ligand exchange that are much slower than originally thought. The influence of organic complexation on scavenging is now a key parameter in biogeochemical models of biologically essential metals, especially iron. New insights about the sources and sinks of ligands are required to enhance the usefulness of these models.

Geochemical and Isotopic Compositions of Fluorites from the Yama Fluorite Deposit in the Qilian Orogen in Northwest China, and Their Metallogenic Implications

The Yama area is characterized by numerous large-scale fluorite–quartz veins that are located along faults within the widespread Late Devonian–Late Silurian syenogranites in the Tataleng granitic batholith, Qilian Orogen, Northwest China. These fluorite–quartz veins contribute to an important fluorite reserve, but their ore genesis remains unresolved so far. In this study, trace elements, rare earth elements (REEs), and hydrogen, oxygen, and strontium isotopic compositions of fluorites are analyzed. The studied fluorite samples have similar chondrite-normalized REEs, including Y patterns, with relatively strong enrichment in heavy REEs, negative Eu anomalies, strongly positive Y anomalies, and comparably invariable Y/Ho ratios of 41.43–73.79, suggesting a unique hydrothermal genesis. The relatively variable values of δD and δ18O are −77.4‰ to −102.4‰ and −12.7‰ to −4.3‰, respectively, close to the meteoric water line. These fluorites yield relatively invariable analytical 87Sr/86Sr ratios of 0.749089−0.756628 (except for an anomalously high ratio), and their calculated initial 87Sr/86Sr ratios, based on the ore-forming ages provided, are apparently higher than the calculated initial 87Sr/86Sr ratios of syenogranite wall rocks. Collectively, the geochemistry of trace elements, REEs, and stable isotopes (H, O, and Sr) suggests that the ore-forming fluids were of meteoric origin and that the Sr sources were directly derived from the ore-forming fluids themselves rather than syenogranite wall rocks. Finally, it was considered that the Yama fluorite deposit is a fault-controlled hydrothermal vein-type deposit which was possibly related to the evolution of the Paleo-Tethys Ocean in the Permian–Triassic.

Omnivariant Generalized Least Squares regression: Theory, geochronological applications, and making the case for reconciled Δ47 calibrations

Least-squares regression methods are mathematically powerful, conceptually and computationally simple, and widely used in many fields. However, none of the commonly-used flavors of least-squares regression, such as York regression or Generalized Least Squares (GLS), take into account the full set of covariances between all observed (x, y) values. Here we describe the Omnivariant Generalized Least Squares (OGLS) method to fit a model of the form y = f(x), accounting for the full error correlation structure of the (x, y) data, based on a first-order linear propagation of the uncertainties in all variables into errors in y residuals, followed by minimizing the vector of y residuals with respect to the Mahalanobis norm defined by its covariance matrix. This approach may be described as a generalization of both York regression and GLS. It is mathematically exact for straight-line fits, and is also suitable for many non-linear models. Here we describe the principles of OGLS regression and discuss its properties, caveats, and practical use, and provide two consistent open-source implementations in Python and R. To illustrate how various fields of geochronology and stable-isotope geochemistry may benefit from this new method, we discuss how OGLS may specifically apply to 40Ar/39Ar dating and how it provides robust mathematical evidence that Δ47 carbonate calibrations in the recently defined I-CDES metrological scale are statistically indistinguishable, effectively solving long-standing methodological discrepancies.

Barnacle-rich facies as a tool for palaeoenvironmental reconstructions

Palaeoenvironmental data are fundamental in determining the manifold impacts of climate change. This paper argues that sessile barnacles are an excellent palaeoenvironmental proxy: they are present in nearly all nearshore environments, and their shell consists of diagenetically stable low-magnesium calcite and grows fast enough to record short-term variations. To demonstrate their utility, specimens from several Western Mediterranean Pliocene and Pleistocene barnacle-rich deposits are analysed herein, using for the first time a combination of sedimentology, taphonomy, stable isotope geochemistry and detailed comparisons with modern counterparts. Within shelf carbonate systems, barnacle diversity is highest in the shallow, nearshore waters and decreases moving offshore, thus providing a good proxy for the reconstruction of water depth and distance from the coastline. Barnacle taphonomy is also informative. Well-preserved complete specimens are characteristic of protected areas, whereas less well-preserved specimens occur in high-energy areas. The presence/absence of opercular plates is also particularly relevant for evaluating hydrodynamic conditions. As regards the C and O stable isotope ratios, due to the porous and coarse-grained nature of the deposits in which barnacle remains are usually found, the shells are often exposed to meteoric water percolation during diagenesis. Among the analysed specimens, only those collected from fine-grained deposits display no evidence of alteration and have isotopic ratios in line with those of their modern counterparts. These fossils display intra-shell variations that in modern barnacles have been related to short-term environmental changes (e.g., seasonal cycles). These results demonstrate that barnacles can always be useful for detailed palaeoenvironmental reconstructions based on skeletal assemblages. Furthermore, with further research aimed at gathering more data and assessing potentially interfering signals, they could become useful proxies for palaeoseasonality.

Influence of high-frequency lake level fluctuations on organic matter accumulation in the northern Qaidam Basin, NW China: Insights from spectral attribute analysis and geochemistry

Assemblages of multiple organic matter-rich sedimentary energy carriers are frequently found in Jurassic nonmarine basins of China. These basins are strongly influenced by high-frequency fluctuations in lake levels. A series of coal- and oil shale-bearing successions reflecting periodic lake level variations is also present in the Shimengou Formation, northern Qaidam Basin, NW China. These Middle Jurassic coal and oil shale seams provide an excellent basis for studying the effects of high-frequency lake level fluctuations on organic matter accumulation. Moreover, additional factors influencing the primary organic matter input (e.g., wildfires) and its preservation and later diagenetic transformation (e.g., processes during coalification) must be considered. In the present study, organic matter maturity, source potential, and paleoenvironmental conditions during source rock formation are investigated based on macro- and micropetrographic data, proximate analyses, bulk geochemical parameters, biomarker analyses, stable isotope geochemistry, and spectral attribute analysis to provide a sequence stratigraphic framework for the accumulation of organic-rich intervals. According to the established depositional model, the Shimengou Formation can be subdivided into four depositional sequences, including three organic matter-rich intervals. These include the thick mixed gas- and oil-prone Sq1 coal seam with a relatively high ash yield, which represents a highstand systems tract, the gas-prone Sq3 coal seam corresponding to a transgressive systems tract, and the Sq4 oil shale layers likely corresponding to a subsequent highstand systems tract, indicating a drowned mire. The results provide insights for the optimization of high-quality sedimentary mineral resource production in similar basins worldwide.

Microbialites on the northern shelf of Lake Van, eastern Türkiye#: Morphology, texture, stable isotope geochemistry and age

ABSTRACTLake Van, the world's largest alkaline lake, hosts some of the largest microbialite towers worldwide, which are considered as modern analogues of ancient stromatolites. This study investigates the links between microbialite evolution, geology, climate and hydrology, and the role of biotic and abiotic processes in microbialite growth and morphology. For these objectives, the northern shelf of Lake Van was surveyed by sub‐bottom seismic profiling and diving, and two 9 m and 15 m high microbialite chimneys were sampled at 25 m water depth. Samples were analysed for stable oxygen and carbon isotopes, X‐ray diffractometry, scanning electron microscopy and U/Th age dating. Lake Van microbialites precipitate wherever focused Ca‐rich groundwater flows onto the lake floor to mix with alkaline lake water. Variable columnar, conical and branching morphologies of the microbialites indicate various processes of formation by groundwater channelling within the chimneys. Collectively, our data suggest that the microbialite chimneys have formed within the last millennium, most likely starting during the warm and humid Medieval Climate Anomaly (ca ad 800–1300), when lake level rose approximately to the present level due to enhanced Inputs of riverine Ca‐rich freshwater and groundwater. Our new scanning electron microscopy observations indicate that the internal structure of the microbialites below the outer cyanobacteria‐covered crust is constructed by calcified filaments, globular aggregates and nanocrystals of algal, cyanobacterial and heterobacterial origins and inorganically precipitated prismatic calcite crystals. These textural features, together with dive observations, clearly demonstrate the important role of inorganic carbonate precipitation at sites of groundwater discharge, followed by cyanobacteria and algal mucilage deposition and microbially meditated calcification in the photic zone in the rapid growth of the microbialite chimneys. Considering the close similarities of some textures with those of ancient stromatolites and meteorites, the results of this study provide new insights into the environmental conditions associated with stromatolite formation and extra‐terrestrial life evolution.

Late Miocene paleoecology and paleoclimate in the central High Plains of North America reconstructed from paleopedological, ichnological, and stable isotope analyses of the Ogallala Formation in western Kansas, USA

The late Miocene was a critical time in the development of the North American Great Plains marked by paleoclimate-driven biotic change, including faunal turnovers and the spread of C4 dominated grasslands. The large volume of sediment shed from the Rocky Mountain region during this time preserves a record of these transitions, which can be informed by previously undescribed paleosol and trace fossil properties from the Ogallala Formation of the central High Plains. The purpose of this paper is to reconstruct paleoenvironments, paleoclimate, and paleoecology from outcrops of the Ogallala Formation in western Kansas by integrating paleopedology, ichnology, and stable isotope geochemistry. Eleven lithofacies are recognized in the study area, mostly massive to crudely stratified, fine-to coarse-grained sandstone and pebbly gravel with stratigraphically uncommon fine-grained lithofacies restricted to thinly bedded intervals or lens-shaped geometries within the sand-dominated strata. These host five pedotypes: 1) calcic Vertisols developed on overbank fines, 2) Entisols developed on braid bar gravels, 3) Entisols developed on volcaniclastic sediment lenses, 4) calcic Inceptisols developed on coarse sandy channel fills, and 5) calcareous Mollisols developed on fine sandy bedforms and channel fills. We recognize ten ichnogenera within paleosols, including burrows attributed to ants, bees, beetles or hemipterans, vinegarroon-like arthropods, fossorial reptiles, seed caching mammals, and large carnivorous mammals. Organic carbon stable isotopes indicate that the flora consisted entirely of C3 plants, and paleosols and trace-fossil evidence suggest a tree-limited savanna environment with patches of unvegetated soil. Paleoclimate proxies from paleosol and trace fossil properties indicate mean annual air temperatures between 8 °C and 20 °C with seasonal differences of up to 14 °C between mean monthly temperatures of the warmest and coolest months. Mean annual precipitation was likely between 250 mm and 460 mm with a seasonal difference of up to 250 mm between mean monthly precipitation of the driest and wettest months. While hymenopteran tracemakers were active, soil surface temperatures reached at least 30 °C and moisture content was between 10% and 20%. With timing of deposition constrained biostratigraphically to the Barstovian through Hemphillian, our paleoclimate interpretations are most consistent with the period of relative climate stability after Middle Miocene Climate Transition cooling and before Late Miocene Cooling (∼13.8 Ma–7 Ma). The trace-fossil assemblage reveals previously unknown biodiversity among soil arthropods, as well as important trophic connections between the belowground and aboveground components of the terrestrial food web.

Ion and Stable Isotope Geochemistry of Produced Water in Coalbed Methane Wells in the Tiefa Basin.

The potential geochemical information in the produced water of coalbed methane (CBM) wells is conducive to the exploration and development of CBM in the case that the produced water is primitive formation water. A total of 58 produced water samples collected from 13 CBM wells in the Daxing Mine, Tiefa Basin, were investigated. Ionic composition tests and stable isotope analysis were conducted to explore the geochemical characteristics and sources of produced water as well as the method for determining whether the produced water is primitive formation water. The results suggest that the fracking fluid for CBM stimulations is the main factor affecting the ion change of the produced water in the initial stage of drainage. The concentrations of Cl- and Ca2+ + Mg2+ could be taken as the indices to identify whether the produced water is primitive formation water. When the Cl- concentration is lower than 20 mEq/L and the Ca2+ + Mg2+ concentration is lower than 1 mEq/L, the produced water is close to the pristine formation water. Biogenic methanogenic activity may result in a high δ13CDIC and high concentrations of HCO3- in the pristine formation water in the Tiefa Basin. The data of δD and δ18O in the study area suggest that the formation water might come from atmospheric precipitation, which is later affected by evaporation and the water-rock reaction. The hydrogen isotope values in the produced water derived from the lower coal group display a substantial elevation compared to those from the upper coal group. This disparity in the hydrogen isotope composition presents an opportunity to utilize δD in produced water as a tool for distinguishing the formation water between these two groups.