Isotopic Signatures Research Articles

The Greenland spatial fingerprint of Dansgaard–Oeschger events in observations and models

Pleistocene Ice Ages display abrupt Dansgaard-Oeschger (DO) climate oscillations that provide prime examples of Earth System tipping points-abrupt transition that may result in irreversible change. Greenland ice cores provide key records of DO climate variability, but gas-calibrated estimates of the temperature change magnitudes have been limited to central and northwest Greenland. Here, we present ice-core δ15N-N2 records from south (Dye 3) and coastal east Greenland (Renland) to calibrate the local water isotope thermometer and provide a Greenland-wide spatial characterization of DO event magnitude. We combine these data with existing records of δ18O, deuterium excess, and accumulation rates to create a multiproxy "fingerprint" of the DO impact on Greenland. Isotope-enabled climate models have skill in simulating the observational multiproxy DO event impact, and we use a series of idealized simulations with such models to identify regions of the North Atlantic that are critical in explaining DO variability. Our experiments imply that wintertime sea ice variation in the subpolar gyre, rather than the commonly invoked Nordic Seas, is both a sufficient and a necessary condition to explain the observed DO impacts in Greenland, whatever the distal cause. Moisture-tagging experiments support the idea that Greenland DO isotope signals may be explained almost entirely via changes in the vapor source distribution and that site temperature is not a main control on δ18O during DO transitions, contrary to the traditional interpretation. Our results provide a comprehensive, multiproxy, data-model synthesis of abrupt DO climate variability in Greenland.

Hydrological controls of a riparian wetland based on stable isotope data and model simulations.

Isotopic evidence of groundwater and stream water is frequently used to investigate water exchanges with groundwater. Monthly sampling of rain, stream water, and groundwater was conducted at Tims Branch watershed in South Carolina for the oxygen and hydrogen stable isotope (δ2H and δ18O) measurement, as well as pH and oxidation-reduction potential (ORP). Together with a mass balance perspective, it was determined that it takes a few weeks to one month for groundwater in the hyporheic zone to fully exchange with stream water. From hydrodynamic modelling, we show that substantial (up to 70 %) groundwater exchange occurs at gaining and losing sites. Groundwater exfiltration, i.e. inflow into stream water, contributes up to 4 % to stream water, with the remainder from upstream exfiltration. A 2-4 % per day renewal rate of adjacent groundwater would indirectly indicate a groundwater residence time in the order of half a month to a full month (assuming either a well-mixed case or large dispersion rate in pulse flow case), in agreement with a greatly reduced variability of δ2H and δ18O of groundwater compared to stream water and rain. This reduced variability of stable isotope signal from groundwater confirms our hypothesis that riparian groundwater mixing at Tims Branch is more of a mixed type rather than a pulse flow type. A monthly time scale is sufficient for groundwater to become anoxic at exit points into stream water resulting in the episodic production of natural organic matter- and iron-rich flocs upon oxidation.

Organic geochemical and compound specific stable carbon isotope analyses of n-alkanes and saturated carboxylic acids extracted from late Paleozoic coals

AbstractIsotopic studies of coal organic matter are often conducted to gain information about past ecosystems and plant communities e.g. under changing climate conditions. While many studies focused on isotope analysis of bulk coal organic matter or extractable aliphatic hydrocarbons, the polar fraction and compounds that are bound to kerogen and not freely extractable have received less attention. The aim of this study was to provide a systematic comparison and evaluation of information gained from different molecular compounds (n-alkanes, n-carboxylic acids) extracted from Paleozoic coals before and after alkaline hydrolysis. Stable carbon isotope analysis of these compounds were used to evaluate a possible application of extractable and ‘bound’ lipids for paleoenvironmental analyses. Coal samples of different stratigraphic age, low thermal maturity (VRr < 1.02%, mostly VRr < 0.8%) and from different paleogeographic locations were selected to investigate organic matter deposited under different paleoenvironmental and paleoclimatic conditions. Molecular distributions show prominent carbon preference suggesting preservation of biologic signatures in coal organic matter. Permian Gondwana coals show similar n-alkane and n-carboxylic acid distribution which may be related to Glossopteris flora. Molecular distributions of Carboniferous coal from Europe are more variable with unimodal or bimodal patterns and maxima in the short- or long-chain range, reflecting higher diversity of paleovegetation and different contribution from algae or bacteria in limnic and paralic environments. The isotope signals of free as well as bound fatty acids show closer response for different depositional environments, whereas signals of paraffins and bulk organic matter are less variable. However, averaged fatty acid isotope signals in coals from different paleovegetational realms, e.g. Euramerica and Gondwana differed only marginally. Graphical abstract

AGE AND PETROGENESIS OF DOLERITES ON THE MARA RIVER (SAYAN MARGINAL UPLIFT OF THE BASEMENT, SOUTHERN PART OF THE SIBERIAN CRATON)

This work focuses on petrological-and-geochemical features, as well as age of dolerites widespread within the basins of the Mara, Kamenka and Uvat rivers. The isotope geochronological data acquired for baddeleyite allowed referring origination of these rocks to the time interval 1600–1620 Ma, interpreted as the time of their emplacement. It was ascertained, that the age of dolerites represents particular geological event proceeding independently of formation of Neoproterozoic Nersinsk gabbro-dolerite complex. The Sm-Nd isotope signature indicates that parent melt generated from the metasomatic lithosphere mantle.

Characterization of Phytoplankton-Derived Amino Acids and Tracing the Source of Organic Carbon Using Stable Isotopes in the Amundsen Sea.

We utilized amino acid (AA) and carbon stable isotope analyses to characterize phytoplankton-derived organic matter (OM) and trace the sources of organic carbon in the Amundsen Sea. Carbon isotope ratios of particulate organic carbon (δ13C-POC) range from -28.7‱ to -23.1‱, indicating that particulate organic matter originated primarily from phytoplankton. The dissolved organic carbon isotope (δ13C-DOC) signature (-27.1 to -21.0‱) observed in the sea-ice melting system suggests that meltwater contributes to the DOC supply of the Amundsen Sea together with OM produced by phytoplankton. A negative correlation between the degradation index and δ13C-POC indicates that the quality of OM significantly influences isotopic fractionation (r2 = 0.59, p < 0.001). The AA distribution in the Amundsen Sea (5.43 ± 3.19 µM) was significantly larger than previously reported in the Southern Ocean and was associated with phytoplankton biomass (r2 = 0.49, p < 0.01). Under conditions dominated by P. antarctica (DI = 2.29 ± 2.30), OM exhibited greater lability compared to conditions co-dominated by diatoms and D. speculum (DI = 0.04 ± 3.64). These results highlight the important role of P. antarctica in influencing the properties of OM, suggesting potential impacts on carbon cycling and microbial metabolic activity in the Amundsen Sea.

The Permian to late Triassic magmatic evolution of SW Pangea: Reconciling evidence from Patagonia and the Antarctic Peninsula

The geodynamic setting across the Paleozoic to Mesozoic transition in Patagonia and the Antarctic Peninsula (SW Pangea) has been strongly debated. Hypotheses of terrane accretion, episodes of shallower to flattened subduction, long-lived stages of crustal extension, or even subduction arrest have been variably proposed. We have compiled and re-evaluated the available whole-rock geochemistry and zircon Hf-isotope data for Permian to Triassic rocks from Patagonia and the Antarctic Peninsula, and compared these findings with the orogenic events in these regions.We have identified that two orogenic cycles occurred along the SW margin of Pangea during the Permian-Triassic interval, namely the Gondwanide and Chonide/Peninsula orogenies. Both orogenies coexisted with the development of magmatic arcs; the Permian arc exhibits an overall I-type signature that switched to A-type towards ca. 252 Ma, whereas the Triassic arc has an S-type signature in the Antarctic Peninsula and intraplate features in Patagonia. The Hf isotope data for zircon exhibit broadly subchondritic values, suggesting significant crustal contribution in the magmatic source during both cycles. The short- and long-term temporal behavior of the isotopic trends suggests variations that may be attributable to the participation of primitive and/or evolved sources. We conclude that the geochemical and isotopic signatures of the magmas, together with different styles of crustal deformation, resulted from the interaction of the upper and lower plates, consistent with the evolution of an accretionary-type margin along SW Pangea during Permian and Triassic times.

Global mantle perturbations following the onset of modern plate tectonics.

Plate tectonics drives the compositional diversity of Earth's convecting mantle through subduction of lithosphere. In this context, the role of evolving global geodynamics and plate (re)organization on the spatial and temporal distribution of compositional heterogeneities in the convecting mantle is poorly understood. Here, using the geochemical compositions of intracontinental basalts formed over the past billion years, we show that intracontinental basalts with subchondritic initial neodymium-144/neodymium-143 values become common only after 300 million years, broadly coeval with the global appearance of kimberlites with geochemically enriched isotopic signatures. These step changes in the sources of intraplate magmatism stem from a rapid increase in the supply of deeply subducted lithosphere during the protracted formation of Pangea following the widespread onset of "modern" (cold and deep) subduction in the late Neoproterozoic. We argue that the delay (~300 million years) in the appearance of enriched intraplate magmas reflects the time required for the sinking and (re)incorporation of slabs into the sources of mantle-derived magmas.

Unravelling different mechanisms of metasomatism and geodynamic evolution of pyroxenite-veined subcontinental lithospheric mantle beneath the Central European Variscides

Abstract Pyroxenite-veined garnet peridotites from the Gföhl Unit of the Moldanubian Zone in the Bohemian Massif provide direct constraints on diverse mechanisms of mantle metasomatism and refertilization driven by a single pulse of melt beneath the Central European Variscides. Here, we provide a detailed study on an intriguing example of this rock association where the garnet peridotites show a fertile character (high Al2O3, CaO, TiO2), corresponding to the subcontinental lithospheric mantle (SCLM). By contrast, their conspicuous LREE depletion and Sr–Nd isotopic signatures (87Sr/86Sr338 ≤ 0.7028; εNd338 ~7.3) are typical of depleted mantle residue after melt extraction. Such signatures reflect transformation of an original refractory protolith (likely harzburgite) to fertile lherzolite through percolation of primitive tholeiitic melts, parental to garnet pyroxenite in veins. The SCLM refertilization is further documented by the whole-rock positive correlation between incompatible elements (Zr, Yb, Sc, V), and trace element composition of clinopyroxene (high Ti/Eu and Ti/Nb) and garnet (elevated ∑REE, Zr, Ti). Trace element and Sr–Nd isotopic systematics of pyroxenites (87Sr/86Sr338 ~0.7025–0.7029; εNd338 ≤ 7.9) correspond to a source of melt similar to the depleted MORB mantle (DMM). Three mechanisms of metasomatism related to the interaction of this melt with the host peridotites were distinguished: (i) stealth metasomatism, reflected by extensive clinopyroxene and garnet crystallization in lherzolite adjacent to pyroxenite veins, (ii) cryptic metasomatism, recorded by lower Mg# values of orthopyroxene and olivine in lherzolite, and (iii) modal metasomatism, resulting in crystallization of amphibole and phlogopite in lherzolite close to the veins. The percolating basaltic melt was hydrous, moderately enriched in fluid-mobile elements (Cs, Rb, Ba, Pb, U, Li). Immiscible liquids, dense Ti-Mg-Fe-rich oxide melt and C-O-H fluid, trapped and crystallized as mono/multiphase solid inclusions in garnet, likely separated from a basaltic melt upon cooling. The lherzolite-pyroxenite interface reveals strong micro-scale element fractionation due to differentiation of a basaltic melt within the percolation channel. Volatile-bearing liquids that segregated from the melts migrating through wall-rock peridotites most likely caused chromatographic enrichment in highly incompatible elements (e.g. LREE) in distal peridotites relative to the LREE-depleted lherzolites adjacent to the veins. The DMM-like affinity of pyroxenites and pressure-temperature estimates for lherzolite (3.9–5.4 GPa/1010–1200 °C) and pyroxenites (2.8–4.2 GPa/860–1020 °C) point towards exhumation-driven SCLM refertilization. This was linked to decompression-induced partial melting of upwelling asthenosphere producing basaltic melts penetrating through and metasomatizing the SCLM beneath the Variscan orogenic belt in Central Europe.

Palaeogeographical and eodiagenetic settings of host‐replacing phreatic calcrete intervals developed in mud deposits of the Famennian Kinnesswood Formation in the Pennyseorach Subbasin of south‐west Scotland

ABSTRACTIn the Pennyseorach Subbasin of south‐west Scotland, the Famennian Kinnesswood Formation of the Inverclyde Group includes several, ca 1 to 3 m thick erosional remnants of host‐replacing phreatic calcrete hardpans developed in mud deposits. The latter are most unusual hosts for such calcretes due to their relative impermeability, which would normally prevent them from sufficiently accommodating the circulation of an aquifer. In previously documented phreatic calcretes, mud deposits clearly acted as aquicludes that sharply constrained calcrete development. In the Kinnesswood Formation at Pennyseorach, tall desiccation fissures allowed groundwater to circulate in thick, semi‐consolidated mud deposits. Because of the inferred development of an adjacent evaporitic basin, the mixing of fresh and evaporitic groundwaters raised the pH enough for the replacement of phyllosilicates by calcite to occur along the fissure walls, forming ‘fissure calcretes’. The latter gradually expanded and eventually coalesced into mature, ‘columnar host‐replacing phreatic calcrete hardpans’ in which 90 to 100% of the muddy host material was replaced by calcrete. At Pennyseorach, host‐replacing phreatic calcrete hardpan formation not only affected the transition zone between the Doughend Sandstone and Foul Port Members of the Kinnesswood Formation (the Dunagoil Calcrete interval), as in other localities of south‐west Scotland, but also affected the uppermost part of the formation, which is marked by several erosion surfaces downcutting into columnar host‐replacing phreatic calcrete hardpan intervals in association with the episodic rise and fall of base‐level. These newly recorded host‐replacing phreatic calcrete hardpan intervals from the upper part of the Kinnesswood Formation have a tightly constrained stable isotopic signature that is distinct from that of both the Dunagoil Calcrete and the successive host‐replacing phreatic calcrete hardpans of the Visean Clyde Sandstone Formation within the same group, underlining their potential as stratigraphic markers and palaeoenvironmental indicators.

Assessing Human Iron Kinetics Using Stable Iron Isotopic Techniques.

Stable iron isotope techniques are critical for developing strategies to combat iron deficiency anemia, a leading cause of global disability. There are four primary stable iron isotope methods to assess ferrokinetics in humans. (i) The fecal recovery method applies the principles of a metabolic balance study but offers enhanced accuracy because the amount of iron isotope present in feces can be directly traced back to the labeled dose, distinguishing it from endogenous iron lost in stool from shed intestinal cells. (ii) In the plasma isotope appearance method, plasma samples are collected for several hours after oral dosing to evaluate the rate, quantity, and pattern of iron absorption. Key metrics include the time of peak isotope concentration and the area under the curve. (iii) The erythrocyte iron incorporation method measures iron bioavailability (absorption and erythrocyte iron utilization) from a whole blood sample collected 2 weeks after oral dosing. Simultaneous administration of oral and intravenous tracers allows for separate measurements of iron absorption and iron utilization. These threemethods determine iron absorption by measuring tracer concentrations in feces, serum, or erythrocytes after administration of a tracer. In contrast, (iv) in iron isotope dilution, an innovative new approach, iron of natural composition acts as the tracer, diluting an ad hoc modified isotopic signature obtained via prior isotope administration and equilibration with body iron. This technique enables highly accurate long-term studies of iron absorption, loss, and gain. This review discusses the application of these kinetic methods and their potential to address important questions in hematology andiron biology.

Hidden deep sulfide cumulates beneath the Jinchuan Ni−Cu−platinum-group element deposit (China) inferred from Ni−Cu isotopes

The mechanisms that concentrated metals in the world’s single largest nickel−copper−platinum-group element (Ni−Cu−PGE) sulfide deposit, the Jinchuan deposit in northwestern China, remain enigmatic. Nickel and Cu isotopes are novel isotopic systems that may fill this knowledge gap as they are major constituents of sulfide melt, the main carrier of economically important metals. Sulfide ores in the Jinchuan deposit are characterized by systematically high δ60/58Ni and δ65Cu values, which are positively correlated (r2 = 0.84), and show well-defined correlations with PGEs, S, Ni, and Cu contents, and Ni/Pd, Cu/Pd, and Pd/Ir ratios. The isotopic signatures can be best explained by the early segregation of sulfide melt at depth prior to ascent of the parental magmas, storing isotopically light Ni and Cu in deep magma chambers. Subsequent sulfide melt segregation and fractionation in shallow portions of the magmatic conduit generated the currently explored sulfide ores, with heavy and positively correlated Ni−Cu isotopic signatures. Therefore, hidden deep orebodies are promising targets for further exploration beneath the Jinchuan deposit.

Elucidating the Fate of the Organochlorine Pesticide Chlordecone under Abiotic Reductive and Oxidative Processes: Kinetics, Transformation Products, and C vs Cl Isotope Fractionation.

Pollution of French West Indies (FWI) soils by the organochlorine pesticide chlordecone poses environmental and societal concerns due to its long-term persistence. Assessing chlordecone degradation remains challenging due to analytical constraints to identify transformation products. Here, multielement compound-specific isotope analysis (ME-CSIA) was used to identify changes in stable isotope signatures of chlordecone produced during abiotic transformation reactions under reducing and oxidative conditions. Effective chlordecone transformation was shown in reactions with zerovalent iron (ZVI), vitamin B12 and sodium sulfide (VSS), alkaline ascorbic acid (AA), and sodium persulfate activated by microwave irradiation (MWPS). Significant enrichment of 13C and 37Cl was observed in all abiotic reactions, with εC,bulk and εCl,bulk values ranging from -4.3 ± 0.4‰ to -2.3 ± 0.2‰ and from -2.6 ± 0.4‰ to -1.3 ± 0.3‰, respectively. Distinct mechanisms were evidenced in dual isotope plots, resulting in Λ values of 1.17 ± 0.28 for ZVI, 1.26 ± 0.50 for VSS, 2.06 ± 0.30 for AA, and 2.90 ± 0.50 for MWPS. Two major products were formed, 10-monohydrochlordecone and 8-monohydrochlordecone. Cl-CSIA data suggested that the first Cl substitution at the C10-position likely produced secondary Cl isotope effects (via nucleophilic substitution). Overall, results suggest that ME-CSIA can help quantify in situ chlordecone degradation, distinguishing between different ongoing degradation mechanisms and fingerprinting pollutant sources from chlordecone formulations (Curlone).

Magnesite hosted by the Neoarchean ultramafic rocks in Attappadi, southern India: Insights from spectral and stable isotope investigation

Magnesite is an economically important mineral commonly found in ultramafic complexes worldwide, primarily in Archean to Proterozoic ultramafic complexes. This study focuses on the chemical and spectral characterization of magnesite found in the Neoarchean ultramafic rocks in the Attappadi region in the Southern Granulite Terrane of southern India. The research utilizes x‐ray diffraction analysis, hyperspectral, laser Raman, Fourier Transform Infrared, and Isotope Ratio Mass Spectrometry. The studied ultramafic rocks are part of a well‐exposed ophiolitic suite known as the Agali ophiolitic complex. Magnesite primarily occurs as veins, veinlets, and lenses within weathered ultramafic rocks. The hyperspectral analysis of the magnesite samples shows absorption bands in the shortwave infrared region, particularly around 2.3 and 2.5 μm, which correspond to the stretching and bending of the CO bond in the (CO3)2− ion in MgCO3. The laser Raman spectra show intensity peaks at 1095, 738, and 330 cm−1, which may be attributed to the translational and librational vibrations. The Fourier transform infrared data reveal transmittance at 1434, 880, and 747 cm−1, corresponding to MgO bond stretching and asymmetrical CO stretching. The x‐ray powder diffraction spectra exhibit diffraction peaks at 32°, 35°, 42°, 46° and 53°, characteristic of pure magnesite. The spectroscopic parameters derived from various analyses indicate that the magnesite is high quality and free from gangue minerals. Stable isotope analysis of the magnesite samples yielded δ13C values ranging from −5‰ to −9‰ and δ18O values in the range of 21‰–25‰. The estimated water temperature from which the magnesite has been precipitated is ~59 ± 3.9°C. Based on the field relations, mode of occurrence and isotopic signatures, the mineralization is considered to have been formed by the low‐temperature alteration of ultramafic rocks facilitated by CO2‐rich fluids in the near‐surface environment. This study compares the characteristics of magnesite from the study area with a few Neoproterozoic serpentinite‐hosted magnesite veins in the ophiolitic sequence of the Egyptian Eastern Desert, which is part of the Arabian Nubian shield. The research aims to contribute to understanding magnesite formation in Archaean to Proterozoic mafic–ultramafic rocks on the Earth's crust. It also provides insights into the geological processes that govern the genesis of ultramafic‐hosted magnesite globally, particularly in East Gondwana fragments. This information can enhance mineral exploration and resource evaluation in these regions, helping to identify economic prospects and assess the feasibility of magnesite resource extraction and utilization in East Gondwana fragments.

Quantifying free tropospheric moisture sources over the western tropical Atlantic with numerical water tracers and isotopes

AbstractTropical free‐tropospheric humidity plays a crucial role for the Earth's radiative balance and climate sensitivity. In addition to atmospheric humidity, stable water isotopes can provide important information about the hydrological cycle. We use the isotope‐ and water tagging‐enabled version of the COSMOiso model to determine isotopic fingerprints of diagnosed moisture pathways over the western tropical Atlantic (WTA). A convection‐permitting, high‐resolution (5 km) nudged simulation is performed for January–February 2020. During this period, the target region is characterized by alternating large‐scale circulation regimes with different humidity and isotope signatures. Moist conditions in the middle troposphere (300–650 hPa) are associated with moisture transport from the south, east, southeast, as well as evaporation from the North Atlantic, while dry conditions correspond to extratropical transport from the north and west. To predict the contribution of different moisture sources, we used a statistical model based on the local specific humidity and temperature as predictors and obtained an R‐squared (R2) of 0.52. Adding water isotopes improved the prediction (R2 = 0.73), showing that isotopes provide unique information on moisture sources and transport patterns beyond conventional local observations.

To pretreat, or not to pretreat, that is the question. The value of pretreatment protocols in the stable carbon and nitrogen isotope analysis of archaeobotanical cereal grains from Croatia and Serbia

ABSTRACT Isotopic analysis of archaeological charred plant remains is a useful tool to infer past agricultural practices. However, debate continues over whether charred seeds should be untreated or pretreated before analysis, to counteract any residual contamination and retrieve the “true” isotopic signature of the seed. This paper presents a case study examining whether archaeobotanical remains from Croatia and northern Serbia should be pretreated before isotopic analysis with the aim to provide a pragmatic technique for wider application. A small subset was first examined with an ATR-FTIR and then four different protocols were examined: water rinse only, two different acid-only methods and ABA (acid–base-acid). The results were inconsistent, displaying variability in the effect each protocol had on the isotopic values. Overall, it was concluded that the slight differences between untreated and pretreated sub-samples should not impact the archaeological interpretation, removing the need for pretreatment of the remaining archaeobotanical material.

Isotopic study for evaluating complex groundwater circulation patterns, hydrogeological zoning, and water-rock interaction in a Mediterranean coastal karst environment

In this study groundwater provenance, circulation, and rock interaction processes have been assessed by cross processing the spatial distribution of chemical and isotopic signatures in freshwater with the hydrogeological features of the coastal karst carbonate aquifer of Murgia, located in the southeastern end of Italy, along the Adriatic Sea. Thanks to widespread groundwater quality monitoring (major, minor, and trace-element analyses) and multi-isotopic measures of O, H, Sr, and B, some assumptions about complex groundwater circulation patterns, hydrogeological zoning, and water-rock interaction have been drawn. Three sectors have been distinguished into the Adriatic side of the Murgia aquifer all fed by two main recharge areas located on the most elevated, inner side of the aquifer. Each sector is characterized by different groundwater circulation patterns, residence time, and hydrogeochemical features. The water samples collected into the western sector evidence a certain degree of water-rock interaction, which allows us to assume long groundwater flow paths and residence time. On the contrary, the eastern sector of Murgia has been proven to be characterized by short residence times and a possible direct freshwater contribution even in the downstream course due to the massive presence of karst forms. Herein, the isotopic analysis of the water samples does not provide evidence of water-rock interaction. Finally, in the third, central sector, water infiltrated at different locations mixes flowing through relatively long paths even though not sufficient to allow groundwater to gain the rock's isotopic signature.

Primitive asteroids as a major source of terrestrial volatiles.

The origins of Earth's volatiles are debated. Recent studies showed that meteorites display unique mass-independent isotopic signatures of the volatile element Zn, suggesting that Earth's Zn originated from materials derived from different regions of the Solar System. However, these studies largely omitted meteorites from the differentiated planetesimals thought to represent the Earth's building blocks, which underwent melting and substantial volatile loss. Here, we characterize the mass-independent Zn isotope compositions of meteorites from such planetesimals. We incorporate these results in mixing models that aim to reproduce Earth's abundance and isotope compositions of Zn and other elements. Our results suggest that, while differentiated planetesimals supplied ~70% of Earth's mass, they provided only ~10% of its Zn. The remaining Zn was supplied by primitive materials that did not experience melting and associated volatile loss. Combined with other findings, our results imply that an unmelted primitive material is likely required to establish the volatile budgets of the terrestrial planets.

Origin and preservation mechanisms of organic matter in carbonate concretions from Lower Cambrian black shales in South China

Carbonate concretions are widely used in paleoclimate, paleoenvironmental, and paleontological studies, and even in the study of potential life on Mars. These petrological, elemental, isotopic, and lipid biomarker signals in Meso-Cenozoic carbonate concretions (relatively low thermal maturity) can effectively preserve details of seawater conditions and benthic ecosystems during the deposition of their host sediments/rocks. However, such research on Precambrian-Cambrian carbonate concretions under highly mature conditions remains scarce, and the ability of these ancient carbonate concretions to retain their original biogenic information remains uncertain. To achieve that, this study examines two Cambrian carbonate concretions, using samples from the center, transition, and rim of each, and their adjacent host black shales from the Lower Cambrian Qiongzhusi Formation in the Yangtze Block, South China. Organic and inorganic geochemical analyses were combined to elucidate the origin and preservation process of organic matter (OM) in these ancient Cambrian carbonate concretions. The results show that the thermal maturity of OM within these concretions (1.8 % EqVRo) is relatively low compared to their adjacent host shales (2.9 % EqVRo). Hopanes and steranes are detectable in both free and calcite-occluded hydrocarbons within these concretions, with concentrations of individual compounds ranging from 0.001 to 0.800 μg/g TOC, whereas kerogen-bound hydrocarbons lack detectable biomarkers. The results indicate that the two Cambrian carbonate concretions were formed mainly within the iron reduction and bacterial sulfate reduction zones, extending to depths of 10 to 38 m below the sediment-water interface. The OM within these concretions mainly inherited the initial unaltered signature of OM from the Qiongzhusi host shale. The carbonate concretions protected the internal OM from further thermal and secondary (e.g., biodegradation) alteration processes and might also prevent the formation of the conventional macromolecular skeletal kerogen manifested by the absence of bound biomarkers. The biomarkers, in both free and occluded forms, in the Cambrian carbonate concretions still retained their original source information, providing valuable insights into ancient biogeochemical processes during sediment burial and ancient seawater chemistry during the early Cambrian.

Effects of urbanization on diet in eastern chipmunks (Tamias striatus) as determined by stable isotopes

Urban environments offer wildlife a consistent supply of anthropogenic food waste, divergent from natural food sources in nutrient composition. This study investigates the dietary impact of urbanization on eastern chipmunks (Tamias striatus (Linnaeus, 1758)) by analyzing stable isotope signatures (∂13C and ∂15N) in their hair. The hypothesis posits that chipmunks in urban locales consume more corn-based and high-protein foods, reflected in elevated isotopic signatures compared to their rural counterparts. Sampling encompassed 20 sites across Sudbury, Ontario, varying in urbanization levels. Urbanization was gauged via surveys capturing human activity and sources of anthropogenic food waste. Contrary to expectations, chipmunks did not exhibit δ13C signatures indicative of substantial corn consumption from human food waste. However, δ15N signatures positively correlated with urbanization, suggesting heightened animal protein intake in urban habitats. Elevated δ15N signatures may also result from the use of fertilizers in urban areas . Future avenues involve using stable isotope mixing models to pinpoint dietary sources and exploring the health and reproductive ramifications of urban diets, including effects on gut microbiome composition.

Marine clay maturation induces systematic silicon isotope decrease in authigenic clays and pore fluids

Marine silicate alteration exerts a major influence on marine carbon and cation cycles, but has proven difficult to quantify. In this context, silicon isotopes of marine pore fluids became an important tracer. However, poorly constrained silicon isotope signatures of precipitates produced during silicate alteration (i.e. authigenic clays) remain a major source of uncertainty. Here we present in situ silicon isotope analyses of marine authigenic clays (intergrown iron-smectites and iron-glauconites) occurring within recent sediments from the Oregon margin, eastern North Pacific. We identify a trend to lower silicon isotopes (from −2.24‰ to −3.17‰), accompanied by decreasing aluminum/silicon ratios and increasing potassium oxide contents, which we interpret as an isotopic shift caused by progressive clay maturation via dissolution-reprecipitation reactions. Our modelling suggests that this clay maturation pathway, together with mixing of other fluid sources, may induce pore fluid silicon isotope shifts of up to −1.7‰, if sufficient newly precipitated clays are re-dissolved. This could potentially produce silicon isotopes values significantly lower than seawater and implies that conventional isotope-based approaches underestimate the prevalence of marine silicate alteration. Our findings highlight that clay maturation must be considered when interpreting silicon isotope signatures in terms of marine silicate alteration and upscaling to global element cycles.