Metal Stable Isotope Research Articles

Low-Consumption and High-Efficiency Isotope Analysis by Microultrasonic Single-Droplet Nebulization Sampling Multicollector Inductively Coupled Plasma Mass Spectrometry.

Metal stable isotopes are increasingly applied in various fields, including planetary science and medical research, highlighting the need for isotope analysis methods capable of handling precious and microvolume samples. This study introduces a novel, low-consumption, high-efficiency isotope analysis method using MC-ICP-MS based on microultrasonic single-droplet nebulization (MUSDN). The proposed MUSDN enables the complete nebulization of microliter-sized droplets, delivering high-sensitivity transient analytical signals with a duration of several seconds. Under optimized conditions, MUSDN exhibited significantly enhanced sensitivity compared to conventional pneumatic nebulization, achieving 17-fold and 12-fold improvements for 7Li and 63Cu, respectively. The achieved external precisions (2SD) for δ7Li and δ65Cu were 0.3 and 0.08‰, with single analysis consuming only 1 ng of Li and 2 ng of Cu, respectively. This represents a reduction in sample consumption by 1-2 orders of magnitude compared to conventional PN-MC-ICP-MS while also improving the analysis speed by at least 10-fold due to rapid residual washout. Furthermore, our method demonstrated superior δ65Cu analytical precision compared to other high-sensitivity transient analysis methods (0.19‰ with a laser ablation system) with similar sample consumption. Finally, the accuracy of the proposed method was validated through the analysis of geological CRMs, serum CRMs, in-house standard samples, and a series of real serum samples. This novel isotope analysis method provides a promising approach for isotope applications involving precious and microvolume samples.

Mesoarchean Microbial Cd, Ba, and Ni Cycling: Evidence for Photosynthesis in Pongola Group Stromatolites through Novel Stable Isotopes and High-Resolution Trace Element Maps.

Nontraditional stable isotopes of bioactive metals emerged as novel proxies for reconstructing the biogeochemical cycling of metals, which serve as cofactors in major metabolic pathways. The fractionation of metal isotopes between ambient fluid and microorganisms is ultimately recorded in authigenic minerals, such as carbonates, which makes them potentially more reliable than standard biomarkers in organic matter. Stromatolitic carbonates are geochemical archives that allow for the study of the long-term interplay of the biosphere, atmosphere, and hydrosphere through deep time, with the unique potential to investigate early life environments and the evolution of the metallome. The present study uses stromatolites from the ∼2.95-billion-year-old Pongola Supergroup (S. Africa) as a field laboratory for combined in situ trace metal mapping and layer-specific, novel stable metal isotope compositions to infer early Earth microbial metal cycling via phototrophic and chemo-litho-autotrophic metabolisms. Quantitative in situ trace element maps reveal intrinsic biosedimentary enrichments of nickel (Ni), cadmium (Cd), phosphorus (P), iron (Fe), and manganese (Mn) in stromatolitic laminae. In contrast, barium (Ba) shows a more homogeneous distribution. Authigenic carbonates from pristine stromatolite laminae show distinct δ138Ba and δ112Cd fractionation above detrital background and bulk silicate Earth values, but opposing correlation with trace metal concentrations. Authigenic δ60Ni values overlap with Mesoarchean diamictite compositions. Nickel isotopic compositions in authigenic stromatolitic carbonates, potentially a new proxy for methanogenic metal uptake, do not show any proof of the presence of this metabolism in the samples of this study. Meanwhile, Cd isotopic compositions in authigenic carbonates follow typical Rayleigh-type isotope fractionation; that is, the isotopic composition of Cd evolves to heavy values close to modern surface compositions. Correlations of δ112Cd with the micronutrients copper (Cu), molybdenum (Mo), and P, at positively fractionated carbon (C) isotopes (δ13C ∼+2‰), argue for active photosynthesis in the Pongola microbial habitat. We show that Ba isotopes can be used to infer carbonate precipitation rates similar to modern microbial carbonates. Thus, the combination of Cd and Ni isotopes has the unique potential as novel isotope biomarkers for the biochemical sedimentary record of early Earth where traditional lipid biomarkers are not applicable due to the incomplete preservation of organic matter. Key Words: Early life-Stromatolites-Novel stable isotopes-Cadmium isotopes-Nickel isotopes-Barium isotopes-Trace element mapping.

Metal Isotopes in Mammalian Tissues

Ecologists rely on a wealth of data, including field observations and light stable isotopes, to infer dietary preferences and other ecological and physiological properties in living mammals. But inferring such important traits (e.g., trophic position, metabolism, pathologies) in extinct animals, including humans, can be challenging because biological processes rarely mirror morphology as preserved in the fossil record. For instance, dietary behavior does not necessarily reflect tooth morphology. As an additional challenge, some isotopic mammal tissues commonly used in modern ecology, such as collagen in bone or dentin or keratin from hair, hoof, or horn, do not generally preserve in fossil remains older than ∼200 kyr. In contrast, major constituents of bioapatite often retain their initial isotopic composition through fossilization processes. Recent analytical developments in mass spectrometry now allow, using small samples, for assessment of isotopic variability of major and trace elements such as calcium or zinc. Here, we review the application potentials of metal (nontraditional isotopes) for (paleo)ecological, (paleo)physiological, and (paleo)mobility inferences as applied to mammalian research. ▪ Mammals are key elements of modern ecosystems and possess a rich evolutionary history, yet inferences about their past ecologies and physiologies are challenging to retrieve using traditional geochemical toolkits. ▪ Metal stable isotopes provide a novel and complementary approach to unveil paleoecological and paleophysiological characteristics of extinct mammal species. ▪ Within a 20-year time frame, the core of metal isotopic data in mammalian research remains small compared to traditional isotopic systems (C, O, N), which is inviting for designing cost-effective instrumentation and increasing dissemination across scientific disciplines.

Imbalances in Dissolved Elemental Export Fluxes Disclose “Hidden” Critical Zone Compartments

AbstractIn streams, short‐term element‐specific solute fluxes are often not balanced with long‐term chemical weathering fluxes determined in the residual solids from fractional element loss and denudation rate. The ratio of both estimates—the “Dissolved Export Efficiency” (DEE)—is frequently <1, indicating deficits in the stream dissolved load. To explore the cause of the stream deficits, we performed a daily water sampling campaign for one year in a forested headwater watershed in Southern Germany. We sampled surface runoff, above‐canopy and below‐canopy precipitation, subsurface flow from the organic soil layer, upper, and deep mineral soil, and groundwater. Regolith samples were obtained from a drill core and revealed the weathering front to lie between 7 and 15 m depth. We found a DEE < 1 for K, Si, Al, Fe. These elements are characterized by shallow slopes in C‐Q relationships, and the imbalances were found to originate in the deep saprolite. Their export pathway potentially includes “hidden” Critical Zone compartments or fluxes, presumably unsampled colloids that are exported preferentially during rare flushing events with stochastic temporal distribution. The DEE of nutritive elements like Ca, Mg, and P is also <1. These elements are characterized by steeper C‐Q slopes, and their imbalance can be explained by deep nutrient uptake followed by nutrient retainment in re‐growing forest biomass or export in plant debris. The collective evidence for these imbalances, including previous evidence from metal stable isotopes, suggests that the deep Critical Zone represents the location for chemical or biogenic retention and release of solutes.

Sphalerite Records Cd Isotopic Signatures of the Parent Rocks in Hydrothermal Systems: A Case Study From the Nayongzhi Zn–Pb Deposit, Southwest China

AbstractMetal stable isotopes (e.g., Zn, Cd, and Cu) have been used to track metal sources in different types of hydrothermal systems. However, metal isotopic variations in sulphides could be triggered by various factors such as mineral precipitation and fluid mixing. Thus, tracking the metal sources of hydrothermal systems is still a big challenge for metal isotopes. In this study, we investigated the Cd isotopic systematics of sphalerite from the Nayongzhi Zn–Pb deposit, which is a Mississippi Valley‐type (MVT) deposit in the Sichuan–Yunnan–Guizhou mineralization province (SYGMP). We reinterpreted the published S isotope data for the SYGMP and found that the large S isotopic variations were controlled by Rayleigh fractionation between sulphide and reduced S. As such, a model that involves mixing of a metal‐rich fluid with a reduced S pool formed by thermochemical sulfate reduction (TSR) can explain the ore formation in the Nayongzhi deposit. Based on this model, no Cd isotopic fractionation was observed due to its low solubility in fluids during mixing, and thus the Cd isotopic variations of sphalerite were inherited from the source rocks. The large range of Zn/Cd ratios and uniform Cd isotopic compositions of the sulphides are similar to those of igneous rocks but different from those of sedimentary rocks, indicating that Zn and Cd were derived mainly from basement rocks (e.g., migmatite, gneiss, and granulite). Our results reaffirm that metal stable isotopes, particularly Cd isotope compositions of sphalerite, are powerful geochemical tracers for investigating the formation mechanisms of ore deposits.

The composition and differences of antimony isotopic in sediments affected by the world's largest antimony deposit zone

Antimony (Sb) isotopic fingerprinting is a novel technique for stable metal isotope analysis, but the use of this technique is still limited, especially in sediments. In this study, the world's most important Sb mineralization belt (the Xikuangshan mineralization belt) was taken as the research object and the Sb isotopic composition and Sb enrichment characteristics in the sediments of water systems from different Sb mining areas located in the Zijiang River (ZR) Basin were systematically studied. The results showed that the ε123Sb values in the sediments of the ZR and its tributaries, such as those near the Longshan Sb-Au mine, the Xikuangshan Sb mine, and the Zhazixi Sb mine, were 0.50‒3.13 ε, 2.31‒3.99 ε, 3.12‒5.63 ε and 1.14‒2.91 ε, respectively, and there were obvious changes in Sb isotopic composition. Antimony was mainly enriched in the sediments due to anthropogenic sources. Dilution of Sb along the river and adsorption of Sb to Al-Fe oxides in the sediment did not lead to obvious Sb isotopic fractionation in the sediment, indicating that the Sb isotopic signature was conserved during transport along the river. The Sb isotopic signatures measured in mine-affected streams may have differed from those in the original Sb ore, and further investigation of Sb isotopic fingerprints from other possible sources and unknown geochemical processes is needed. This study reveals that the apparent differences in ε123Sb values across regions make Sb isotopic analysis a potentially suitable tool for tracing Sb sources and biogeochemical processes in the environment.

Metals Could Reveal Corals’ Past Lives

Examining the role of stable metal isotopes in biological activities such as photosynthesis provides a promising new avenue of research into how coral responds to environmental stressors.

A Perspective on Probing Coral Resilience to Climate and Environmental Changes Using Stable Isotopes of Bio‐Utilized Metal Elements

AbstractIn the face of diverse challenges like global warming, ocean acidification, and human activities, the world's coral reefs are confronting a severe ecological crisis. Understanding the historical coevolution of corals with their environment and their resilience to current climate change is crucial for protecting these ecosystems and predicting their future. In this context, metal stable isotopes in corals present a novel and alternative methodology. Their significant fractionation during coral biological processes, persistent presence in coral skeletons, and relatively straightforward sources make them a valuable tool. However, the complexity of coral biology necessitates a deeper investigation into the fundamental mechanisms behind the isotopic fractionation of these biologically utilized metal elements. A comprehensive and systematic study of the roles of metal stable elements in coral biological processes is essential. This includes examining the fractionation of metal isotopes across different parts of the corals, such as tissues, zooxanthellae, and skeletons. To achieve these goals, multidisciplinary collaborations are essential. They should focus on several key areas: interpreting metal stable isotopes data in the context of coral physiology and ecology; conducting controlled laboratory experiments on coral cultivation; engaging in comparative studies with inorganically precipitated aragonites; and developing a holistic understanding within the framework of coral biomineralization models.

Contrasted redox-dependent structural control on Fe isotope fractionation during its adsorption onto and assimilation by heterotrophic soil bacteria.

Despite the importance of structural control on metal stable isotope fractionation in inorganic and abiotic systems, the link between metal structural changes and related isotopic fractionation during reactions with organic surfaces and live cells remains poorly established. We conducted reversible adsorption of Fe(II) and Fe(III) on the surface of exopolysaccharide (EPS)-rich and EPS-poor Pseudomonas aureofaciens, and we allowed Fe intracellular uptake by growing cells. We analyzed the Fe isotopic composition of the remaining fluid and cell biomass, and compared the isotopic fractionation during adsorption and assimilation reaction with relative changes in Fe structural status between aqueous solution and bacterial cells, based on available and newly collected X-ray absorption spectroscopy (XAS) observations. Iron(III) adsorption onto P. aureofaciens at 2.8 ≤ pH ≤ 6.0 produced an enrichment of the cell surface in heavier isotopes with Δ57Fecell-solution ranging from +0.7 to +2.1‰, without a link to pH in EPS-rich cultures. In contrast, the magnitude of isotopic fractionation increased with pH in EPS-poor cultures. Iron(II) adsorption produced an even larger enrichment of the cell surface in heavier isotopes, by up to 3.2‰, tentatively linked to Fe(III) hydroxide precipitation. Intracellular assimilation of Fe(II) favored heavier isotopes and led to Δ57Fecell-solution of +0.8‰. In addition, Fe(III) cellular uptake produced an enrichment of the bacterial biomass in lighter isotopes with Δ57Fecell-solution of -1‰. The XAS analyses demonstrated the dominance of Fe(III)-phosphate complexes both at the cell surface and in the cell interior. We suggest that heavier isotope enrichment of the cell surface relative to the aqueous solution is due to strong Fe(III)-phosphoryl surface complexes and Fe complexation to ligands responsible for metal transfer from the surface to the inner cell. In case of Fe(II) adsorption or assimilation, its partial oxidation within the cell compartments may lead to cell enrichment in heavier isotopes. In contrast, loss of symmetry of assimilated Fe(III) relative to the aqueous Fe3+ ion and longer bonds of intracellular ions relative to aqueous Fe(III)-citrate or hydroxo-complexes could produce an enrichment of cells in lighter isotopes. The versatile nature of Fe(II) and Fe(III) fractionation without a distinct effect of pH and surface exopolysaccharide coverage suggests that, in natural soil and sedimentary environments, Fe isotope fractionation during interaction with heterotrophic bacteria will be primarily governed by Fe complexation with DOM and Fe redox status in the soil pore water.

Iron, Nickel, Copper, Zinc, and their stable isotopes along a salinity gradient in the Pearl River Estuary, southeastern China

Although the crucial role that dissolved trace metals (dTMs) play in both carbon cycling and climate have been revealed over the past three decades, much about the oceanic budgets of dTMs remains unknown. Rivers are one of the most important dTM sources to the ocean, and estuaries are a key interface between land and ocean. However, our understanding of how dTMs behave as they pass through the estuarine transition is limited, leading to uncertainties in estimating fluvial metal fluxes to the ocean and balancing oceanic dTM budgets. Alongside concentrations, metal stable isotopes offer an additional dimension to constrain estuarine processes, but data on metal isotopes in estuaries are scarce. Here we present dTM concentrations and their stable isotope ratios along a full salinity gradient in the Pearl River Estuary (PRE), southeastern China. Concentration data show a large apparent loss of dFe (86%) during estuarine mixing, moderate losses of dNi (13%) and dZn (36%), and nearly conservative behavior for dCu. However, examination of metal isotope data (δ56Fe, δ60Ni, δ65Cu, and δ66Zn) reveals more complex biogeochemistry, requiring either a two-stage scenario or a three-endmember mixing process. The two-stage process involves fractionation of dTM isotopes at low salinities, likely driven by particle adsorption and colloidal flocculation, followed by conservative mixing between intermediate-salinity estuarine waters and South China Sea waters. Alternatively, the three-endmember mixing process includes influences from riverine, oceanic endmembers, and external sources such as benthic flux and industrial activities, shaping dTM isotope distributions. Specifically, capturing δ56Fe fully proves challenging, yet it appears strongly influenced by inputs of benthic Fe within the PRE, characterized by dFe > 13 nmol kg−1 and δ56Fe < −0.80‰. δ60Ni and δ66Zn can be described by either two-stage or there-endmember mixing processes. In the former, the Rayleigh fractionation with αd-p of 1.00004 for δ60Ni and 1.0001 for δ66Zn, or the steady state fractionation with αd-p of 1.00005 for δ60Ni and 1.0002 for δ66Zn, could be derived to explain their patterns at low salinity, likely driven by colloidal flocculation. Additionally, a third source with dNi > 33 nmol kg−1 and δ60Ni > +1.26‰ and a third source with dZn > 13 nmol kg−1 and δ66Zn > +0.96‰, both influenced by human activities, could also shape the δ60Ni and δ66Zn patterns in the PRE, respectively. The description of δ65Cu is best achieved by a three-endmember mixing process, with the external source having dCu > 20 nmol kg−1 andδ65Cu < +1.3‰, indicative of processes like organic matter remineralization or discharge from wastewater treatment plant. Our study highlights the need for more extensive and detailed studies on estuarine settings to elucidate their potentially crucial role in global dTMs budgets.

Depth profile analyses by femtosecond laser ablation (multicollector) inductively coupled plasma mass spectrometry for resolving chemical and isotopic gradients in minerals

Abstract. Femtosecond laser ablation (fs-LA) coupled to a multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) instrument has been proven to be a powerful means to analyze isotope ratios of “non-traditional” stable isotope systems with high spatial resolution, precision, and accuracy. The technique has been successfully applied, e.g., to investigate diffusion-generated isotopic zoning of the elements Li, Mg, and Fe in magmatic crystals. Here, we present a novel sampling technique employing a fs-LA system that is equipped with a computer numerical control (CNC) laser stage, using the open-source software LinuxCNC. Combining this laser set up with ICP-MS or MC-ICP-MS allows us to perform depth profile analyses of major and trace elements, respectively, as well as metal stable isotope variations of Fe and Mg in olivine crystals and in experimental diffusion couples. Samples are ablated in circular patterns with profile diameters of 100–200 µm using a laser spot size of 25–30 µm. Depending on the scan speed and the repetition rate of the laser, each ablated sample layer is between 300 nm and 3.0 µm thick. The integrated signal of one ablated layer represents one data point of the depth profile. We have tested this technique by analyzing 5–50 µm deep depth profiles (consisting of 15–25 individual layers) of homogeneous and chemically zoned olivine crystal cuboids. The minor and trace element analyses of the zoned cuboids, conducted by fs-LA-ICP-MS, were compared with “horizontal” profiles analyzed in polished sections of the cuboids with electron probe microanalysis (EPMA). Furthermore, we analyzed Fe–Mg isotopic depth profiles of the same cuboids with fs-LA-MC-ICP-MS, of which the chemically zoned ones also showed isotopic zoning at identical scales. Isotopic depth profiles were also conducted on an unzoned olivine cuboid that was coated with a 26Mg- and 56Fe-enriched olivine thin film (of ∼ 800 nm) in order to investigate top-to-bottom contamination during depth profiling. Our results indicate that (i) concentration data acquired by fs-LA depth profiling match well with EPMA data, (ii) precise and accurate Fe and Mg isotopic data can be obtained (i.e., precision and accuracy are ≤ 0.12 ‰ and ≤ 0.15 ‰ for both δ26Mg and δ56Fe, respectively), and (iii) potential top-to-bottom contamination during depth profiling of isotope ratios can be avoided. The technique presented herein is particularly suitable for the investigation of minerals or glasses with chemical and/or isotopic gradients (e.g., diffusion zoning) vertical to planar surfaces. It can also be applied in materials sciences in order to analyze thin films, coatings, or surface contaminations on solids.

Contrasting copper concentrations and isotopic compositions in two Great Lakes watersheds

Copper (Cu) stable isotopes can elucidate the biogeochemical controls and sources governing Cu dynamics in aquatic environments, but their application in larger rivers and catchments remains comparatively scarce. Here, we use major and trace element hydrogeochemical data, Cu isotope analyses, and mixing modeling, to assess Cu loads and sources in two major river systems in Ontario, Canada. In both the Spanish River and Trent River catchments, aqueous hydrochemical compositions appeared reasonably consistent, but Cu concentrations were more variable spatially. In the Spanish River, waters near (historic) industrial mining activities displayed positive Cu isotope compositions (δ65CuSRM-976 between +0.75 ‰ and +1.01 ‰), but these signatures were gradually attenuated downstream by mixing with natural background waters (δ65Cu −0.65 ‰ to −0.16 ‰). In contrast, Trent River waters exhibited more irregular in-stream Cu isotope patterns (δ65Cu from −0.75 ‰ to +0.21 ‰), beyond the variability in Cu isotope signatures observed for adjacent agricultural soils (δ65Cu between −0.26 ‰ and +0.30 ‰) and lacking spatial correlation, reflective of the more diffuse sourcing and entwined endmember contributions to Cu loads in this catchment. This work shows that metal stable isotopes may improve our understanding of the sources and baseline dynamics of metals, even in large river systems.

Tightly coupled Ca-Zn-Sr isotope co-variations in basalts caused by recycled calcium carbonate in the mantle source

The deep carbon cycle requires tracers to understand carbon sequestration and mobility in the deep Earth. Recently, the use of metal stable isotopes has emerged as a promising and innovative approach to address element cycles, such as the use of magnesium and zinc isotopes to trace the magnesium carbonate cycle. However, despite the prevalence of calcium carbonate as the dominant sedimentary carbonate during the Phanerozoic era, its tracking through the use of metal stable isotopes has proven challenging. Here we show that deep subduction of Phanerozoic calcium carbonates can significantly decrease the δ44/40Ca value, while simultaneously increasing the δ66Zn value and 87Sr/86Sr ratio of the mantle. The Neogene Dalihu basalts in Inner Mongolia have high 87Sr/86Sr ratios, ranging from 0.7058 to 0.7063, which are positively correlated with Sr/Nd ratio, indicating the presence of sedimentary carbonate within their mantle source. The Dalihu basalts exhibit significantly lower δ44/40Ca values (0.51 to 0.70‰) but higher δ66Zn values (0.35 to 0.45 ‰) than the mantle. These low δ44/40Ca values cannot be attributed to partial melting, even when considering the jadeite effect. Our calculations indicate that adding 5–10% recycled calcium carbonate into the mantle source explains the high 87Sr/86Sr ratio and δ66Zn values but low δ44/40Ca values of the Dalihu basalt. Therefore, recycled calcium carbonate directly influences correlated Ca-Zn-Sr isotope variation, thereby providing compelling evidence for its role in the deep carbon cycle. Our findings suggest that combining metal stable isotopes with radiogenic Sr isotope is a powerful tracer of the deep carbon cycle.

Inductively Coupled Plasma Mass Spectrometry─A Valid Method for the Characterization of Metal Conjugates in View of the Development of Radiopharmaceuticals.

This study addresses the question whether inductively coupled plasma mass spectrometry (ICP-MS) can be used as a method for the in vitro and in vivo characterization of non-radioactive metal conjugates to predict the properties of analogous radiopharmaceuticals. In a "proof-of-concept" study, the prostate-specific membrane antigen (PSMA)-targeting [175Lu]Lu-PSMA-617 and [159Tb]Tb-PSMA-617 were compared with their respective radiolabeled analogues, [177Lu]Lu-PSMA-617 (PLUVICTO, Novartis) and [161Tb]Tb-PSMA-617. ICP-MS and conventional γ-counting of the cell samples revealed almost identical results (<6% absolute difference between the two technologies) for the in vitro uptake and internalization of the (radio)metal conjugates, irrespective of the employed methodology. In vivo, an equal uptake in PSMA-positive PC-3 PIP tumor xenografts was determined 1 h after the injection of [175Lu]Lu-/[177Lu]Lu-PSMA-617 (41 ± 6% ID/g and 44 ± 12% IA/g, respectively) and [159Tb]Tb-/[161Tb]Tb-PSMA-617 (44 ± 5% ID/g and 44 ± 5% IA/g, respectively). It was further revealed that it is crucial to use the same ratios of the (radio)metal-labeled and unlabeled ligands for both methodologies to obtain equal data in organs in which receptor saturation was reached such as the kidneys (12 ± 2% ID/g vs 10 ± 1% IA/g, 1 h after injection). The data of this study demonstrate that the use of high-sensitivity ICP-MS allows reliable and predictive quantification of compounds labeled with stable metal isotopes in cell and tissue samples obtained in preclinical studies. It can, hence, be employed as a valid alternative to the state-of-the-art γ-counting methodology to detect radioactive ligands.

Seasonal Mg isotopic variation in the middle Yellow River: Sources and fractionation

In order to better understand how stable metal isotope signals in large rivers can be used to constrain present and past weathering, the seasonal riverine MgSr isotopic pattern in the middle Yellow River was systematically investigated based upon weekly collected samples for the whole year of 2013. The results demonstrate that Mg is mainly transported in the dissolved form (65%) in this river system and that 45% of the total dissolved Mg is transported during the monsoon seasons, with 2% exported over 4 days during a single storm event. Dissolved Mg in the middle Yellow River is dominantly derived from both silicate and carbonate (82–89%) in this semi-arid region, with limited evaporite contribution (∼7%). Lithological mixing is the first order control on riverine dissolved Mg and Sr isotopes, with a contribution from ∼40% carbonate dissolution and ∼ 60% from silicate dissolution in the dry seasons, and ∼ 50% carbonate and ∼ 50% silicate during the monsoon seasons according to δ26Mg signals. Furthermore, a significant role of prior calcite precipitation (PCP) can be quantified, which fractionates Mg isotopes by about 0.17‰ to 0.39‰ positively depending on the choice of elemental and isotope partition of Mg in secondary carbonates. Clay formation following the PCP further fractionates riverine Mg isotopes to the negative side. An ∼0.2‰ decrease of riverine Mg isotopes is attributable to (1) a single storm event causing carbonate dissolution and (2) delayed delivery of depleted waters to rivers (∼3 months after the storm event) because of subsurface hydrological circulation. Annually, the weighted average riverine δ26Mg (−1.05‰) in the middle Yellow River is identical to the global average (−1.09‰). Despite the significant impact of lithology on the riverine dissolved Mg isotope signature, the mixing proportions of different Mg sources remain virtually constant, even when there are huge contrast of temperature, hydrology, and precipitation seasonally along the year, providing a basis for dissolved δ26Mg response to climatic forcing on the continental scale. This means that significant changes in the sedimentary Mg isotope records would reflect extreme conditions in deep time.

Exploring the K isotope composition of Göttingen minipig brain regions, and implications for Alzheimer's disease.

Natural stable metal isotopes have shown utility in differentiation between healthy and diseased brain states (e.g. Alzheimer's disease, AD). While the AD brain accumulates some metals, it purges others, namely K (accompanied by increased serum K, suggesting brain-blood transferal). Here, K isotope compositions of Göttingen minipig brain regions for two AD models at midlife are reported. Results indicate heavy K isotope enrichment where amyloid beta (Aβ) accumulation is observed, and this enrichment correlates with relative K depletion. These results suggest preferential efflux of isotopically light K+ from the brain, a linkage between brain K concentrations and isotope compositions, and linkage to Aβ (previously shown to purge cellular brain K+). Brain K isotope compositions differ from that for serum and brain K is much more abundant than in serum, suggesting that changes in brain K may transfer a measurable K isotope excursion to serum, thereby generating an early AD biomarker.

Integrated O, Fe, and Ti isotopic analysis elucidates multiple metal and fluid sources for magnetite from the Ernest Henry Iron oxide copper gold (IOCG) Deposit, Queensland, Australia

Iron oxide copper gold (IOCG) deposits are globally important sources of Cu; however, their origins remain poorly understood with respect to the metal and fluid sources involved in their formation. In this work, we utilize integrated Fe, Ti, and O isotopic data for magnetite to trace major metal and fluid inputs for the Proterozoic-aged Ernest Henry IOCG deposit—the largest known IOCG deposit in the Cloncurry District, Queensland, Australia. Magnetite separates from ore stage and pre-ore biotite-magnetite (bt-mgt) and magnetite-actinolite (mgt-act) alteration assemblages from Ernest Henry were analyzed for their O, Fe, and Ti isotope abundances, reported as δ18O (VSMOW), δ56Fe (IRMM-14), and δ49Ti (OL-Ti). Select magnetite samples were also analyzed for 17O (reported as Δ’17O0.5305) and range from −0.118 to −0.056 ‰—suggesting evaporitic input. The δ18O values from ore stage (+1.57 to +7.36 ‰), bt-mgt (+0.34 to +5.68 ‰), and mgt-act (+1.68 to +2.10 ‰) samples are consistent with a magmatic-hydrothermal origin for ore and pre-ore mineralizing fluids at Ernest Henry; non-magmatic δ18O values > c. 5 ‰ may be explained through localized carbonate wall rock assimilation. Despite this, δ56Fe values for ore stage (−0.50 to +0.33 ‰), bt-mgt (−0.65 to +0.38 ‰), and mgt-act (−0.26 to +0.30 ‰) magnetite are generally isotopically lighter than the accepted range (c. +0.06 to +0.49 ‰) for igneous and magmatic-hydrothermal magnetite and exhibit a relatively large range of c. 1 ‰, suggesting Fe source mixing within the deposit. Ore stage magnetite δ49Ti (−1.64 to + 3.79 ‰; avg: +1.49 ‰; 2σ = 2.63 ‰) compositions are generally higher and more variable than either the bt-mgt (-0.44 to + 1.49 ‰; avg: +0.62 ‰; 2σ = 1.13 ‰) or mgt-act (+0.27 to + 1.89 ‰; avg: +1.05 ‰; 2σ = 1.56 ‰) and suggest that Ti isotope fractionation occurred due to differential mobility in the fluid. The data are best explained by models invoking both magmatic and non-magmatic metal and fluid input. Fluid flow channeled between the footwall and hanging wall shear zones introduced non-magmatic Fe that may have been leached from local mafic units by magmatic-hydrothermal fluids, resulting in neoformed and regeneratively replaced magnetite with magmatic δ18O, but non-magmatic δ56Fe values during pre-ore alteration. These fluids may have mixed with Fe-poor evaporitic fluids prior to magnetite formation. Later magmatic Fe and O contributions during ore stage mineralization resulted in magnetite with variable δ56Fe and irresolvable δ18O overprinting. Ernest Henry is the first known example of an IOCG deposit with a major leached metal component identified through metal stable isotope geochemistry.

Tunnel cation and water structures of todorokite: Insights into metal partitioning and isotopic fractionation

Tectomanganate todorokite and phyllomanganate vernadite are the two major manganese minerals in marine ferromanganese sediments that contain large quantities of trace metals. Todorokite has a less clear metal partitioning mechanism than vernadite, mainly because the metal cation and water structures in the tunnel cavities remain poorly understood. Here, we report the composition-dependent tunnel-cation site disorder of todorokite obtained from molecular dynamics (MD) simulations. Our simulations of homocationic Ni2+-, Zn2+-, Mg2+-, Ca2+-, or Na+-todorokite revealed that tunnel cations form inner-sphere (IS) complexes with Mn octahedral surface at low hydration states, but at higher hydration states, outer-sphere (OS) complexes are the dominant cation species located at the center of the tunnel. However, K+ and Cs+ form only IS complexes regardless of the tunnel hydration state. Optimum water contents were determined based on the free energy changes associated with water intercalation into the tunnel cavities calculated as a function of water content for two heterocationic todorokite models: Mg0.5Na0.4Ca0.1Mn6O12·nH2O (Mg/Mn = 0.08, average Mn oxidation state = +3.73) and Mg1.1K0.1Ca0.1Mn6O12·nH2O (Mg/Mn = 0.18, average Mn oxidation state = +3.58). These models emulate the chemical compositions of well-characterized terrestrial and marine todorokite samples, respectively. At each optimum water content, MD simulations revealed that OS complexes are the major Mg2+ species in the former model. However, IS complexes are the major Mg2+ species in the latter model, indicating that the tunnel cation speciation of diagenetic todorokite can be influenced by the sediment pore-fluid chemistry. The atomic tunnel cation and water structures of todorokite provide a molecular basis for understanding of metal partitioning to Mn oxides and interpretation of metal stable isotopes recorded in ferromanganese nodules.

Iron-Copper-Zinc Isotopic Compositions of Andesites from the Kueishantao Hydrothermal Field off Northeastern Taiwan

The studies of iron (Fe), copper (Cu), and zinc (Zn) isotopic compositions in seafloor andesites are helpful in understanding the metal stable isotope fractionation during magma evolution. Here, the Fe, Cu, and Zn isotopic compositions of andesites from the Kueishantao hydrothermal field (KHF) off northeastern Taiwan, west Pacific, have been studied. The majority of δ56Fe values (+0.02‰ to +0.11‰) in the KHF andesites are consistent with those of MORBs (mid-ocean ridge basalts). This suggests that the Fe in the KHF andesites is mainly from a MORB-type mantle. The Fe-Cu-Zn isotopic compositions (δ56Fe +0.22‰, δ65Cu +0.16‰ to +0.64‰, and δ66Zn +0.29‰ to +0.71‰) of the KHF andesites, which are significantly different from those of the MORBs and the continental crust (CC), have a relatively wide range of Cu and Zn isotopic compositions. This is most likely to be a result of the entrainment of the sedimentary carbonate-derived components into an andesitic magma. The recycled altered rocks (higher δ56Fe, lower δ66Zn) could preferentially incorporate isotopically light Fe and heavy Zn into the magma, resulting in relative enrichment of the lighter Fe and heavier Zn isotopes in the andesites. The majority of the δ56Fe values in the KHF andesites are higher than those of the sediments and the local CC and lower than those of the subducted altered rocks, while the reverse is true for δ66Zn, suggesting that the subseafloor sediments and CC materials (lower δ56Fe, higher δ66Zn) contaminating the rising andesitic magma could preferentially incorporate isotopically heavy Fe and light Zn into the magma, resulting in relative enrichment of the heavier Fe and lighter Zn isotopes in the andesites. Thus, the characteristics of the Fe and Zn isotopes in back-arc and island-arc volcanic rocks may also be influenced by the CC and plate subduction components.

Integrated petrological and Fe-Zn isotopic modelling of plutonic differentiation

The upper continental crust is formed from chemically diverse granitic plutons. Active debate surrounds the range of physical conditions (P-T-X-fO2) and differentiation processes which occur in mush bodies that solidify to form plutons. Transition metal stable isotopes are increasingly employed to trace magmatic processes in both extrusive lavas and intrusive plutonic suites, with a focus on analysis of whole rock powders. However, studies of plutonic suites often overlook the complex textures represented within coarse grained samples, and how these will influence whole rock isotopic compositions.Here we examine the calc-alkaline Boggy Plain Zoned Pluton, SE Australia, which closely approximates closed system behaviour during magmatic differentiation. We combine petrological examination with Fe and Zn isotopic analysis of biotite, hornblende and magnetite mineral separates and whole rock powders. Whole rock Fe isotopic composition (as δ56Fe) increases from 0.038‰ to 0.171‰ with decreasing MgO content, while mineral separates display heavy Fe isotope enrichment in the order magnetite > biotite = hornblende > pyroxene. A lack of correlation between whole rock Fe and Zn isotopic compositions suggests that the Fe isotopic variation is predominantly driven by closed system fractional crystallisation: specifically by the balance between crystallisation of isotopically heavy magnetite, and isotopically light silicates. To demonstrate this quantitatively, temperature dependent mineral-melt fractionation factors were derived from the mineral separate data (Δ56Femag-melt = 0.17 × 106/T2 and Δ56Febt/hbd-melt = −0.12 × 106/T2) and used to construct models that successfully reproduce the observed Fe isotopic variation during fractional crystallisation. These fractionation factors are compared to theoretical and empirical estimates from previous studies. We highlight that accurate determinations of temperature and modal mineralogy are critical when modelling Fe isotopic variations in plutonic suites. Successful interpretation of equilibrium Fe isotopic fractionation in a relatively simple calc-alkaline suite like the Boggy Plain Zoned Pluton paves the way for Fe isotopes to be used to investigate more complex mush bodies.