Calcium Isotopes Research Articles

Magnitude and timescales of Ca isotope variability in human urine: implications for bone mass balance monitoring.

Calcium (Ca) isotopes in blood/urine are emerging biomarkers of bone mineral balance (BMB) in the human body. While multiple studies have investigated Ca isotopes in patients suffering from diseases affecting BMB, comparatively little effort has been devoted to understanding the homeostasis of Ca isotopes in healthy individuals. Here, we report on a longitudinal study of the urine Ca isotope composition (δ44/42CaUrine) from 22 healthy participants (age 19 to 60) over timescales ranging from days to months. Data from a single participant collected over a 30-day period show that morning urine is an excellent proxy for 24 hr pooled urine fractions. Data from all participants reveal large inter-individual variability in δ44/42CaUrine (up to 2.2 ‰), which is partly due to anthropometric differences, as shown by a correlation between the participants' body mass index (BMI) and δ44/42CaUrine values. In contrast, intra-individual data reveal encouraging stability (within ∼ ±0.2-0.3 ‰) over timescales>160 days, indicating that self-referencing approaches for BMB monitoring hold greater promise than cross sectional ones. Our data confirm that intra-individual δ44/42CaUrine variations are mainly a function of Ca reabsorption in the kidney, but also reveal the impact of other (and at times equally important) drivers, such as diet, alcohol consumption, physical exercise, or fasting. We also find that a magnetic resonance imaging contrast agent (gadolinium) can lead to artifacts during Ca isotope analysis. Based on our results, a series of practical considerations for the use of Ca isotopes in urine as tracers of BMB is presented.

Impact of correlations on nuclear binding energies

A strong effort will be dedicated in the coming years to extend the reach of ab initio nuclear-structure calculations to heavy doubly open-shell nuclei. In order to do so, the most efficient strategies to incorporate dominant many-body correlations at play in such nuclei must be identified. With this motivation in mind, the present work analyses the step-by-step inclusion of many-body correlations and their impact on binding energies of Calcium and Chromium isotopes. Employing an empirically-optimal Hamiltonian built from chiral effective field theory, binding energies along both isotopic chains are studied via a hierarchy of approximations based on polynomially-scaling expansion many-body methods. More specifically, calculations are performed based on (i) the spherical Hartree–Fock–Bogoliubov mean-field approximation plus correlations from second-order Bogoliubov many-body perturbation theory or Bogoliubov coupled cluster with singles and doubles on top of it, along with (ii) the axially-deformed Hartree–Fock–Bogoliubov mean-field approximation plus correlations from second-order Bogoliubov many-body perturbation theory built on it. The corresponding results are compared to experimental data and to those obtained via valence-space in-medium similarity renormalization group calculations at the normal-ordered two-body level that act as a reference in the present study. The spherical mean-field approximation is shown to display specific shortcomings in Ca isotopes that can be understood analytically and that are efficiently corrected via the consistent addition of low-order dynamical correlations on top of it. While the same setting cannot appropriately reproduce binding energies in doubly open-shell Cr isotopes, allowing the unperturbed mean-field state to break rotational symmetry permits to efficiently capture the static correlations responsible for the phenomenological differences observed between the two isotopic chains. Eventually, the present work demonstrates that polynomially-scaling expansion methods based on unperturbed states that possibly break (and restore) symmetries constitute an optimal route to extend ab initio calculations to heavy closed- and open-shell nuclei.

A Comparative Study of Cave System Calcium Isotope Ratios: Implications for Quantitative Reconstruction of Paleorainfall From Speleothems

AbstractVariations in speleothem calcium isotope ratios (δ44Ca) are thought to be uniquely controlled by prior carbonate precipitation (PCP) above a drip site and, when calibrated with modern data, show promise as a semi‐quantitative proxy for paleorainfall. However, few monitoring studies have focused on δ44Ca in modern cave systems. We present a multi‐year comparative study of δ44Ca, carbon isotopes (δ13C), and trace elemental ratios from cave drip waters, modern calcite, and host rocks from two cave systems in California—White Moon Cave (WMC) and Lake Shasta Caverns (LSC). Drip water and calcite δ44Ca from both caves indicate PCP‐driven enrichment, and we used a simple Rayleigh fractionation model to quantify PCP variability over the monitoring period. Modern calcite trace element and δ44Ca data positively correlate at WMC, but not at LSC, indicating a shared PCP control on these proxies at WMC but not at LSC. At both WMC and LSC, we observe an inverse relationship between PCP and rainfall amounts, though this relationship is variable across individual drip sites. Our modeled data suggest that WMC experiences ∼20% more PCP than LSC, consistent with the fact that WMC receives less annual rainfall. This work supports speleothem δ44Ca as an independent constraint on PCP that can aid in the interpretation of other hydrologically sensitive proxies and provide quantitative estimates of paleorainfall. Additional, long‐term monitoring studies from a variety of climate settings will be key for understanding δ44Ca variability in cave systems more fully and better constraining the relationship between PCP and rainfall.

Determination of Calcium Isotopes Using Inductive Coupled Plasma-Tandem Mass Spectrometry with Ozone-Induced Oxidation.

In this study, we propose a new method for determination of calcium (Ca) isotopes using inductive coupled plasma-tandem mass spectrometry (ICP-MS/MS). The most abundant isotope of Ca, 40Ca, has a spectrum identical with that of argon (Ar), which is often used as the carrier gas in ICP-MS analysis. The detection capability for 40Ca is thus significantly reduced in the presence of 40Ar. To avoid interference from 40Ar during the 40Ca measurements, ozone (O3) was used as the reaction gas in the ICP-MS/MS analysis. The reaction of Ca+ with O3 in the collision cell preferentially produced CaO3+. In contrast, the reaction between Ar+ and O3 produced ArO+, which further reacted with the oxidized O3 to produce Ar+. Because Ar+ does not produced ArO3+ as the main product of the reaction with O3, the measurement of Ca+ as CaO3 via O3-induced oxidation resulted in considerably less interference from Ar+. The detailed mechanism of CaO3+ formation was investigated via quantum chemistry calculations by using density functional theory. The interaction between Ca+ and O3 yielded CaO3+, which immediately dissociated into either Ca+ and O3 or CaO+ and O2 because the pressure in the collision cell was approximately 1 Pa in the MS/MS experiments. Consequently, CaO3+ was formed by the consecutive reaction of Ca+ with O3, with CaO+ and CaO2+ as intermediates. The present method achieved the detection of less abundant Ca isotopes in certified reference materials such as 43Ca, 44Ca, 46Ca, and 48Ca, thereby allowing the determination of Ca isotopes with high sensitivity.

Carbon–sulfur–calcium isotopic variability of lower Cambrian shale-hosted carbonate concretions: Insights into growth mechanisms and calcium cycling

Marine calcium cycling is closely linked with carbon cycling in the ocean, in which authigenic carbonates precipitated in sediments play a non-negligible role. However, calcium cycling during authigenic carbonate precipitation in organic-rich, shaly sediments in geological history remains underexplored. This study focuses on carbonate concretions (aggregates of authigenic carbonates) in the lower Cambrian Niutitang Formation, South China, to provide insights into calcium cycling during their growth. Sedimentological and mineralogical observations suggest that these concretions were formed through concentric growth by authigenic calcite and pyrite precipitation during the early diagenetic stage. Geochemical analyses reveal internal variations in “M-shaped” δ13Ccarb trends (from −11.9 ‰ to −4.4 ‰) and diverse δ34Spyr trends (from 4.7 ‰ to 14.0 ‰) along core-to-rim transects. These findings suggest formation through microbial sulfate reduction by organic matter in a shallow depth beneath the sediment–water interface. In contrast to the dynamic δ13Ccarb and δ34Spyr variations and multi-stage concentric growth, these carbonate concretions display nearly uniform δ44/40Cacarb values (from 0.80 ‰ to 1.03 ‰, average 0.96 ± 0.06 ‰, 1SD) and consistent internal trends, which are further attributed to strongly seawater-buffered porewater calcium geochemistry and small calcium isotope fractionation due to calcite precipitation at slow rates. This study confirms that early diagenetic carbonate concretions in the lower Cambrian Niutitang Formation are characterized by much heavier δ44/40Ca values compared to coeval shallow platform carbonates. In light of abundant authigenic carbonates observed in the lower Cambrian successions, their roles in calcium isotope mass balance in the early Cambrian ocean warrant further investigation in the future. Therefore, early diagenetic carbonate concretions in black shales could provide valuable insights into porewater and seawater calcium isotope signals, as well as early diagenetic and marine calcium cycling in geological history.

Theoretical comparison of transition rate B(E2) and deformation parameter with experimental data for calcium (20Ca) isotopes using shell model theory

A theoretical comparison has been made for some calcium isotopes ([Formula: see text]Ca) which are even–even nuclei and have the atomic mass (Z = 20) with its previous experimental data. Theoretical calculations of some [Formula: see text]Ca isotopes (A = 42, 44, 46, 48, 50, 52) adopted by the shell model theory were performed to calculate the transition rate B(E2), theoretical intrinsic quadruple moments ([Formula: see text] and theoretical deformation parameters ([Formula: see text], [Formula: see text] were calculated by two methods by using different effective interactions for each isotope such as, su3fp, fpbm, fprkb, fpd6, kb3. Through code NuShellX@MSU, the single-body density matrix was calculated. The effects of the core polarization were neglected by adopting various effective charges that were employed, effective charges of conventional (Con-E), effective charges of standard (St-E) and effective charges of Bohr and Mottelson (B-M-E) which were calculated. The theoretical values of the B(E2)Th, the [Formula: see text] and the ([Formula: see text], [Formula: see text] were then compared with the previous experimental data where values of the transition rate B(E2)Th, theoretical intrinsic quadrupole moments [Formula: see text] and theoretical deformation parameter ([Formula: see text], [Formula: see text], using the fpbm, the fpd6 and the kb3 interactions were the best.

An Implementation of Nuclear Many-Body Wave Functions by the Superposition of Localized Gaussians

Abstract We introduce a new framework for the nuclear structure calculations, which describes the single-particle wave function as a superposition of localized Gaussians. It is a hybrid of the Hartree–Fock and antisymmetrized molecular dynamics (AMD) models. In the numerical calculations of oxygen, calcium isotopes, and $^{100}{\rm Sn}$, the framework shows its potential by significantly improving upon AMD and yielding results that are consistent with or even better than Hartree–Fock(–Bogoliubov) calculations based on harmonic oscillator expansions. In addition to the basic equations, general forms of the matrix elements are also given.

Calcium isotope composition in serum and urine for the assessment of bone mineral balance (BMB) – The Osteolabs post-market follow-up study

To further explore the clinical applicability of the calcium (Ca) isotope marker (CIM), we determined the 44Ca/42Ca isotope ratio in blood serum and urine. This ratio is expressed in the conventional δ-notation (as defined in the text below) specifically as CIM-serum for serum and as CIM-urine for urine. Our study tested the hypothesis that CIM values can differentiate between positive and negative bone mineral balance (BMB) across a diverse clinical population considering variables such as age, gender, and diet. The threshold values (CIM-serum: −0.85 ± 0.06 ‰ and CIM-urine: 0.23 ± 0.06 ‰) established in the OsteoGeo study (NCT02967978, Eisenhauer et al., 2019) were evaluated in 2320 participants as part of a surveillance study referred to as Osteolabs study. The earlier study revealed women with osteoporosis had an average CIM-serum value of −0.91 ± 0.21 ‰ (N = 24) and a CIM-urine value of 0.18 ± 0.33 ‰ (N = 71) that are significantly below the threshold values (p = 0.02 for urine, one-sided Wilcoxon rank test, p < 0.001 for serum, one-sided Student's t-test). Diseases affecting BMB such as osteoporosis, acute and chronic kidney disease (CKD), hyperthyroidism, breast cancer, prostate cancer, and myeloma were associated with significantly lower average CIM values, falling below the equilibrium thresholds and indicating negative BMB. In contrast, patients receiving osteoprotective treatments such as denosumab, Romosozumab, bisphosphonates, or hormone replacement therapy for certain diseases, had CIM values above the equilibrium thresholds indicating a positive BMB. Additionally, Ca supplements taken by some of the patients ((N = 22 (serum), N = 49 (urine), median dose: 500 mg) showed a Ca isotope composition approximately 1 ‰ higher than that from a normal diet. Consequently, their CIM values need to be adjusted to account for the amount and duration of supplementation to be comparable to those with a normal diet. Participants taking vitamin D (237 women; 58 men) showed no significant difference from the average values of the study group. Counterintuitively, the possible impact of malnutrition on individual BMB was most pronounced in vegans, who exhibited the highest average CIM-urine values compared to patients on a normal diet (p < 0.001, N = 17). The results of this study were consistent with the registered OsteoGeo study (NCT02967978) and other earlier published Ca isotope-based studies on BMB. We confirm that the CIM threshold values determined in the OsteoGeo study are generally valid for this much larger and diverse surveillance study group covering a diverse population encompassing various medical conditions and therapies.

Spectroscopy of deeply bound orbitals in neutron-rich Ca isotopes

The calcium isotopes are an ideal system to investigate the evolution of shell structure and magic numbers. Although the properties of surface nucleons in calcium have been well studied, probing the structure of deeply bound nucleons remains a challenge. Here, we report on the first measurement of unbound states in 53Ca and 55Ca, populated from 54,56Ca(p,pn) reactions at a beam energy of around 216 MeV/nucleon at the RIKEN Radioactive Isotopes Beam Factory. The resonance properties, partial cross sections, and momentum distributions of these unbound states were analyzed. Orbital angular momentum l assignments were extracted from momentum distributions based on calculations using the distorted wave impulse approximation (DWIA) reaction model. The resonances at excitation energies of 5516(41)keV in 53Ca and 6000(250)keV in 55Ca indicate a significant l =3 component, providing the first experimental evidence for the ν0f7/2 single-particle strength of unbound hole states in the neutron-rich Ca isotopes. The observed excitation energies and cross-sections point towards extremely localized and well separated strength distributions, with some fragmentation for the ν0f7/2 orbital in 55Ca. These results are in good agreement with predictions from shell-model calculations using the effective GXPF1Bs interaction and ab initio calculations and diverge markedly from the experimental distributions in the nickel isotones at Z=28.

Calcium isotope fractionation during weathering of argillaceous carbonates in a humid climate

The continental weathering is a key process that controls calcium (Ca) transportation from the continental crust to the waters. To elucidate the behavior of Ca isotopes during carbonate weathering, the concentrations and δ44/40Ca (relative to NIST SRM 915a) of bulk saprolites, exchangeable, acid-leachable and residual phases of a weathering profile developed on the marine carbonates, Guangdong province, South China, were investigated. Upwards the profile, δ44/40Ca values of the bulk saprolites systematically decrease from 0.77 ± 0.12 ‰ to −0.44 ± 0.12 ‰, suggesting that significant Ca isotope fractionation occurred during chemical weathering. The exchangeable fractions have δ44/40Ca values higher than those of the bulk saprolites with Δ44/40Caexchangeable-saprolite varying from −0.01 ‰ to 0.73 ‰, suggesting that heavy isotopes are preferentially adsorbed onto the clays. The acid-leachable phases display a relatively narrow δ44/40Ca range from 0.52 ‰ to 0.74 ‰ with Ca fractions varying from 7.4 % to 100.3 %, potentially indicating that limited Ca isotopic fractionation occurs during the dissolution of primary carbonates. The residual Ca pool is strongly fractionated with δ44/40Ca ranging from 0.64 ± 0.08 ‰ to −0.98 ± 0.02 ‰, systematically lower than their bulk saprolites, perhaps indicating light Ca isotopes are preferentially incorporated into the clay lattices. Altogether, it seems that the Ca isotopic fractionation directions are opposite between clay structural incorporation and adsorption. Our study provides important insight of Ca behavior and Ca isotopic fractionation during chemical weathering, which is critical to shape Ca isotopic compositions of the upper continental crust and trace the global biogeochemical cycle of Ca.

The Genesis of A‐Type Granites in Lower Yangtze River Belt: Evidence From Calcium Isotopes

AbstractA‐type granite is a favorable rock for the study of crustal evolution, crust‐mantle interaction and metallogenesis. However, the origin of A‐type granite remains controversial. In this study, we report high‐precision Ca isotopic compositions of a co‐genetic suite of A‐type granites from the Lower Yangtze River Belt (LYRB) in eastern China. Our results show that the δ44/40Ca of the A‐type granites ranges from 0.55 ± 0.11‰ to 1.44 ± 0.06‰, and is negatively correlated with CaO, Sr and Ba contents and Eu/Eu*, indicating that the Ca isotope fractionation of A‐type granites is dominated by plagioclase and potassium feldspar. There is kinetic fractionation of Ca isotopes during A‐type granite magma evolution. Sample BSL‐7, the least evolved sample, revealed that it had a low δ44/40Ca of 0.59‰, which is significantly lower than that of the upper continental crust (δ44/40Ca = 0.71–0.72‰) and the bulk silicate earth (δ44/40Ca = 0.94‰). The low δ44/40Ca can be best explained by partial melting of the enriched mantle metasomatized by subduction material. Combined with the geodynamic background of the LYRB, we propose that the formation of A‐type granites in the LYRB originates from partial melting of the enriched mantle, triggered by early Cretaceous ridge subduction of the Pacific and Izanagi plates.

Early Mississippian global δ13C excursion is not a diagenetic artifact

Shallow-water platform carbonate δ13C may provide a record of changes in ocean chemistry through time, but early marine diagenesis and local processes can decouple these records from the global carbon cycle. Recent studies of calcium isotopes (δ44/40Ca) in shallow-water carbonates indicate that δ44/40Ca can be altered during early marine diagenesis, implying that δ13C may also potentially be altered. Here, we tested the hypothesis that the platform carbonate δ13C record of the Kinderhookian-Osagean boundary excursion (KOBE), ∼353 m.y. ago, reflects a period of global diagenesis using paired isotopic (δ44/40Ca and clumped isotopes) and trace-element geochemistry from three sections in the United States. There is little evidence for covariation between δ44/40Ca and δ13C during the KOBE. Clumped isotopes from our shallowest section support primarily sediment-buffered diagenesis at relatively low temperatures. We conclude that the δ13C record of the KOBE as recorded in shallow-water carbonate is consistent with a shift in the dissolved inorganic carbon reservoir and that, more generally, ancient shallow-water carbonates can retain records of primary seawater chemistry.

Sizeable net export of base cations from a Carpathian flysch catchment indicates their geogenic origin while the 26Mg/24Mg, 44Ca/40Ca and 87Sr/86Sr isotope ratios in runoff are indistinguishable from atmospheric input.

Nutrient imbalances may negatively affect the health status of forests exposed to multiple stress factors, including drought and bark beetle calamities. We studied the origin of base cations in runoff from a small Carpathian catchment underlain by base-poor flysch turbidites using magnesium (Mg), calcium (Ca) and strontium (Sr) isotope composition of 10 ecosystem compartments. Our objective was to constrain conclusions drawn from long-term hydrochemical monitoring of inputs and outputs. Annual export of Mg, Ca and Sr exceeds 5-to-15 times their atmospheric input. Mass budgets per se thus indicate sizeable net leaching of Mg, Ca and Sr from bedrock sandstones and claystones. Surprisingly, δ26Mg, δ44Ca and 87Sr/86Sr isotope ratios of runoff were practically identical to those of atmospheric deposition and soil water but significantly different from bedrock isotope ratios. We did not find any carbonates in the studied area as a hypothetical, easily dissolvable source of base cations whose isotope composition might corroborate the predominance of geogenic base cations in the runoff. Marine carbonates typically have lower δ26Mg and 87Sr/86Sr ratios, and silicate sediments often have higher δ26Mg and 87Sr/86Sr ratios than runoff at the study site. Mixing of these two sources, if confirmed, could reconcile the flux and isotope data.

Towards heavy-mass ab initio nuclear structure: Open-shell Ca, Ni and Sn isotopes from Bogoliubov coupled-cluster theory

Recent developments in nuclear many-body theory enabled the description of open-shell medium-mass nuclei from first principles by exploiting the spontaneous breaking of symmetries within correlation expansion methods. Once combined with systematically improvable inter-nucleon interactions consistently derived from chiral effective field theory, modern ab initio nuclear structure calculations provide a powerful framework to deliver first-principle predictions accompanied with theoretical uncertainties. In this Letter, controlled ab initio Bogoliubov coupled cluster (BCC) calculations are performed for the first time, targeting the ground-state of all calcium, nickel and tin isotopes up to mass A≈180. While showing good agreement with available experimental data, the shell structure evolution in neutron-rich isotopes and the location of the neutron drip-lines are predicted. The BCC approach constitutes a key development towards reliable first-principles simulations of heavy-mass open-shell nuclei.

Calcium isotope variability among ocean islands reveals the physical and lithological controls on mantle partial melting

Major geodynamic processes, including mantle convection and plate tectonics, govern the exchange of mass between Earth's interior and its surface. These processes drive mass-transfer mechanisms such as partial melting and crustal recycling, which have generated a lithologically and compositionally heterogeneous mantle over time. Ocean island basalts (OIB) directly sample these heterogeneities, making them excellent tools to constrain the mantle’s dynamic geochemical evolution. In this study, we probe the connection between crustal recycling, mantle mineralogy, and partial melting using the stable Ca isotope compositions of OIB, ultimately contextualizing their Ca isotope variability using conventional mantle “endmember” components including DMM, HIMU, EM-1, and EM-2. Using the state-of-the-art Nu Sapphire collision cell MC-ICP-MS, we measured the Ca isotope compositions of 27 well-characterized OIB samples from 11 different ocean island groups. By supplementing our new data with additional high-precision Ca isotope measurements from the literature, we create an expanded dataset consisting of 15 ocean islands, facilitating a global-scale investigation of Ca isotope variability among hotspots. Our findings reveal that island-averaged Ca isotope compositions form two distinct groups on the basis of their radiogenic isotope compositions. The first group, consisting of OIB with un-enriched radiogenic isotope compositions (non-EM-type), exhibits robust negative correlations with both lithospheric thickness and primitive TiO2 contents, providing compelling evidence that Ca isotopes are sensitive to the degree of partial melting (F) as well as to the effects of crustal recycling. This joint signal appears to trace the process of decompression melting beneath oceanic lithosphere of variable thickness, as recycled lithologies rich in garnet and pyroxene (i.e., pyroxenites)—which generate large solid-melt Ca isotope fractionations—disproportionally control the Ca isotope composition of the final aggregate melt when F is limited by thick overlying lithosphere. In contrast, the island-averaged Ca isotope compositions of OIB with enriched radiogenic isotope compositions (EM-type) form a distinctly light negative correlation with primitive TiO2 contents without exhibiting a relationship with lithospheric thickness. In addition to lithology-dependent partial melting effects, the Ca isotope compositions of EM-type OIB appear to be sensitive to the compositional effects of crustal recycling, which may explain their decoupling from the physical controls of partial melting. Calcium isotopes show exceptional potential for elucidating the origin of both enriched and ultra-depleted mantle sources, emphasizing the need to prioritize localities with these signatures in future studies.

Calcium isotope fractionation by intracellular amorphous calcium carbonate (ACC) forming cyanobacteria.

The formation of intracellular amorphous calcium carbonate (ACC) by various cyanobacteria is a widespread biomineralization process, yet its mechanism and importance in past and modern environments remain to be fully comprehended. This study explores whether calcium (Ca) isotope fractionation, linked to ACC-forming cyanobacteria, can serve as a reliable tracer for detecting these microorganisms in modern and ancient settings. Accordingly, we measured stable Ca isotope fractionation during Ca uptake by the intracellular ACC-forming cyanobacterium Cyanothece sp. PCC 7425. Our results show that Cyanothece sp. PCC 7425 cells are enriched in lighter Ca isotopes relative to the solution. This finding is consistent with the kinetic isotope effects observed in the Ca isotope fractionation during biogenic carbonate formation by marine calcifying organisms. The Ca isotope composition of Cyanothece sp. PCC 7425 was accurately modeled using a Rayleigh fractionation model, resulting in a Ca isotope fractionation factor (Δ44Ca) equal to -0.72 ± 0.05‰. Numerical modeling suggests that Ca uptake by these cyanobacteria is primarily unidirectional, with minimal back reaction observed over the duration of the experiment. Finally, we compared our Δ44Ca values with those of other biotic and abiotic carbonates, revealing similarities with organisms that form biogenic calcite. These similarities raise questions about the effectiveness of using the Ca isotope fractionation factor as a univocal tracer of ACC-forming cyanobacteria in the environment. We propose that the use of Δ44Ca in combination with other proposed tracers of ACC-forming cyanobacteria such as Ba and Sr isotope fractionation factors and/or elevated Ba/Ca and Sr/Ca ratios may provide a more reliable approach.

Calcium isotope fractionation during tropical weathering of granites

Calcium (Ca) is a highly soluble and mobile element during silicate weathering, and its isotopes could be a promising tracer for continental weathering processes. However, it remains controversial whether Ca isotopes fractionate during granitoids’ weathering. Here we investigated Ca isotope fractionation (measured by δ44/42Ca) behaviours on the weathering profile of the late middle Jurassic Fogang granite (165 ± 2 Ma) under a tropical climate with the help of radiogenic anomaly data (i.e., ε40/44Ca) (both relative to the NIST standard SRM 915a), as well as its implications for the Ca isotopic composition in the hydrosphere. A total of 15 saprolite samples, 2 fresh parent rocks, 3 fresh individual minerals of one granite weathering profile from Fogang county, South China, and 8 stream water samples nearby the profile have been analysed for their Ca isotopic compositions by thermal ionisation mass spectrometry using a double spike method. Results reveal extreme radiogenic and stable Ca isotopic variations among saprolites. The saprolites have ε40/44Ca ranging from 0.8 to 55.6, whereas fresh granite rocks exhibit uniform ε40/44Ca close to 0. The large variation of ε40/44Ca in the saprolites can be attributed to the preferential dissolution of plagioclase and exsolved albite in K-feldspar or the variation of K/Ca molar ratios in K-feldspar. In general, saprolites are enriched in lighter Ca isotopes compared to the parent rocks (0.39 ± 0.04 ‰) and have δ44/42Ca values ranging from −0.45 ‰ to 0.43 ‰. This suggests that newly formed clay minerals preferentially absorb the lighter Ca isotopes (e.g., 40Ca). However, the δ44/42Ca of stream waters draining highly weathered granite catchments reflect δ44/42Ca of bedrock, rather than δ44/42Ca of the saprolites. One possible reason is that too little Ca was adsorbed by secondary clay minerals in the saprolite to shift the Ca isotope composition of dissolved Ca from the bedrock. Our study shows that a combination of radiogenic and stable Ca isotope data is a promising tracer for the sources, migration, and transformation processes of this key element during continental weathering processes. This research contributes to a broader understanding of Ca isotopes as a tracer for tropical weathering and their implications for global biogeochemical cycles.

A dolomite-based record of seawater calcium isotope composition over the Neogene

The calcium isotope composition of seawater (δ44/40Casw) records important information on the evolution of the calcium and carbon cycles over geologic time. Over the past two decades, many attempts have been made to reconstruct the Neogene δ44/40Casw variation using various calcium isotope records of seawater or seawater-like pore fluids. Nonetheless, large discrepancies still exist among these Neogene δ44/40Casw records. Here we report δ44/40Ca values in a suite of Neogene island dolomites (20.8–3.4 Ma, n = 18) from the South China Sea. Combining multiple geochemical proxies (δ44/40Ca, δ13C, and δ18O, this study; Sr/Ca, ∑REY, δ7Li, δ26Mg, 87Sr/86Sr, and Δ47, previous studies) and evidence from petrography, fluid inclusions, and magnetostratigraphy, we suggest that the dolomitization for these dolomites was buffered by seawater-like fluids in the shallow marine burial domain or even marine diagenetic domain (<180 m) over a considerable period of time (<2 Myr). Then, we apply the equilibrium calcium isotope fractionation factor between dolomite and seawater of −0.52 ± 0.20 ‰ (2SD, n = 13) estimated from the literature to these fluid-buffered dolomites and reconstruct a new Neogene δ44/40Casw record. After using the Locally Weighted Regression (LOWESS) curve fitting method, our dolomite-based δ44/40Casw record is consistent with the reconciled seawater record from other calcium isotope archives, including shark teeth, corals, foraminifera, brachiopods, barites, phosphates, and bulk pelagic carbonates. Our results support the use of fabric-retentive early marine diagenetic dolomites to trace the evolution of δ44/40Casw through Earth’s history.

Calcium isotope fractionation during melt immiscibility and carbonatite petrogenesis

Calcium isotope fractionation during melt immiscibility and carbonatite petrogenesis

Calcium isotope compositions of subduction-related leucite-bearing rocks: Implications for the calcium isotope heterogeneity of the mantle and carbonate recycling in convergent margins

Large Ca isotope variations recorded in mantle xenoliths and mantle-derived igneous rocks have been widely used to decode the origin of mantle heterogeneity, especially to trace recycled sedimentary carbonates. However, it is still unclear whether and how the subduction of sedimentary carbonate causes significant Ca isotope fractionation in the mantle in correspondence of convergent margins. In this study, we present Ca isotope data for sixteen silica-undersaturated ultrapotassic leucite-bearing rocks and their clinopyroxene (Cpx) phenocrysts from the “Colli Albani” volcano (Italy), and for six carbonate-bearing sediments from nearby Apennine Chain. These subduction-related volcanic rocks have been widely accepted as deriving from a mantle source that involves recycled carbonated sediments indicated by their enriched incompatible trace elements and radiogenic isotopes, and olivine geochemistry. The δ44/40Ca values (normalized to NIST SRM 915a) of leucite-bearing rocks are uniform (from 0.64 to 0.79 ‰, with one exception of 0.86 ‰) with an average of 0.72 ± 0.03 ‰, 2SE, N = 16, which is 0.12 ± 0.03 ‰ (2SE) and 0.22 ± 0.03 ‰ (2SE) lower than MORBs (0.84 ± 0.02 ‰, 2SE, N = 25) and BSE (0.94 ± 0.01 ‰, 2SE, N = 14) respectively. In contrast, the carbonate-bearing sediments show variable and notably low δ44/40Ca values, ranging from 0.44 to 0.77 ‰. The δ44/40Ca of Cpx (0.70 to 0.76 ‰) is indistinguishable from their host rocks (0.73 to 0.76 ‰). In addition, the lack of correlations between δ44/40Ca and SiO2, CaO, Ni and P2O5, and the Ca isotopic simulation result indicate that Ca isotope fractionation caused by fractional crystallization is insignificant. Given that the Ca isotope fractionation is limited during the melting of spinel wehrlite-like mantle source (within ∼0.04 to 0.11 ‰), the slightly low δ44/40Ca values of the Italian leucite-bearing rocks require 10 % to 20 % addition of carbonated sediments in their mantle source. This indicates that recycled carbonated sediments can cause slight δ44/40Ca heterogeneity (∼0.1 to 0.2) of the mantle wedge in local/regional scales.