Ca Isotopes Research Articles

High-Precision Measurements of 44Ca/40Ca Using Multiple-Collector Inductively Coupled Plasma Mass Spectrometry without Collision-Cell Technology.

Herein, we present a new method for determining the Ca isotopic composition of geological samples. To eliminate matrix elements from Ca, a column chromatography method was developed using a N,N,N'N' tetraoctyl-1,5-diglycolamide (TODGA) resin. The Ca isotopic compositions were measured by a multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) without collision cell equipment, especially that direct measurement to 44Ca/40Ca can be achieved. To mitigate the interference from 40Ar during 40Ca measurement, the cold plasma technique was used to suppress the Ar+ generation, resulting in a background Ar+ intensity of <300 mV, in contrast to the conventional hot plasma conditions, which typically yield thousands of volts for Ar+ intensities. Given the potential for a concentration mismatch between the sample and bracketed standard solutions to cause an intensive shift in measured Ca isotopic compositions, a correction for the [Ca] match is needed. To avoid matrix effects arising from residue matrix elements, it is crucial to limit the concentrations below 1% of Ca for most matrix elements (including Al, Mg, K, Na, and Sr) and below 1‰ for Fe. Notably, the tolerance of residue Sr is effectively improved compared to measurements with CC-MC-ICP-MS and traditional Hot-plasma-SSB-MC-ICP-MS methods with the conventional hot plasma technique, thereby lowering the complexity of column chemistry. The measured δ44/40Ca, δ44/42Ca, and ε40Ca values for eight reference materials agree well with previously reported values within analytical uncertainties. This method demonstrates long-term precision is better than 0.10‰ (two standard deviations) for both δ values (i.e., δ44/40Ca and δ44/42Ca). We anticipate that the proposed method will benefit the growth of the Ca isotope data set and foster an increase in the application of Ca isotope in Earth science studies.

Insights on the origin of oldhamite in enstatite meteorites from Ca stable isotopes

In order to understand the origin of oldhamite (CaS) in enstatite meteorites, we report Ca isotopic compositions (δ44/40Ca) of oldhamite (obtained from water leachate of bulk chondrites and aubrites and mineral separates from the Norton County aubrite) and silicate minerals from different types of enstatite chondrites and aubrite. The δ44/40Ca of the bulk enstatite chondrites range from 1.05 ‰ to 1.24 ‰, with an average of 1.13 ± 0.12 ‰, higher than that of the estimate of the bulk silicate earth (∼0.94 ‰). Major and trace element analyses show that the water leachates of enstatite chondrites are mainly composed of oldhamite, and they take over 20.6–68.5 % Ca of the bulk meteorite Ca budget. The Ca isotope fractionation between oldhamite and residual silicate (Δ44/40Caoldhamite-silicate) for the studied enstatite chondrites is minimum (−0.44 ‰) for Abee (impact-melt breccia) and maximum (+0.16) for St.Marks (EH5). The Ca isotope fractionation between oldhamite (individual mineral grains and leachate) and silicates in Norton County varies from −0.47 ‰ to −0.31 ‰ with an average of −0.41 ‰. These Δ44/40Caoldhamite-silicate correlate well with previous theoretical calculation and suggests that the oldhamites in Norton County are in isotopic equilibrium with co-existing silicates, and therefore were formed during magmatic processes. However, in enstatite chondrites, the large variation on Δ44/40Caoldhamite-silicate and its negative correlation with metamorphic temperature reflects the redistribution and equilibration of Ca isotopes during metamorphism. The variable Δ44/40Caoldhamite-silicate found in unequilibrated chondrites reflect kinetic Ca isotope fractionation between oldhamite and nebular gas and therefore is evidence for the formation of oldhamite by condensation in the solar nebula.

Ca isotopic gradients in epeiric marine carbonates: Diagenetic origins of and significance for Ca cycle reconstructions

Marine carbonates record geochemical information on the state of Earth’s surface environment in the geological past, but recrystallization during burial can make the records difficult to interpret. Here, we report shore to basin gradients in δ44Ca values in matrix limestone and burrow dolomite across a sequence of Late Ordovician (Katian Stage) burrow-mottled carbonates in the Williston Basin, an intracratonic epeiric marine basin in North America. Both gradients are interpreted to have diagenetic origins. The gradient in limestone δ44Ca values developed in a bathymetrically controlled sediment- to fluid-buffered diagenetic system operating between the center and the edges of the basin. Two dolomitizing events formed the gradient in dolomite δ44Ca values. The sediment-buffered end of the limestone gradient preserves the δ44Ca value of the original carbonate mud (∼–1.28 ± 0.10 ‰). The fluid-buffered end of the gradient conserves the δ44Ca value of contemporaneous seawater (–0.47 ± 0.10 ‰), because: (1) pore water exchange drivers operated with greater variety and intensity in shallow water settings, (2) shallow nearshore deposits exchanged more Ca with seawater during recrystallization to diagenetic calcite than deeper offshore deposits, and (3) diagenetic calcite formed with negligible fractionation under equilibrium conditions. The gradient conserves the local value of Δsed (–0.81 ± 0.20 ‰) despite its diagenetic origin, and the magnitude of Δsed is consistent with primary calcite precipitation in a ‘calcite sea’. Field assessment of the equilibrium Ca isotope fractionation factor between calcite and dolomite of –0.41 ± 0.17 ‰ at ambient temperature is applied to correct basin-centered dolomite for fractionation, yielding –1.62 ± 0.27 ‰, which is very different from the –0.25 ± 0.07 ‰ value of Ca in evaporatively concentrated seawater from which the dolomite originally formed. Applying the same fractionation factor to correct literature data on early diagenetic dolomite in the Great Basin, North America, yields –0.69 ± 0.22 ‰ for the δ44Ca value of seawater, which is ∼0.2 ‰ lower than ‘normal marine’ waters in stratigraphically equivalent deposits in the Willison Basin, and 0.44 ‰ lower than evaporatively concentrated seawater during a brief period of basin restriction and anhydrite deposition. The nearly 0.5 ‰ variation in the δ44Ca value of Katian seawater falls within the range of scatter in the brachiopod reconstruction of seawater Ca isotopes. Here, we propose that the true ocean record of secular change lies towards the bottom of the range of scatter, and that the higher values in the record reflect local Ca cycling and circulation restriction in epeiric seas. Epeiric seas cultivate the fluid-buffered diagenetic conditions required to promote Ca isotope exchange between reactive carbonate sediments and seawater through carbonate mineral dissolution/recrystallization, crystal coarsening by way of Ostwald ripening, and replacive dolomitization. It is not the apportioning of kinetically fractionated aragonite and calcite in the carbonate deposition flux that drove secular changes in global value of Δsed between ‘calcite’ and ‘aragonite’ seas, but rather the replacement of kinetic fractionations with equilibrium fractionations during fluid-buffered diagenesis with seawater.

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 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.

Mg-Ca-Fe isotopes of post-collisional magmatic rocks record the crust-mantle interaction processes beneath southern Tibet

The non-traditional Mg, Ca and Fe isotopes have proven to be useful tools for investigating the petrogenesis of the mantle- and crust-derived rocks. Individual non-traditional isotopes in continental basalts are well-studied, particularly in subduction settings. In contrast, there is a significant lack of comprehensive research on various non-traditional stable isotopes related to magmatic processes within continental collision zones, especially during post-collisional stage. To address this knowledge gap, this study presents stable Mg-Ca-Fe isotopic data for the Miocene post-collisional magmatic rocks including ultrapotassic, potassic, and adakitic rocks from the Lhasa Terrane in southern Tibet. The ultrapotassic rocks exhibit slightly lower δ26Mg (−0.28 ± 0.07‰, 2SD, n = 18) and significantly lower δ44/40Ca (0.69 ± 0.03‰, 2SD, n = 18) values than the depleted mantle. The high CaO/Al2O3 and CaO/TiO2 ratios of the ultrapotassic rocks are typical characteristics of carbonate metasomatism, suggesting that the light Mg and Ca isotopic composition may be attributed to the involvement of recycled Ca-rich sedimentary carbonate in the mantle source. Additionally, these ultrapotassic rocks display δ56Fe values (0.026–0.163‰, 2SD, n = 18) ranging from the normal peridotite mantle to much higher values, suggesting a likely origin from a pyroxenite-bearing lithospheric mantle source. These findings imply that subducted oceanic crust and overlying Ca-rich sediments plausibly account for the formation of a mantle source characterized by distinctive Mg-Ca-Fe isotope compositions. The adakitic rocks exhibit the highest δ26Mg (−0.13 ± 0.10‰, 2SD, n = 15) and δ56Fe (up to 0.304‰) values, along with the lowest δ44/40Ca values (0.60 ± 0.07‰, 2SE, n = 15) among these post-collisional magmatic rocks. They also demonstrate strong correlations between δ56Fe and (Gd/Lu)N ratios, indicating a significant role of garnet in their source, consistent with their origin from the thickened lower crust associated with the collision between India and Asia continents. Given the consistent δ56Fe values (0.102 ± 0.067‰, 2SD, n = 5) observed in the adakitic rocks from the western Lhasa Terrane, we posit that it reflects the Fe isotopic composition of the thickened lower crust in southern Tibet. The potassic rocks display lighter Ca isotopes (δ44/40Ca = 0.67 ± 0.03‰, 2SE, n = 5) than the mantle, consistent with a carbonate metasomatized source. They exhibit varying δ26Mg (−0.31 ± 0.07‰ to −0.04 ± 0.07‰, 2SD) and relatively uniform δ56Fe (0.186 ± 0.051‰, 2SE, n = 6) values, falling within the range of nearly contemporaneous ultrapotassic and adakitic rocks. This suggests that potassic rocks may be formed through the mixing of mantle materials resembling ultrapotassic rocks and thickened crustal components resembling adakitic rocks in the lower crust. Building upon these findings, we propose that the distinctive geochemical characteristics, as well as the spatial and temporal distribution of post-collisional magmatic rocks in southern Tibet, are the outcome of partial melting within a carbonated pyroxenite-bearing lithospheric mantle, coupled with the involvement of thickened crust and their subsequent interactions.

Development of a blue-violet high-power single-frequency diode laser system for 48Ca isotope separation

Development of a blue-violet high-power single-frequency diode laser system for ⁴⁸Ca isotope separation

Calcium isotopic compositions of eclogite melts and negligible modification during reaction with lithospheric mantle

Subduction-driven recycling of crustal materials plays a substantial role in the generation of geochemical and lithological heterogeneities in the Earth’s mantle. Because the distinct compositions and/or mineral-specific equilibrium isotopic fractionation effects are present in eclogitized crustal materials, stable isotopes of major elements that exert significant impacts on geochemical and petrologic properties of the mantle may serve as powerful tracers for linking the geochemical anomaly to lithological heterogeneity within the Earth’s interior. Here we present high-precision Ca isotope data, combined with previously reported Mg-Fe isotopes, for a suite of intraplate basalts with a large contribution from recycled crustal material in their mantle sources. The δ44/40Ca in these potassic basalts are consistently lower (0.66–0.78 ‰) than those of mid-ocean ridge basalt (MORBs; 0.85 ± 0.09 ‰), with an average of 0.72 ± 0.09 ‰. The co-variations of major elements with radiogenic isotopes (e.g., MgO-ɛNd) reflect the mixing of two distinct endmembers, one of which is the low-MgO primitive melts and the other is the lithospheric mantle. The low-MgO, SiO2-rich primitive melts are characterized by low CaO/Al2O3 (<0.4) and high Dy/Yb (>5). Remarkably, the primitive melts exhibit low δ44/40Ca (ca. 0.70 ‰)-δ26Mg (ca. –0.60 ‰), and elevated δ57Fe (ca. 0.30 ‰) relative to MORBs. These features are consistent with their origin as partial melts of eclogitic crustal materials. During ascending to the surface, these melts reacted with the surrounding lithospheric peridotite. This process resulted in a noticeable shift of the Mg-Fe isotopes towards the typical mantle values but very limited δ44/40Ca modification. These results suggest that Ca isotopes largely hold the signature of primary melts and are a promising tracer of eclogite in the mantle source of basalts. We further show that the combined isotopes of Ca-Mg-Fe, which are stoichiometrically incorporated into mantle minerals, offer substantial potential to establish the links between lithological and geochemical heterogeneity in the mantle.

Stable isotope composition and concentration systematics of Ca and trace elements (Zn, Sr) in single aliquots of fossil bone and enamel

Measurements of modern bone and tooth enamel show that calcium stable isotopes (δ44Ca), zinc (δ66Zn), and strontium (δ88Sr) have great potential as ecological and dietary tracers for studies on fossil material. Despite the fact that these three elements can be recovered using sequential chromatographic extraction from a single aliquot, a multi-proxy study has not been attempted yet, which would allow a less destructive analysis of precious fossil material. The present study consists of analyzing δ44Ca, δ66Zn, δ88Sr, and 87Sr/86Sr values in fossil bone and tooth enamel of carnivore and herbivore mammals from the Camiac cave (Upper Pleistocene, Gironde, France). Our study aims at (1) developing a protocol for Ca, Zn, and Sr stable isotope analyses from a single fossil bone or enamel aliquot; (2) testing the respective preservation of biological isotopic signatures in bone and tooth enamel; and (3) comparing the patterning of the different isotopic systems in a fossil mammal community. In the present study, fossil enamel samples have not been leached, as it has been done so far for Zn isotope analyses, but fossil bone samples have been leached using diluted acetic acid or were left unleached. Using inclusive statistical analyses, we identify the effect of leaching on bone chemical compositions, and the concentration and isotope composition of Ca, Zn, and Sr in leached bone and unleached enamel show no sizeable diagenetic overprint. We report for the first time δ66Zn values in fossil bone. The results show that bone δ66Zn values mirror the pattern already observed in enamel, e.g., a significant trophic 66Zn depletion between herbivores and carnivores. Bone δ44Ca and δ88Sr values also mirror those in enamel, and the results highlight a clear distinction between ruminants and non-ruminants, the latter being 44Ca-enriched. The present study focuses on the importance of analyzing several isotopic systems in a single fossil bone or enamel aliquot and shows encouraging results for the preservation of biological isotopic signatures in fossil bone, despite the longstanding dread of a so-called associated pervasive diagenesis. The present study will therefore be useful to consider any precious fossil material with limited destructive sampling possibilities.

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.

Calcium isotopic variability in hotspot lavas controlled by partial melting and source lithological heterogeneity

Crustal recycling can induce significant chemical and lithological heterogeneity of the mantle. Ocean island basalts (OIBs) are the surface expressions of rising mantle plumes from the Earth's deep interior and thus can be a probe of the compositional heterogeneity in the deep mantle. Endmember OIBs sampled the most isotopically extreme mantle components including EM1 (Enriched mantle 1), EM2 (Enriched mantle 2), HIMU (high μ; μ =238U/204Pb), and FOZO (Focus zone), but the lithological properties of their source regions are still not well understood. Here we explore the potential of stable calcium (Ca) isotopes in identifying mantle source lithology by investigating OIBs from the type localities for the several mantle components. We find that the δ44/40Ca values of classic HIMU OIBs (0.77 ± 0.09‰; 2SD, N = 15) and Louisville FOZO OIBs (0.78 ± 0.06‰; 2SD, N = 4) are indistinguishable from the average MORB (mid-ocean ridge basalt) value (0.84 ± 0.09‰; 2SD, N = 31), while the δ44/40Ca values of the Pitcairn EM1 (0.65–0.72‰) and the Samoan (Tutuila) EM2 OIBs (0.61–0.71‰) are distinctly lower than those of MORBs. Such Ca isotopic distinction cannot be attributed to magmatic differentiation because the EM1 and EM2 OIBs have obviously lower δ44/40Ca values than the HIMU and FOZO OIBs even at a same MgO content. Equilibrium fractionation during partial melting of garnet peridotite with bulk silicate Earth (BSE) δ44/40Ca (0.94 ± 0.05‰) can explain the Ca isotopic compositions of the HIMU and FOZO OIBs but is unable to reproduce the Ca isotopic variation of all OIBs in this study. Quantitative modeling suggests that the coupling of low δ44/40Ca (< 0.7‰) and high Gd/Yb (> 3.5) ratios in the EM1 and EM2 OIBs most likely points to an eclogitic source component with MORB-like or even lower δ44/40Ca (e.g., < 0.8‰), possibly reflecting contributions from recycled oceanic crust and sediments. A negative correlation between average δ44/40Ca and δ57Fe values (a useful proxy for mantle source lithology) of all endmember OIBs further confirms this proposal and highlights the significant contribution of distinct source lithologies to the Ca isotopic variations in these basalts. Therefore, our study indicates that Ca isotopes of basalts can be another promising tracer of lithological heterogeneity in the mantle.

Calcium isotopes track volatile components in the mantle sources of alkaline rocks and associated carbonatites

The volatile components CO2 and H2O induce mantle melting and thus exert major controls on mantle heterogeneity. Primitive intraplate alkaline magmatic rocks are the closest analogues for incipient mantle melts and provide the most direct method to assess such mantle heterogeneity. Given the considerable Ca isotope differences among carbonate, clinopyroxene, garnet, and orthopyroxene in the mantle (up to 1 ‰ for δ44/40Ca), δ44/40Ca of alkaline rocks is a promising tracer of lithological heterogeneity. We present stable Ca isotope data for ca. 1.4 Ga lamproites, 590–555 Ma ultramafic lamprophyres and carbonatites, and 142 Ma nephelinites from Aillik Bay in Labrador, eastern Canada. These primitive alkaline rock suites are the products of three stages of magmatism that accompanied lithospheric thinning and rifting of the North Atlantic craton. The three discrete magmatic events formed by melting of different lithologies in a metasomatized lithospheric mantle column at various depths: (1) MARID-like components (mica-amphibole-rutile-ilmenite-diopside) in the source of the lamproites; (2) phlogopite-carbonate veins were an additional source component for ultramafic lamprophyres during the second event; and (3) wehrlites at shallower depths were an important source component for nephelinites during the final event.The Mesoproterozoic lamproites show lower δ44/40Ca values (0.58 to 0.66 ‰) than MORBs (0.84 ± 0.03 ‰, 2se). This cannot be explained by fractional crystallization or melting of the clinopyroxene-dominated source but can be attributed to a source enriched in the alkali amphibole K-richterite, which has characteristically low δ44/40Ca. The δ44/40Ca values of the ultramafic lamprophyre suite during the second rifting stage are remarkably uniform, with overlapping ranges for primary carbonated silicate melts (aillikite: 0.67 to 0.75 ‰), conjugate carbonatitic liquids (0.71 to 0.82 ‰) and silicate-dominated damtjernite liquid (primary damtjernite: 0.68 to 0.72 ‰). This suggests negligible Ca isotope fractionation during liquid immiscibility of carbonate-bearing magmas. Combined with previously reported δ44/40Ca values for carbonatites and kimberlites, our data suggest that carbonated silicate melts in Earth's mantle have δ44/40Ca compositions resolvably lower than those for MORBs (0.74 ± 0.02 ‰ versus 0.84 ± 0.03 ‰, 2se). The δ44/40Ca values of the Cretaceous nephelinites (0.72 to 0.78 ‰) are homogenous and similar to those of the 590–555 Ma ultramafic lamprophyres, suggesting that the wehrlitic source component for the nephelinites formed by mantle metasomatism during interaction with rising aillikite magmas during the second rifting stage. Our results highlight that both K-richterite and carbonate components in mantle sources can result in the systematically low δ44/40Ca values of alkaline magmas, which may explain previously reported low δ44/40Ca values of alkaline rocks and some carbonatites. Our study indicates that Ca isotopes are a robust tracer of lithological variation caused by volatiles in the Earth's upper mantle.

Reconstructing Pleistocene Australian herbivore megafauna diet using calcium and strontium isotopes.

Isotopes in fossil tooth enamel provide robust tools for reconstructing food webs, which have been understudied in Australian megafauna. To delineate the isotopic composition of primary consumers and understand dietary behaviour at the base of the food web, we investigate calcium (Ca) and strontium (Sr) isotope compositions of Pleistocene marsupial herbivores from Wellington Caves and Bingara (New South Wales, Australia). Sr isotopes suggest small home ranges across giant and smaller marsupial herbivores. Ca isotopes in Pleistocene marsupial herbivores cover the same range as those in modern wombats and placental herbivores. Early forming teeth are depleted in heavy Ca isotopes compared to late-forming teeth of a given individual, suggesting a weaning signal. Distinct Ca compositions between taxa can be interpreted as dietary niches. Some niches conform to previous dietary reconstructions of taxa, while others provide new insights into niche differentiation across Australian herbivores. Combined with the small roaming ranges suggested by Sr isotopes, the Ca isotope niche diversity suggests rich ecosystems, supporting a diversity of taxa with various diets in a small area.

Distinctive calcium isotopic composition of mice organs and fluids: implications for biological research.

The stable calcium (Ca) isotopes offer a minimally invasive method for assessing Ca balance in the body, providing a new avenue for research and clinical applications. In this study, we measured the Ca isotopic composition of soft tissues (brain, muscle, liver, and kidney), mineralized tissue (bone), and blood (plasma) from 10 mice (5 females and 5 males) with three different genetic backgrounds and same age (3 months old). The results reveal a distinctive Ca isotopic composition in different body compartments of mice, primally controlled by each compartment's unique Ca metabolism and genetic background, independent of sex. The bones are enriched in the lighter Ca isotopes (δ44/40Cabone = - 0.10 ± 0.55 ‰) compared to blood and other soft tissues, reflecting the preferential incorporation of lighter Ca isotopes through bone formation, while heavier Ca isotopes remain preferentially in blood. The brain and muscle are enriched in lighter Ca isotopes (δ44/40Cabrain = - 0.10 ± 0.53 ‰; δ44/40Camuscle = 0.19 ± 0.41 ‰) relative to blood and other soft tissues, making the brain the isotopically lightest soft tissues of the mouse body. In contrast, the kidney is enriched in heavier isotopes (δ44/40Cakidney = 0.86 ± 0.31 ‰) reflecting filtration and reabsorption by the kidney. This study provides important insight into the Ca isotopic composition of various body compartments and fluids.

Moon’s high-energy giant-impact origin and differentiation timeline inferred from Ca and Mg stable isotopes

Mass-dependent stable isotopic variations recorded in lunar samples provide novel resolution to the formation and differentiation history of the Moon. In this study, we report new high-precision Ca-isotope measurements for lunar rocks and minerals. Ca-isotope data and modeling of the lunar magma ocean together demonstrate indistinguishable mass-dependent Ca isotopic compositions of the bulk silicate Earth and Moon. This implied Earth-Moon isotope equilibration is consistent with the Moon’s high-energy giant-impact (Synestia) origin and not readily compatible with the traditional giant-impact models. Moreover, a cross-comparison between Ca and Mg isotopic data for an important anorthosite sample (60025) consistently clarifies its formation near the completion of the lunar magma ocean crystallization. Therefore, the various existing radiometric dating for 60025 sets the lunar magma ocean to have fully solidified by either 4.51 or 4.38 billion years ago, constraining the two respective lunar differentiation timescales to <30 (short-lived) or ~130–150 (long-lived) million years.

Surprising Charge-Radius Kink in the Sc Isotopes at N=20.

Charge radii of neutron deficient ^{40}Sc and ^{41}Sc nuclei were determined using collinear laser spectroscopy. With the new data, the chain of Sc charge radii extends below the neutron magic number N=20 and shows a pronounced kink, generally taken as a signature of a shell closure, but one notably absent in the neighboring Ca, K, and Ar isotopic chains. Theoretical models that explain the trend at N=20 for the Ca isotopes cannot reproduce this puzzling behavior.

Identification of alkaline amendment sources (slash and burn versus marling) for cereal crops grown in the North of France: A multiple isotope approach (87Sr/86Sr, δ44/40Ca, δ88/86Sr)

Early farmers used at least two types of agrarian amendments that could raise pH and base saturation levels to allow the cultivation of cereals: marling and plant ash. Ash can be input in many different ways: felling and burning in place, transferring plant material from wastelands and spreading the ash, charring sod or peat blocks, burning stubble after harvest. Marling includes all the practices of amending limestone, from marl to chalky limestone composed of 99% CaCO3. In order to understand the evolution of these agricultural practices, it is important to identify which of the two techniques was used to amend cereal crops in the past. In order to test the potential of δ44/40Ca-δ88/86Sr-87Sr/86Sr multiple isotope approach for archaeological samples, we first applied the technique to currently grown crops, amended either with marl or with ash from freshly-cut and burned trees. We found that this approach makes it possible to discriminate cereal grains amended either by marling (less radiogenic Sr) or with tree ash (more radiogenic Sr). We also identified a positive correlation between stable Ca and Sr isotope values, suggesting that the Ca and Sr came from similar sources and had undergone similar mass-dependent isotopic fractionation mechanisms. Consequently, we later on mainly focused on stable and radiogenic Sr isotopes. Stable Sr isotope fractionation was also observed between different locations, different organs of a given cereal species and between different cereal types, but also within the same cereal species or the number of grains studied for a given locality, pointing to biological fractionation combined with source variation.

Shell evolution and emerging paradigm changes

The shell structure conceived by Mayer and Jensen in 1949 has been shown to be quite appropriate for stable and near-stable nuclei, but substantial deviations from it have also been observed more recently for exotic nuclei with notable neutron excess. Such changes of the basic picture of the nuclear shell structure, called the shell evolution, seem to be the subject studied most extensively and most elaborately by RI beam experiments worldwide. An overview of the shell evolution is presented in this talk, from both theoretical and experimental perspectives. The shell structure is shown to be varied, for instance, from the one presented by Mayer and Jensen, by particular types of the monopole components of the effective nucleon-nucleon interaction in nuclei. Among various contributions, the importance of the tensor force is illuminated here, with an outstanding example: the emergence of new neutron magic number 34 in neutron-rich Ca isotopes. The mechanism of the shell evolution produces significant impacts also on the nuclear shapes. Type II shell evolution shifts the excitation energies of intruder deformed bands, for instance, in some Ni isotopes. In other more general cases, the monopole interaction is shown to produce unexpected crucial effects on the patters of rotational bands of heavy deformed nuclei. In fact, the shape of the ellipsoidal deformation is investigated by large-scale shell model calculations, which is nothing but the Monte Carlo Shell Model. The unique role of the monopole component of the tensor force is clarified: the interplay between this monopole interaction and the quadrupole interaction provides us with various patterns of triaxial shapes for many nuclei, such as 166Er, one of the traditional prolate deformed heavy nuclei. Thus, the prolate preponderance hypothesis by Aage Bohr is investigated for its microscopic validity. Some of the nuclear paradigms are changing now in this way, due to emerging aspects of nuclear-force effects.

Inferring odontocete life history traits in dentine using a multiproxy approach (δ15 N, δ44/42 Ca and trace elements).

Understanding the interactions between marine mammals and their environment is critical for ecological and conservation purposes. Odontocetes offer a continuous record of their life history from birth as recorded in annual increments of their tooth dentine. Because dentine is not remodeled and contains collagen, nitrogen stable isotope compositions (δ15 N) reflect nursing and weaning events, life history traits that would otherwise be impossible to retrieve in such elusive marine animals. Yet, capturing the magnitude and temporal changes in these events is constrained by tooth size and sampling resolution. Moreover, historical and fossil specimens undergo collagen decay, hence the need to develop the measurements of other proxies. Here, we present a multiproxy approach to investigate the use of Ca isotope compositions (δ44/42 Ca) in relation to δ15 N and laser ablation profiles for different trace metal (Ba, Mg, Sr, Zn) concentrations across the dentine of a single individual of the common bottlenose dolphin Tursiops truncatus. To help interpret the dentine data, we provide milk elemental compositions and δ44/42 Ca values for two odontocete individuals. We discuss the observed changes in δ44/42 Ca across the dentine as potential markers of birth, weaning interval, incidental ingestion of seawater, trophic level and physiology. Incidental ingestion of seawater during nursing induces a positive offset in δ44/42 Ca values recorded in the early formed dentine. Life history parameters of individual marine mammals are extremely difficult to retrieve due to limitations in observing specimens in the wild and the methodology presented here offers new ecological and paleoecological perspectives.

Enrichment of heavy calcium isotopes in saprolite due to secondary mineral formation

Calcium stable isotopes were analyzed in well-characterized saprolite samples developed on a Mesozoic metadiabase dike near Cayce, South Carolina, to determine the degree and sense of isotopic fractionation during chemical weathering. The δ44/40Ca values (relative to NIST SRM 915a) of the saprolites, measured using double-spike TIMS, vary significantly (0.91‰ to 1.26‰), and are generally higher than the δ44/40Ca value of the unweathered metadiabase (0.98‰), which overlaps, within analytical uncertainties, with the δ44/40Ca estimate of the bulk silicate Earth. The δ44/40Ca values of the saprolites negatively correlate with bulk density, and Ti-normalized calcium concentrations, and positively correlate with chemical index of alteration (CIA) values. These trends reflect loss of light Ca isotopes to the hydrosphere during metadiabase weathering. Using insoluble incompatible elements ratios (e.g., Th/Nb) we estimate that the influence of aeolian dust is minimal (3% - 11%) and therefore unable to explain the observed variation in δ44/40Ca values of the saprolites. Selective weathering of rock-forming minerals like plagioclase and clinopyroxene cannot explain the high δ44/40Ca values (> 1 ‰) of the saprolites based on mass balance constraints. Samples with higher kaolinite/smectite ratio have higher δ44/40Ca values and lower concentrations of Ca, which suggests the loss of Ca from smectite-rich clays during progressive weathering. In this case, the lighter isotopes are preferentially lost, leaving the residual clays enriched in heavier isotopes of Ca. The δ44/40Ca values of saprolites correlate positively with δ26Mg and negatively with δ7Li values of the same samples, which further suggests that Ca stable isotopic variability of the Cayce metadiabase saprolites is controlled by formation of clay minerals and progressive loss of Ca during saprolitization. The enrichment of heavy Ca isotopes in saprolites with progressive loss of Ca can be modeled using Rayleigh distillation, with apparent fractionation factors between saprolites and fluid (α) of 1.00005 to 1.00015.