Preferential Incorporation Research Articles

Substantial in situ Ti isotope variations in rutile record source and fluid evolution of porphyry copper mineralization systems

Titanium (Ti) and its stable isotopes have been widely used as tracers for magmatic processes. However, our understanding of Ti isotope behavior in magmatic-hydrothermal systems remains limited. Hence, the in situ Ti isotope composition (δ49Ti) of magmatic titanite and hydrothermal rutile associated with magnetite and chalcopyrite mineralization was determined for the first time in four well-characterized porphyry copper deposits in southern Tibet. The rutile formed through the alteration of primary Ti-rich minerals during fluid-rock interaction in the early high-temperature magnetite and later moderate-temperature chalcopyrite stages of mineralization. Hydrothermal rutile, altered from magmatic titanite, exhibits δ49Ti values similar to those of residual magmatic titanite. This suggests that hydrothermal rutile inherited the Ti isotope composition of magmatic titanite. The average δ49Ti values of rutile are negatively correlated with whole-rock εNd(t) and zircon εHf(t) data, and positively correlated with whole-rock (87Sr/86Sr)i values, which suggests that the initial Ti isotope compositions of hydrothermal rutile in porphyry copper deposits primarily reflect their source. Rutile from the Qulong deposit sometimes exhibits fractionation of δ49Ti at levels exceeding 0.5‰, displaying a negative correlation with Zr and FeO, which may be attributed to the formation of magnetite and rutile at an early potassic alteration stage. Isotopically light Ti is preferentially incorporated into magnetite and rutile. Thus, the rutile associated with sulfide mineralization that formed from the remaining fluids during a later stage of phyllic alteration is enriched in heavy δ49Ti. These findings contribute to the understanding of how rutile fractionates Ti isotopes in hydrothermal systems related to porphyry copper deposits. In local contexts, the substantial crystallization of magnetite, along with the preferential incorporation of isotopically light Ti during the early stages, leads to a decrease in oxygen fugacity within the ore-bearing fluid. This, in turn, facilitates the formation of sulfides during later stages. The results of this study demonstrate the efficacy of in situ Ti isotope analysis as a powerful tool for tracking fluid and metal sources, and can be used to help interpret ore precipitation throughout different stages of magmatic-to-hydrothermal ore-forming processes.

Garnet clinopyroxenite formation via amphibole-dehydration in continental arcs: Evidence from Fe isotopes

Lower-crustal garnet clinopyroxenite (sometimes termed “arclogite”) fractionation in thick-crustal (>35 km) arc settings presents a compelling model to explain Fe-depletion trends, high oxygen fugacity, and evidence of recent delamination observed in many continental arcs. However, the origin of the garnet clinopyroxenites via igneous or metamorphic processes remains unclear. Due to the preferential incorporation of light Fe isotopes in garnet relative to clinopyroxene or amphibole, Fe isotopes are ideally suited for studying the effects of garnet fractionation on magmatic systems. Here, we present whole-rock and mineral Fe isotope data from a suite of lower to mid/upper-crustal Andean xenoliths from Mercaderes, Colombia. This data is combined with petrography, major and trace element mineral and whole-rock chemistry, geothermobarometry, and thermodynamic modeling to explore the xenoliths' petrogenesis and the Northern Andes' crustal structure. Whole-rock samples display a narrow range of Fe isotope compositions (δ56Fe = –0.02 to +0.11 ‰), which do not correlate with lithology, chemistry, or pressure-temperature conditions. This result is inconsistent with previous studies predicting the existence of an isotopically light Fe reservoir in the garnet-rich lower Andean crust. Through thermodynamic modeling, we show that the lack of isotopic fractionation in the Mercaderes xenoliths is more consistent with the suite representing a prograde metamorphic sequence, in which amphibole dehydration reactions drive metamorphism of mid/upper-crustal diorite protoliths. While our data do not preclude the presence of garnet clinopyroxenite cumulates at the base of the Andean crust, or that the delamination of such cumulates played an important role in the evolution of the Andes, they do indicate that not all garnet clinopyroxenites are cumulate in origin. Instead, the lower Andean crust represents an amalgamation of igneous and metamorphic rock, with metamorphism of mid-crustal lithologies and partial melting of mafic cumulate roots acting in tandem to drive densification and delamination of the lower crust in a self-feeding mechanism.

Lithium isotope systematics in an endorheic saline lacustrine system: Insights from Qinghai Lake, China

The study of lithium isotopic (δ7Li) signatures in sedimentary deposits has become a powerful tool to infer past silicate weathering regimes, thus informing our knowledge of the geological carbon cycle and paleoclimate evolution. Sediments from Qinghai Lake, the largest saltwater lake in China (4625 km2), offer an unparalleled archive for investigating the climatic history of the Qinghai-Tibet Plateau. However, prior to leveraging the δ7Li proxy in this context, it is imperative to unravel the mechanisms of lithium (Li) isotope fractionation and elemental cycling within the lake's aqueous and sedimentary systems. In this study, we collected and analyzed samples of Qinghai Lake's water, sediments, and recharge waters (rivers, groundwater, and rainfall) to investigate the processes controlling the δ7Li value recorded in Qinghai Lake sediments.Our data reveal subtle variances in Qinghai Lake water Li concentration ([Li]), ranging from 652 to 873 ng/g, suggesting interactions with iron oxides or suspended matter. The δ7Li signature, however, exhibits remarkable uniformity across the lake at 32.1‰ (±0.4‰). Near the estuary of the Buha River, there is a swift homogenization of [Li] and δ7Li, stabilizing within just 3 km of the inflow. Lake sediments exhibit δ7Li values ranging from 1.5‰ to 6.6‰, exceeding those of the upper continental crust (∼0‰ ± 4‰), yet approximately 30‰ lower than those in lake waters. This significant discrepancy between the δ7Li of lake water and sediments is likely due to the preferential incorporation of 6Li over 7Li during the neoformation of clay minerals.Lithium mass balance modeling for Qinghai Lake, incorporating inputs from river and groundwater (∼46.5 t/a with δ7Li ∼18.3‰) and outputs via clay mineral uptake (∼44 t/a with δ7Li ∼5.1‰), indicates that the lake's Li system is currently out of steady state. The model predicts a gradual rise in the lake's Li inventory, estimated to achieve steady state within 1.2 ka and the δ7Li value of lake water will increase until reaching ∼45‰ assuming constant climate conditions.

An influence of geothermal water, temperature and pressure on the hydration of multicomponent cement binders

Cement pastes of different compositions were hydrated in a geothermal solution with the simultaneous action of high temperature (150 °C) and pressure (18 MPa) for 7 days. The influence of solution on phase composition and compressive strength of pastes was investigated based on the comparison with hydration in water and using TGA, XRD, FTIR, 29Si, and 27Al NMR. The geothermal solution accelerated hydration and pozzolanic reactions. A higher amount of more thermally stable products was formed. Undesired transformation to crystalline α-C2SH in the samples with the highest C/S ratio was restricted. The uptake of carbonates from the solution led to an increased amount of calcite. As a result, increased compressive strength values were determined. Preferential incorporation of Al3+ into the structure of C-(A-)S-H or hydrogrossular phases depended on the composition of cement pastes.

Occurrence and enrichment of cobalt and nickel in the Yindongshan ultramafic–mafic intrusion-hosted iron deposit, western Hubei Province, China

The Yindongshan iron deposit in western Hubei Province of China is hosted within Ordovician ultramafic–mafic intrusions. Recent field geological surveys have detected cobalt (Co) and nickel (Ni) enrichment within the Yindongshan clinopyroxenite, suggesting good potential for subeconomic Co-Ni mineralization. This study investigated the occurrence modes and enrichment processes of Co and Ni in the Yindongshan deposit through field geology and in situ analysis of the rock texture, geochronology, and geochemistry of sulfides, Fe-Ti oxides, and silicate minerals. The Yindongshan clinopyroxenites were emplaced at 440.2 ± 7.2 Ma via titanite LA-ICP-MS U-Pb dating, and underwent extensive post-magmatic metamorphism at 401.2 ± 8.6 Ma via apatite U-Pb dating. This metamorphism led to the widespread formation of amphibole via the replacement of clinopyroxene. Subsequently, hydrothermal epidote-albite veins, calcite-pyrite veins, and later actinolite veins developed. Pyrites from both clinopyroxenites and calcite veins show limited δ34S variations from −5.4 ‰ to −1.2 ‰, suggesting a magmatic sulfur source. Late-vein actinolites display geochemical characteristics distinct from those of amphiboles, indicating possible involvement of external fluids. LA–ICP–MS trace element results reveal a general increase in Co and Ni contents from silicate minerals and Fe-Ti oxides to pyrite and from earlier-crystallized coarse-grained clinopyroxenite to later medium- to fine-grained clinopyroxenite. The highest Co and Ni contents observed in pyrite from coarse-grained clinopyroxenite suggest their preferential incorporation into early sulfide minerals and then progressively depleted through magmatic evolution such as fractional crystallization. The positive correlation between Co and Ni with Fe in pyrite, along with the consistent parallel time-resolved LA–ICP–MS depth profiles among different mineral phases, indicates that isomorphic substitution occurred in pyrite. In silicate minerals, the Co and Ni contents increase from pyroxene, amphibole, to actinolite, with almost no Co or Ni present in epidote. The elevated Co and Ni contents in metamorphic amphiboles are attributed to their remobilization from magmatic pyrite to newly formed amphiboles. During the late hydrothermal phase, external fluids might transport additional Co and Ni, contributing to higher concentrations in late actinolite veins. In general, Co and Ni in the Yindongshan iron deposit are primarily hosted in sulfide minerals and can be remobilized during regional metamorphism and metasomatism. Thus, magmatic iron or iron–titanium oxide deposits hosted by mafic–ultramafic intrusions with sulfide mineralization may serve as promising targets for further Co-Ni exploration.

Germanium and its isotopes as indicators of hydrogeochemical conditions in a terrestrial geothermal system (Karkonosze granitoid, Sudetes, Poland)

The germanium content and its isotope ratio in thermal waters, aquifer rocks and main silicate minerals in a terrestrial groundwater system located in a granitic pluton (Karkonosze granitoid, Sudetes, Poland) have been investigated. This is the first extensive Ge isotope study carried out in both groundwater and aquifer rocks to better understand previously the identified enrichment of groundwater relative to rocks. This research also provides the first data on δ74/70Ge for hybrid acid rocks formed by mixing magmas from two different sources (mantle- and crustal-derived) and main silicate minerals. The Ge isotopic composition in different facies of granite (porphyritic, equigranular) is comparable (δ74/70Ge of 0.43–1.23‰) to its hybrid rocks (quartz diorite–granodiorite, microgranular magmatic enclaves, composite dykes) – 0.79–1.27‰. However, the range of variability of this feature is quite wide. The minerals have δ74/70Ge values of 1.01–1.04‰ in quartz, 0.84–0.90‰ in alkali feldspars, 0.76–0.88‰ in plagioclase, and 0.36–0.39‰ in biotite. The thermal waters are enriched in heavy Ge isotopes (δ74/70Ge of 1.21–2.78‰) relative to the aquifer rocks (δ74/70Ge of 0.43–1.27‰). Currently, the most likely explanation for this is the influence of secondary mineral phases formed in the geothermal granitic system. This comprises the preferential incorporation and adsorption of light Ge isotopes in/onto iron oxide/hydroxides and clay minerals. The other theoretical explanation, i.e., sulfide formation, is unlikely due to the unfavourable hydrogeochemical conditions in the studied system. The δ74/70Ge values of thermal waters are similar to those of previously studied continental geothermal waters (1.65–3.29‰; Siebert et al., 2011) and fresh groundwater (2.24–4.02‰; Baronas et al., 2020), confirming that groundwater enrichment in heavy Ge isotopes relative to aquifer rocks may be widespread in the upper continental crust. Variation in the isotopic composition of the studied thermal waters is a result of the aquifer rock mineralogy and, in some cases, mixing of the old deep-circulating thermal water with the shallow modern cold groundwater. The general similarities in the chemical composition of the studied waters are due to the influence of porphyritic granite, which is the dominant rock type in this aquifer system. Some differences in chemical composition, including differences in the Ge isotopic composition, are related to the local distribution of hybrid rocks and sulfides. The δ74/70Ge and Ge/Si ratios have been shown to be sensitive indicators of local hydrogeochemical conditions in an alimentation zone and a near-borehole zone of particular water intakes.

Zinc isotope fractionation during the sorption of Zn to minerals and organic matter in sediment cores affected by anthropogenic pollution

Zinc stable isotopes (δ66Zn) serve as a widely fingerprinting tool for detecting anthropogenic Zn contamination. However, there is a limited understanding of δ66Zn behavior during the sorption of Zn to minerals and organic matter. In this study, we have determined the δ66Zn values in specific fractions to investigate their effectiveness in tracing anthropogenic Zn. The revised Community Bureau of Reference (BCR) extraction procedure was applied to a coastal marine core from Osaka Bay and from a lacustrine core from Lake Biwa, both with a history of anthropogenic metal pollution. The δ66Zn values varied from −0.14 ‰ to +1.00 ‰ across the four to five chemical fractions with up to 0.9 ‰ variation within a single horizon. The highest δ66Zn values in the acid-soluble fraction (up to +1.00 ‰) could be explained by the preferential sorption of 66Zn to carbonates and/or the preferential incorporation of 66Zn into calcite. The complex isotopic fractionation during the sorption of Zn to and co-precipitation with Fe–Mn oxyhydroxides likely resulted in an unclear pattern of the δ66Zn values of the reducible fraction. Low δ66Zn values in the oxidizable fraction (Osaka Bay) agree with the 64Zn enrichment in phytoplankton. Higher δ66Zn values of the reducible and oxidizable fractions of the Lake Biwa core indicate that environmental conditions (e.g. ionic strength) and for instance different phytoplankton species or dissolved and suspended particulate matter input drive the Zn isotope fractionation depending on the system (marine vs. lacustrine). The δ66Zn values of the acid-soluble fraction (Osaka Bay and Lake Biwa), of the reducible fraction (only Lake Biwa) and of oxidizable fraction (only Osaka Bay) better reflected the temporal changes in the Zn concentration than the bulk sediment, indicating that these fractions could be a sensitive fingerprinting tool for anthropogenic Zn contamination.

Zircon Zr[sbnd]Hf isotope disequilibrium during crustal anatexis: A record from the Mesozoic migmatite in the eastern Gangdese arc, South Tibet

Stable zirconium (Zr) isotopes have become the focus of attention as potential tracers of magma crystallization and differentiation processes. However, the effects of partial melting, especially disequilibrium melting, on Zr isotope fractionation remain unclear. Here we report in-situ zircon UPb ages, major and trace elements, and ZrHf isotope data for the migmatites in the eastern Gangdese arc, South Tibet. The leucosomes from the metatexite and diatexite migmatites are generally concordant with the foliation of the paleosome and display diffuse and gradational contacts with the melanosomes, indicating that they are in-source leucosomes. Zircon in the paleosome, the protolith of the migmatites, have UPb age of 361 ± 2 Ma and low 176Hf/177Hf ratios of 0.282399–0.282482. They exhibit intragrain variation in δ94/90Zr values, increasing from the core (−0.10 ‰ to +0.36 ‰) to the rim (+0.14 ‰ to +0.55 ‰) domains. The negative correlation between δ94/90Zr values and Zr/Hf ratios suggests preferential incorporation of light Zr isotopes during the crystallization of the zircon in the protolith. Most zircon in the leucosomes from the metatexite and diatexite migmatites exhibit distinct overgrowth rims around the inherited cores. The inherited cores have consistent UPb ages (ca. 360 Ma), trace elements, and Hf isotopic compositions (0.282362–0.282449) with zircon in the paleosome, indicating in situ partial melting. The inherited cores display δ94/90Zr values ranging from −0.12 ‰ to +0.31 ‰, consistent with the zircon core domains in the paleosome. The overgrowth rims have UPb ages of ca. 102 Ma and display higher 176Hf/177Hf ratios (0.282592–0.282900) and δ94/90Zr values (+0.01 ‰ to +0.63 ‰) than their inherited cores. The elevated 176Hf/177Hf for the overgrowth rims resulted from the retention of unradiogenic 177Hf in the residue due to limited zircon dissolution and more release of radiogenic 176Hf to the melts because of the garnet breakdown, indicating disequilibrium melting. The elevation of δ94/90Zr for the overgrowth rims relative to the inherited cores was not caused by the disequilibrium melting of other Zr-bearing minerals but was mainly controlled by the Zr isotopic composition and dissolution degree of the zircon in the protolith. The preferential melting of isotopically heavy zircon rims would elevate the δ94/90Zr values in the melts relative to their zircon-bearing protoliths. Crustal anatexis may be another important mechanism contributing to the Zr isotope fractionation during crustal differentiation.

Alteration mineralogy, characteristics and shortwave infrared spectroscopy of white mica in the Zijinshan ore field, Fujian Province: Implications for porphyry Cu prospecting

The Zijinshan ore field is situated in the southeastern part of China. in which contains the large Zijinshan high-sulfidation Cu-Au deposit, the Luoboling porphyry Cu-Mo deposit, the Yueyang low-sulfidation Au-Ag deposit, the Longjiangting and the Wuziqilong tansitional Cu deposit, and the Xi’nan porphyry Cu-Mo prospect. Debates on genetic relationship among these deposits, especially the relationship between the Zijinshan Cu-Au deposit and the adjacent Luoboling deposit is a question of importance for further exploration in this ore field. In this contribution, the alteration mineralogy, alteration texture, zonation and mineral chemistry, in combination with shortwave infrared spectroscopy (SWIR) analysis of white mica were used to help focus exploration and assessment of hydrothermal deposits in the Zijinshan ore field.In this study, diaspore-pyrophyllite alteration zone, chlorite-sericite alteration zone and propylitic alteration zone were first identified in the deep drill core of the Zijinshan Cu-Au deposit, which gives way upward to quartz-alunite-kaolinite zone, quartz-alunite zone and the silicic alteration zone. In the Xi’nan Cu-Mo prospect, diaspore-pyrophyllite alteration zone was first recognized in the shallow level with the chlorite-sericite alteration zone and propylitic alteration zone in the deeper level. Andalusite- sericite ± diaspore alteration zone was first recognized in the upper part of the Luoboling Cu-Mo deposit and the deeper part of the Wuziqilong Cu deposit. It indicates that a pervasive occurrence of diaspore -pyrophyllite ± andalusite alteration zones in the Zijinshan ore field, which may potentially represent a transitional environment between the top of porphyry alteration zones and the base of advanced argillic alteration zones. Minerals of the white mica group are extensively distributed in various alteration zones of the Zijinshan ore field. The SWIR analysis of white mica indicated that the wavelength position of the Al-OH (∼2,200 nm; wAlOH) absorption feature increases gradually from the shallow kaolinite-dickite alteration zone to the deep potassic alteration zone. In the advanced argillic alteration zones, the range of wAlOH values of white mica is less than 2205 nm. Conversely, in the porphyry alteration zones, it always exceeds 2205 nm. It is evident that the andalusite-sericite alteration zone with higher wAlOH values (average of 2203 nm) is always proximal to the porphyry mineralization, which may act as indicators for deep porphyry prospecting. The results of electron probe microanalysis (EPMA) reveal that the early enrichment of Mg and depletion of Fe in white mica can be attributed to the preferential incorporation of Fe into iron oxides and iron sulfides in the potassic and propylitic alteration zones. Overall, there is a negative correlation between wAlOH and Al, while wAlOH exhibits a positive correlation with the sum of Fe + Mg + Mn. The distribution characteristics of alteration zones and the variation patterns of the wAlOH of white mica indicate that there are probably several paleo-thermal centers in the deep parts of the Zijinshan ore field, located respectively in the deep parts of the Xi’nan Cu-Mo prospect and the deep part of the Zijinshan Cu-Au deposit and the deep parts of the Wuziqilong Cu deposit, and the latest seems to be more fertile and deserves further exploration.

Centromere diversity: How different repeat-based holocentromeres may have evolved.

In addition to monocentric eukaryotes, which have a single localized centromere on each chromosome, there are holocentric species, with extended repeat-based or repeat-less centromeres distributed over the entire chromosome length. At least two types of repeat-based holocentromeres exist, one composed of many small repeat-based centromere units (small unit-type), and another one characterized by a few large centromere units (large unit-type). We hypothesize that the transposable element-mediated dispersal of hundreds of short satellite arrays formed the small centromere unit-type holocentromere in Rhynchospora pubera. The large centromere unit-type of the plant Chionographis japonica is likely a product of simultaneous DNA double-strand breaks (DSBs), which initiated the de novo formation of repeat-based holocentromeres via insertion of satellite DNA, derived from extra-chromosomal circular DNAs (eccDNAs). The number of initial DSBs along the chromosomes must be higher than the number of centromere units since only a portion of the breaks will have incorporated eccDNA at an appropriate position to serve as future centromere unit sites. Subsequently, preferential incorporation of the centromeric histone H3 variant at these positions is assumed. The identification of repeat-based holocentromeres across lineages will unveil the centromere plasticity and elucidate the mechanisms underlying the diverse formation of holocentromeres.

Experimental and theoretical constraints on lithium isotope fractionation during brine evaporation and halite precipitation

Marine evaporitic halite, precipitating from the advanced stage of extremely evaporated seawater, is the most common and abundant evaporitic mineral. The extent to which lithium (Li) is incorporated into evaporite halite during geological periods of massive halite deposition, and the mechanisms of incorporation, are both unknown. These are each important, however, for the quantification of the isotope effect of the evaporitic sink on δ7Liseawater, and for the potential use of halite as a recorder of seawater δ7Li. Here, new experimental data are presented for the Li fractionation factor for halite from an isothermal evaporation experiment (25∘C for 100 days) using marine-derived brine. The resultant solids were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) to confirm the mineralogy and crystallinity of the product. Our results show that Li isotopes are not constant during the evaporation process implying that there must be a process that fractionates Li isotopes during halite precipitation. We suggest that this results from Li ionic substitution for sodium (Na) in crystalline halite, a scenario supported by ab-initio calculations, but we also show that Li within halite is predominantly present within fluid inclusions. Thus, the Li isotopic composition of halite is controlled by a mixture of Li within the fluid inclusions and Li that is incorporated into the halite crystalline structure. Overall, the brine becomes enriched in Li7 during evaporation due to the preferential incorporation of Li6 into chloride precipitates, and the evolution of δ7Librine is controlled by the precipitated mineral assemblage. The theoretical equilibrium fractionation factor 1000lnαmineral−fluid is -7.8▪ for Li-halite (LiNa26Cl27) at 25 C∘ at equilibrium, which is at the lower limit of Li isotope fractionation factors. Rayleigh fractionation models were fitted to the experimental data yielding a fractionation factor of -25▪3▪. The difference in Li isotope fractionation factor between brine and structurally bound Li may result from kinetic fractionation effects. This study presents a scenario highlighting that extensive halite deposits, formed over geological time in environments with relatively high Li concentration, could potentially impact the δ7Li values of seawater during that period, and place constraints on their utility as an archive for δ7Liseawater.

Lithium isotope fractionation during submarine hydrothermal alteration processes

River water and submarine hydrothermal fluids are the two primary sources of lithium (Li) input to the ocean. However, compared to well-documented weathering processes, the behavior of Li isotopes during hydrothermal alteration processes remains obscure. In this research, we investigated the Li isotopic compositions (δ7Li) of hydrothermally altered sediments from two IODP drilling cores (C0013 and C0014) in the Iheya North Knoll of the middle Okinawa Trough. The sediments, primarily altered from volcanic clasts, exhibit a pristine δ7Li value (5.2 ± 0.7 ‰) similar to that of MORB (3.7 ± 1 ‰). Intense hydrothermal activity led to the complete conversion of primary feldspars into phyllosilicates, predominantly Mg-chlorite, at site C0013 and in the middle and deep parts of C0014. The altered samples showed a depletion of 7Li (ranging in δ7Li from −10.0 ‰ to 4.2 ‰) compared to background sediment, indicating the preferential incorporation of 6Li during the formation of secondary minerals. Furthermore, both drilling sites exhibited increasing trends in δ7Li values with depth, with the deepest samples approaching the pristine δ7Li values of unaltered volcanic rock. These trends were attributed to the significant thermal gradients present at both sites. The temperature-dependent fractionation factor of Li isotopes allowed us to estimate the alteration temperature, which yielded temperature values consistent with those obtained using the δ18O geothermometer. This finding underscores the potential of Li isotopes as a novel geothermometer tool, although further calibration work is required. Based on our research findings, we developed a dissolution-precipitation model (based on mass balance) that establishes a relationship between the δ7Li values of altered solids and hydrothermal fluids, with the aim of elucidating the relatively limited variation observed in global submarine hydrothermal fluids (ranging from 1.6 ‰ to 11.0 ‰, with an averaged value of 5.9 ± 3.0 ‰, mean ± SD). This model quantitatively depicted the strong restriction of the Li concentration in hydrothermal fluids on their isotopic compositions, as high concentrations of Li in the fluids necessitate a substantial release of Li from the solid phase, causing the fluids' δ7Li values to approach that of the bedrock. Additionally, limited fractionation factors at high temperatures further constrain the variations in the fluids' δ7Li values. Model predictions also suggest that the reported δ7Li values of hydrothermal fluids have encompassed the potential δ7Li variation, providing supporting evidence for the assumption that δ7Li values of submarine hydrothermal fluids have exhibited insignificant variations throughout Earth's history.

The mechanistic basis of the membrane-permeabilizing activities of the virulence-associated protein A (VapA) from Rhodococcus equi.

Pathogenic Rhodococcus equi release the virulence-associated protein A (VapA) within macrophage phagosomes. VapA permeabilizes phagosome and lysosome membranes and reduces acidification of both compartments. Using biophysical techniques, we found that VapA interacts with model membranes in four steps: (i) binding, change of mechanical properties, (ii) formation of specific membrane domains, (iii) permeabilization within the domains, and (iv) pH-specific transformation of domains. Biosensor data revealed that VapA binds to membranes in one step at pH 6.5 and in two steps at pH 4.5 and decreases membrane fluidity. The integration of VapA into lipid monolayers was only significant at lateral pressures <20 mN m-1 indicating preferential incorporation into membrane regions with reduced integrity. Atomic force microscopy of lipid mono- and bilayers showed that VapA increased the surface heterogeneity of liquid disordered domains. Furthermore, VapA led to the formation of a new microstructured domain type and, at pH 4.5, to the formation of 5 nm high domains. VapA binding, its integration and lipid domain formation depended on lipid composition, pH, protein concentration and lateral membrane pressure. VapA-mediated permeabilization is clearly distinct from that caused by classical microbial pore formers and is a key contribution to the multiplication of Rhodococcus equi in phagosomes.

Similar Distribution between EPA-containing Phosphatidylcholine and Mesenchymal Stem Marker Positive Cells in the Aortic Wall of Abdominal Aortic Aneurysm Model Rat Fed a Low-EPA Content Diet.

Abdominal aortic aneurysm (AAA) is a vascular disease characterized by progressive dilation of the abdominal aorta. Previous studies have suggested that dietary components are closely associated with AAA. Among those dietary components, eicosapentaenoic acid (EPA) is considered to have suppressive effects on AAA. In the AAA wall of AAA model animals bred under EPA-rich condition, the distribution of EPA-containing phosphatidylcholine (EPA-PC) has been reported to be similar to that of the markers of mesenchymal stem cells (MSCs) and M2 macrophages. These data suggest that the suppressive effects of EPA on AAA are related to preferential distribution of specific cells in the aortic wall. However, the distribution of EPA-PC in the AAA wall of AAA model animals fed a diet containing small amounts of EPA, which has not been reported to inhibit AAA, has not yet been explored. In the present study, we visualized the distribution of EPA-PCs in the AAA wall of AAA model animals fed a diet containing small amounts of EPA (1.5% EPA in the fatty acid composition) to elucidate the vasoprotective effects of EPA. Positive areas for markers of MSCs were significantly higher in the region where EPA-PC was abundant compared to the regions where EPA-PC was weakly detected, but not for markers of M2 macrophages, matrix metalloproteinase (MMP)-2, and MMP-9. The distribution of MSC markers was similar to that of EPA-PC but not that of M2 macrophages and MMPs. These data suggest preferential incorporation of EPA into MSCs under the conditions used in this study. The incorporation of EPA into certain cells may differ according to dietary conditions, which affect the development of AAA.

Impact of grain-dependent boron uptake on the nano-electrical and local optical properties of polycrystalline boron doped CVD diamond

Boron-doped diamond (BDD) films grown by chemical vapor deposition (CVD) exhibit unique electrical and optical properties owing to the non-uniform uptake of boron dopants across grains. This study utilizes scanning probe microscopy and confocal micro- spectroscopy techniques to elucidate the influence of grain-dependent boron incorporation on the nano-electrical and local optical characteristics of polycrystalline BDD. The CVD- grown BDD film contained crystallites up to tens of microns, while the surface comprised 200…800 nm grains. Scanning spreading resistance microscopy (SSRM) revealed significant nanoscale resistance variations among individual grains, attributable to differential boron distributions. No distinct grain boundary features were discernible in SSRM data, likely due to the high boron doping of ~ 3·10 19 cm –3 . SSRM of the Au surface of a BDD/Ti/Pd/Au contact indicated a comparable granular morphology but three orders lower resistance. A network of more resistive grain boundaries was evident, modulated by underlying BDD grain clusters. Photoluminescence spectroscopy showed characteristic bands of nitrogen-vacancy centers and donor-acceptor pairs. Confocal Raman and photoluminescence mapping elucidated substantial spatial heterogeneity in micrometer- scale grains regarding crystal quality, boron and nitrogen concentrations, related to preferential incorporation. The observed peculiarities in BDD’s structural and nano- electrical characteristics stem from inherent growth inhomogeneities and grain-dependent boron uptake influenced by defects and strain fields modifying local chemical potentials. This multifaceted nanoscale examination provides critical insights into optimizing electrical and optical properties of BDD films by controlling synthesis conditions and minimizing defects for tailored performance in electronic, electrochemical, and quantum applications.

Role of Native Defects in Fe-Doped β-Ga2O3.

Iron impurities are believed to act as deep acceptors that can compensate for the n-type conductivity in as-grown Ga2O3, but several scientific issues, such as the site occupation of the Fe heteroatom and the complexes of Fe-doped β-Ga2O3 with native defects, are still lacking. In this paper, based on first-principle density functional theory calculations with the generalized gradient approximation approach, the controversy regarding the preferential Fe incorporation on the Ga site in the β-Ga2O3 crystal has been addressed, and our result demonstrates that Fe dopant is energetically favored on the octahedrally coordinated Ga site. The structural stabilities are confirmed by the formation energy calculations, the phonon dispersion relationships, and the strain-dependent analyses. The thermodynamic transition level Fe3+/Fe2+ is located at 0.52 eV below the conduction band minimum, which is consistent with Ingebrigtsen's theoretical conclusion, but slightly smaller than some experimental values between 0.78 eV and 1.2 eV. In order to provide direct guidance for material synthesis and property design in Fe-doped β-Ga2O3, the defect formation energies, charge transitional levels, and optical properties of the defective complexes with different kinds of native defects are investigated. Our results show that VGa and Oi can be easily formed for the Fe-doped β-Ga2O3 crystals under O-rich conditions, where the +3 charge state FeGaGai and -2 charge state FeGaOi are energetically favorable when the Fermi level approaches the valence and conduction band edges, respectively. Optical absorption shows that the complexes of FeGaGai and FeGaVGa can significantly enhance the optical absorption in the visible-infrared region, while the energy-loss function in the β-Ga2O3 material is almost negligible after the extra introduction of various intrinsic defects.

Linking Significant Zr Isotopic Fractionation in Magmatic Zircons With Petrographic Textures

AbstractThe origin of crystal‐scale Zr isotopic variation remains enigmatic. Here, we report high‐precision Zr isotopic compositions of thin‐sectioned and hand‐picked zircon crystals from monzodiorites and K‐feldspar granites, which represent the mafic and felsic products of a differentiating magma. Our results reveal that zircons from both rock associations are dominated by a rim‐ward increase in the 94Zr/90Zr ratio and accompanied by ∼1‰ intracrystalline and intercrystalline variations, confirming the preferential incorporation of light Zr isotopes and thus kinetic isotopic fractionation during zircon growth. Notably, zircons enclosed by K‐feldspar in monzodiorites generally yield lower 94Zr/90Zr and higher Zr/Hf ratios than that of separated crystals, while in K‐feldspar granites, tiny zircons intergrown with apatite obtain higher 94Zr/90Zr but lower Zr/Hf ratios relative to that of sizable separates. The diversity in petrographic textures and sizes of zircon crystals, corresponding to their crystallization sequence, potentially accounts for some of the heterogeneity of Zr isotopes at the mineral scale.

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.

Alternating Copolymerization of Epoxides and Isothiocyanates to Diverse Functional Polythioimidocarbonates and Related Block Polymers†

Comprehensive SummarySynthesis of diverse polythioimidocarbonates via ring‐opening copolymerization of epoxides and isothiocyanates catalyzed by organoboron catalyst was reported herein. Both aromatic and aliphatic isothiocyanates underwent successful copolymerization with terminal and internal epoxides, allowing for the precise tuning of the performance of the resultant copolymers over a broad range. The wide scope of available isothiocyanates and epoxides enables the direct construction of sulfur‐containing functional polymers featuring both high glass transition temperature and refractive index. Additionally, it was observed that aromatic isothiocyanates polymerize much faster than aliphatic ones, and the reactivity difference facilitated the one‐step synthesis of block polymers from mixed aromatic isothiocyanates, aliphatic isothiocyanates and epoxides due to the preferential incorporation of aromatic isothiocyanates over the aliphatic analogues during their alternating copolymerization with epoxides. The produced polythioimidocarbonates can be used as positive resists for electron beam lithography (sensitivity of 130 μC/cm2 and contrast of 1.53 for poly(CHO‐alt‐EITC)). Coupling with their high refractive index (1.58—1.68), polythioimidocarbonates might find functional applications in optics. These results render ring‐opening copolymerization of epoxides and isothiocyanates a facile route to enrich functional polymer library.

Investigation of Gas Evolution by Operando GC/MS from SEI Forming Additives in Lithium-Ion-Batteries

Due to the chemical reactivity of the electrolyte, electrolyte decomposition often occurs at the electrode-electrolyte interface during cycling, which can lead to a loss in LIB performance. On the anode side, however, the formation of a stable Solid Electrolyte Interphase (SEI) is essential for the safe operation of Lithium-ion batteries (LIBs). The SEI layer, which is permeable for Li+ ions, protects the electroactive materials from direct contact with the electrolyte, thereby inhibiting further electrolyte decomposition. In the formation cycles of fresh cells, electrolyte degradation is primarily attributed to the SEI formation processes at the anode. Several literature reports have confirmed that the newly formed interphase consists of organic and inorganic decomposition products of the electrolyte.1 To increase battery performance, cycle life and safety, it is essential to form a stable SEI.2 A common strategy to stabilize the SEI is to use additives in the electrolyte composition. The additives should exhibit higher reduction potentials than other electrolyte components to enable preferential reduction and incorporation into the SEI. The most common SEI forming additives are fluoroethylene carbonate (FEC) and vinylene carbonate (VC). They both decompose during the formation cycle to form a polymeric layer at the electrode surface.The electrolyte decomposition reactions which lead to SEI formation are usually accompanied by gaseous side products. The evolving gas species form a complex gas mixture which can be separated by gas chromatography (GC) into their individual components and subsequently identified by mass spectrometry (MS). While operando GC/MS gives information on the volatile side products of the electrolyte decomposition reactions, X-ray photoelectron spectroscopy (XPS) can be used to identify the degradation products that form on the surface of the electrode and are incorporated into the SEI. The combination of the two techniques allows a more comprehensive picture of SEI formation processes to be drawn.In this work, operando GC/MS of Lithium-ion full cells with NMC 811 cathodes and graphite anodes was used to compare the gas species evolving during the formation reactions in an electrolyte with the composition of 1M LiPF6 in EC/DEC 1:1 with FEC and VC electrolyte additives in a ratio of 1w%, respectively. In a comparative study we present the decomposition pathways of the electrolytes with and without SEI forming additives by analysing the composition of the gas phase as a function of cell potential. We observe that the complex gas mixture consists of carbonate components originating from transesterification reactions and evaporation of the volatile electrolyte. In addition, inorganic components such as carbon monoxide and carbon dioxide are produced, which mainly stem from the degradation of cyclic carbonates. Furthermore, the gas phase consists of saturated and unsaturated hydrocarbons which can be ascribed to the linear carbonate components as well as ether and carbonyl components. We have also observed that it is possible to distinguish between volatile compounds which form during the charge and discharge processes, respectively. The increased gas evolution at the beginning of the formation cycle confirms that a substantial part of the passivation layer is formed during charge. Finally, operando GC/MS was also used to monitor the evolution of the decomposition products during battery operation at overcharge conditions.Acknowledgement:The author gratefully acknowledges the FFG (Austrian Research Promotion Agency) for funding this research within project No. 879613