Light Isotopes Research Articles

Stable isotope ecology of terra preta in Caxiuanã National Forest, Brazil

The Amazon Basin currently hosts the world’s largest pool of terrestrial biodiversity and prior to European colonization of the Americas there were large human communities living in parkland ecosystems. We examine the formation of archaeological sites in the northeast sector of the Caxiuanã National Forest (CNF) using light stable isotopes of nitrogen and carbon, total carbon and nitrogen and Optically Stimulated Luminescence to characterize long-term human landscape management practices. Previous research in the CNF has documented differences in pH, calcium, total organic carbon (TOC) and nitrogen (TN) between terra preta and terra marrom contexts as well as different forest structures based on remote sensing analysis. Therefore, we adopt a comparative approach, examining the formation processes of on-site (terra preta), near-site (terra marrom) and offsite (latosol) contexts. TOC and TN values obtained in our study augment and support previous research demonstrating significantly higher on-site values relative to near-site and off-site. However, the stable isotopes (δ13C, δ15N) assayed from terra preta, terra marrom and latosols show statistically overlapping values, indicating the persistence of closed canopy in off-site and near-site contexts and the use of this canopy in the formation of on-site soils (terra preta). Our results corroborate the hypothesis that closed canopy ecosystems and human settlements persisted in the Amazon for thousands of years and formed the foundation of the region’s rich biodiversity.

Silicon and iron isotopes in components of enstatite chondrites: Implications for metal–silicate–sulfide fractionation in the solar nebula

AbstractSilicon and iron isotope compositions of different physically separated components of enstatite chondrites (EC) were determined in this study to understand the role of nebular and planetary scale events in fractionating Si and Fe isotopes of the terrestrial planet‐forming region. We found that the metal–sulfide nodules of EC are strongly enriched in light Si isotopes (δ30Si ≥ −5.61 ± 0.12‰, 2SD), whereas the δ30Si values of angular metal grains, magnetic, slightly magnetic, and non‐magnetic fractions become progressively heavier, correlating with their Mg# (Mg/(Mg+Fe)). White mineral phases, composed primarily of SiO2 polymorphs, display the heaviest δ30Si of up to +0.23 ± 0.10‰. The data indicate a key role of metal–silicate partitioning on the Si isotope composition of EC. The overall lighter δ30Si of bulk EC compared to other planetary materials can be explained by the enrichment of light Si isotopes in EC metals along with the loss of isotopically heavier forsterite‐rich silicates from the EC‐forming region. In contrast to the large Si isotope heterogeneity, the average Fe isotope composition (δ56Fe) of EC components was found to vary from −0.30 ± 0.08‰ to +0.20 ± 0.04‰. A positive correlation between δ56Fe and Ni/S in the components suggests that the metals are enriched in heavy Fe isotopes whereas sulfides are the principal hosts of light Fe isotopes in the non‐magnetic fractions of EC. Our combined Si and Fe isotope data in different EC components reflect an inverse correlation between δ30Si and δ56Fe, which illustrates that partitioning of Si and Fe among metal, silicate, and sulfidic phases has significantly fractionated Si and Fe isotopes under reduced conditions. Such isotope partitioning must have occurred before the diverse components were mixed to form the EC parent body. Evaluation of diffusion coefficients of Si and Fe in the metal and non‐metallic phases suggests that the Si isotope compositions of the silicate fractions of EC largely preserve information of their nebular processing. On the other hand, the Fe isotopes might have undergone partial or complete re‐equilibration during parent body metamorphism. The relatively uniform δ56Fe among different types of bulk chondrites and the Earth, despite Fe isotope differences among their components, demonstrates that the chondrite parent bodies were not formed by random mixing of chondritic components from different locations in the disk. Instead, the chondrite components mostly originated in the same nebular reservoir and Si and Fe isotopes were fractionated either due to gas–solid interactions and associated changes in physicochemical environment of the nebular reservoir and/or during parent body processing. The heavier Si isotope composition of the bulk silicate Earth may require accretion of chondritic and/or isotopically heavier EC silicates along with cumulation of refractory forsterite‐rich heavier silicates lost from the EC‐forming region to form the silicate reservoir of the Earth.

Uniquely low stable iron isotopic signatures in deep marine sediments caused by Rayleigh distillation

Dissimilatory iron reduction (DIR) is suggested to be one of the earliest forms of microbial respiration. It plays an important role in the biogeochemical cycling of iron in modern and ancient sediments. Since microbial iron cycling is typically accompanied by iron isotope fractionation, stable iron isotopes are used as tracer for biological activity. Here we present iron isotope data for dissolved and sequentially extracted sedimentary iron pools from deep and hot subseafloor sediments retrieved in the Nankai Trough off Japan. Dissolved iron (Fe(II)aq) is isotopically light throughout the ferruginous sediment interval but some samples have exceptionally light isotope values. Such light values have never been reported in natural marine environments and cannot be solely attributed to DIR. We show that the light isotope values are best explained by a Rayleigh distillation model where Fe(II)aq is continuously removed from the pore water by adsorption onto iron (oxyhydr)oxide surfaces. While the microbially mediated Fe(II)aq release has ceased due to an increase in temperature beyond the threshold of mesophilic microorganisms, the abiotic adsorptive Fe(II)aq removal continued, leading to uniquely light isotope values. These findings have important implications for the interpretation of dissolved iron isotope data especially in deep subseafloor sediments.

Cadmium isotope fractionation during sorption to soil minerals: Lab evidence and field implication

Stable isotope is a potent geochemical tracer unveiling the dynamic sources of cadmium (Cd) in the environment. However, the sorption process of aqueous Cd onto solid surfaces (e.g., soil) fractionates isotopic signatures, which makes it difficult to interpret its sources and migration processes. Understanding how Cd fractionates during sorption to soil minerals, therefore, provides necessary data to open the isotope fractionation black box of liquid-solid phase partition of Cd. In this study, we explored isotopic fractionation characteristics during Cd sorption to typical soil minerals. Distinct Cd isotope fractionation was observed during sorption, including goethite (∆114/110Cdsolid−solution=−0.51∼−0.47‰), montmorillonite (−0.34∼−0.32‰), quartz (−0.34∼−0.30‰), gibbsite (−0.29∼−0.25‰), and kaolinite (−0.09∼−0.07‰), where lighter isotopes tended to be preferentially sorbed to the solid phase in a reversible manner. We've also conducted a field survey in a historical flooding-affected region to explore Cd isotopic compositions of soil samples adjacent to a polluted creek. Distinct isotopic signatures for surficial soils and deep soils were observed, which was depicted by a binary mixing mode. Leaching of Cd from mine tailings to the creek, as well as its re-adsorption to soil during historical flooding events both led to preferential enrichment of light isotopes in the solid phase, which was consistent with findings from lab sorption experiments. Mineralogical analyses including EPMA, TOF-SIMS, Mössbauer spectra, XRD, and chemical extraction tests, were applied to unveil how Cd was bound to soil minerals at field. Possible linkage between lab and field data were discussed on the basis of these findings. Results from this study are encouraging for future application of Cd isotopes for source tracing.

The RICH detector of the AMS-02 experiment aboard the International Space Station

The Alpha Magnetic Spectrometer (AMS) is a high-energy particle physics magnetic spectrometer installed on the International Space Station (ISS) in May 2011, successfully operating and taking data since then. The goal of the experiment is to carry out accurate measurements of galactic Cosmic Rays spectra in a wide energy range from GeV/n to TeV/n and search for rare components as hints of the presence of Dark Matter and Anti-Matter. The AMS instrument includes a Ring Imaging Čerenkov (RICH), which provides a precise measurement of the particle velocity and electric charge. The AMS-RICH layout follows a proximity focusing design with two radiators: at the center there are sodium fluoride tiles surrounded by silica aerogel ones. No significant indications of degradation of the radiator properties have been observed in more than 11 years of operation in space and 95% of the detection sensors is working nominally. The velocity and charge responses are stable in time and their resolution fulfills the design requirements. The impact of the RICH detector in the AMS physics program will be highlighted and the most recent results on light isotopes in cosmic rays will be discussed, with a particular attention to the AMS capabilities to identify Beryllium isotopes.

Neutron Scattering Studies of Heterogeneous Catalysis.

Understanding the structural dynamics/evolution of catalysts and the related surface chemistry is essential for establishing structure-catalysis relationships, where spectroscopic and scattering tools play a crucial role. Among many such tools, neutron scattering, though less-known, has a unique power for investigating catalytic phenomena. Since neutrons interact with the nuclei of matter, the neutron-nucleon interaction provides unique information on light elements (mainly hydrogen), neighboring elements, and isotopes, which are complementary to X-ray and photon-based techniques. Neutron vibrational spectroscopy has been the most utilized neutron scattering approach for heterogeneous catalysis research by providing chemical information on surface/bulk species (mostly H-containing) and reaction chemistry. Neutron diffraction and quasielastic neutron scattering can also supply important information on catalyst structures and dynamics of surface species. Other neutron approaches, such as small angle neutron scattering and neutron imaging, have been much less used but still give distinctive catalytic information. This review provides a comprehensive overview of recent advances in neutron scattering investigations of heterogeneous catalysis, focusing on surface adsorbates, reaction mechanisms, and catalyst structural changes revealed by neutron spectroscopy, diffraction, quasielastic neutron scattering, and other neutron techniques. Perspectives are also provided on the challenges and future opportunities in neutron scattering studies of heterogeneous catalysis.

Calcium isotope fractionation associated with adsorption and desorption on/from δ-MnO2

Small mineral particles present in soils, such as clay minerals and some oxyhydroxides, constitute important nutrient reservoirs. This behavior is due to the negative charges and high specific surface areas of these particles allowing them to adsorb cations such as calcium (Ca), a macronutrient that occupies key physiological and structural functions in plant metabolism. Although the chemical reactivity of clay minerals is rather well-known in the literature, especially toward macronutrients such as Ca, that of oxyhydroxides such as phyllomanganate minerals remains largely unexplored.To enhance our understanding of the mechanisms at the origin of the storage/release of the different isotopes of Ca in a soil solution, the possible fractionation between 40Ca and 44Ca during adsorption and desorption of Ca on a synthetic phyllomanganate, abiotically precipitated in the laboratory [synthetic analog of vernadite (δ-MnO2)], was studied. Experiments were performed in batch (closed system), and several parameters (time, pH of the solution, Ca concentration and nature and concentration of the desorbent) were tested to cover a large range of physicochemical conditions.This study demonstrated that the light 40Ca isotope is preferentially adsorbed on δ-MnO2, with Δ44/40Ca (the apparent fractionation of the aqueous solution at the stationnary state of adsorption compared to the initial one) of the adsorbed Ca that can reach 1.19 ± 0.15‰. The results showed that this isotopic fractionation occurs at chemical equilibrium in a closed system and that the isotopic fractionation measured in this study during Ca adsorption on phyllomanganate is significantly higher than that reported in the literature during Ca adsorption on other soil constituents such as clay minerals. At pH below 4 Ca occupies only the interlayer/basal sites whereas above this pH Ca fills interlayer/basal sites (∼86%) and edges sites (∼14%). By combining the experimental data obtained at different pH values, initial Ca concentrations and interaction times, our results suggest that isotopic signature of the Ca adsorbed on δ-MnO2 is dependent on the nature of the site involved in the adsorption step (i.e., enriched in 40Ca in the interlayer with Δ44/40Ca equal to −0.43‰ and enriched in 44Ca when bound to the edges with Δ44/40Ca equal to +3.5‰). As revealed by surface complexation modeling, such contrasting behavior between the two types of adsorption sites could be due to the bidendate nature of the Ca adsorption occurring on edges and to ion exchange of Ca2+ with H+ in the interlayer sites. Finally, desorption experiments point to total but not instantaneous Ca desorption, probably due to a partial collapse of the interlayer with some ions used to desorb Ca2+ (K+, NH4+, hexaamine-cobalt). This suggests that the amount of bioavailable Ca in soils by simple ion-exchange reactions is highly dependent on the nature of the ions which could desorb Ca present in the soil solution.

Nickel mass balance and isotopic records in a serpentinic weathering profile: Implications on the continental Ni budget

During serpentinite rock weathering, Ni is concentrated in the regolith owing to residual and secondary enrichment, forming a Ni-rich deposit under tropical conditions. This study presents geochemical, isotopic, and mineralogical data for Ni from the Serra do Puma Complex (SPC) weathering profile in Carajas (Brazil). The Ni fluxes, redistribution, and Ni isotopic fractionation magnitudes were quantified along the entire weathering profile: rock, saprock, lower and upper saprolite, and limonite. The results show that chlorite and serpentine are the primary Ni-scavenging phases in saprolite, whereas Fe oxyhydroxides are the main Ni-hosting minerals in the limonite unit. The mass balance model confirmed a global Ni gain at the weathered profile scale, with larger Ni enrichment in the upper saprolite. The isotopic dataset obtained in this study contributes greatly to the knowledge of the current Ni cycle on regional and global scales. The detailed insights into Ni isotopes in the SPC, coupled with chemical and mineralogical composition, allow for the first time a Ni mass balance and Ni isotopic values for an entire weathering profile in an Amazonian context. The Ni isotopic profile agrees with the preferential retention of light Ni isotopes in the residual material relative to the parent rock during weathering processes, with the Δ60Ni limonite-saprock of −0.72‰. In the SPC, major isotopic fractionation was notably recorded during saprolitization, while limonitization was accompanied by an overall Ni loss without significant Ni isotopic fractionation. As already observed in previous studies, heavier Ni isotopes, preferentially leached during weathering processes, can be further mobilized downward and lost from the profile or incorporated in secondary minerals in the saprolite and limonite sections. The Ni isotopic mass balance model indicated that the Ni loss from the weathered serpentinite profile was isotopically heavy, in agreement with the isotopically heavier composition of the dissolved load of Amazonian rivers. The isotopically light Ni pool, associated with the significant Ni gain encountered in the upper saprolite, is notable in the SPC weathering profile and confirms the existence of a light Ni isotope reservoir in the continent.

Site-specific isotope effect: Insights from equilibrium magnesium isotope fractionation in mantle minerals

The equilibrium Mg isotope fractionation factors (lnα) derived from both theoretical calculation and experimental studies are not consistent with the values from natural sample observation. Different cation sites, which have identical coordinate numbers but different bond strengths, contribute equally to lnα in theoretical calculations. These non-equivalent sites might complicate the inter-mineral equilibrium isotope fractionations. Here, we investigate reduced partition function ratios (103lnβ) of non-equivalent Mg cation sites (e.g., M1, M2, and M3) in forsterite, orthoenstatite, clinoenstatite, tremolite, omphacite, pyrope and spinel to explore the site-specific effect on the intra- and inter-mineral equilibrium isotope fractionation. Based on all-electron first-principles calculations, 103lnβ in different cation sites decreases in the following sequence of spinelM1 > tremoliteM3 > orthoenstatiteM1 > forsteriteM1 > omphaciteM1 > tremoliteM1 > tremoliteM2 > clinoenstatiteM1 > forsteriteM2 > orthoenstatiteM2 > clinoenstatiteM2 > pyropeM1. These findings suggest that cation sites with larger polyhedron volumes prefer light Mg isotopes to those with smaller polyhedron volumes inside minerals, and the different contribution of intra-mineral cation sites could result in significant variations of equilibrium Mg isotope fractionation between minerals. The range of lnα between minerals induced by specific sites is defined as the equilibrium isotope fractionation domain. The site-corrected lnα can provide better evaluation of equilibrium fractionation factor of Mg isotopes between spinel and olivine and clarify the equilibrium state between mantle minerals. In addition, we establish spinel-olivine and omphacite-pyrope Mg isotope geothermometers based on the site-specific effect. This study suggests that the site-specific effect could be prevalent in solid materials and thus important for other isotope systems.

Petroleum in the Jurassic Reservoirs within the Eastern Fukang Sub‐depression, Junggar Basin, NW China: Correlation and Source Rock

AbstractThe origin and source of the petroleum in the Jurassic reservoirs within the eastern Fukang sub‐depression were geochemically investigated. They show thermal maturities matching the peak generation stage, while the condensates are at the early stage of intense cracking. Oils and condensates may have experienced mild evaporative fractionation, while mixing of severely biodegraded with non‐biodegraded oils has occurred. Using biomarkers and isotopes, petroleums were classified into Group I, II and III genetic groups, with Group III further divided into IIIa and IIIb subgroups. Group I petroleum displays heavy carbon isotopes, a strong predominance of pristine over phytane, high C19 and C20 tricyclic and C24 tetracyclic terpanes, low gammacerane, and dominant C29 steranes, while Group II shows light carbon isotopes, a predominance of phytane over pristine, high C21 and C23 tricyclic with low C24 tetracyclic terpanes, high gammacerane and dominant C27 steranes. Group IIIa petroleum shows mixing compositions of Group I and II, while Group IIIb displays similar compositions to Group I, but with significantly higher Ts, C29Ts and C30 diahopane proportions. Oil‐source rock correlation suggests Group I and II petroleums originate from Jurassic and Permian source rocks, respectively, while Group IIIa are mixtures sourced from these rocks and IIIb are mixtures from Jurassic and Triassic source rocks.

Impact of Snowmelt Conditions on the Isotopic Composition of the Surface Waters of the Upper Ob River during the Flood Period

For many of the Siberian rivers, and the Upper Ob in particular, 70–80% of the volume of the annual water runoff is formed during the spring flood. Thus, factors influencing the formation of water runoff during the spring flood are paramount. We explain changes in the isotopic composition of the Upper Ob surface waters by changing different components’ contribution to the runoff water discharge over the spring flood period. We suggest estimating the time of meltwater flow from the Upper Ob watershed to the outlet section using the difference between the date of the complete melting of the snow cover in the catchment area and the date of the maximum light isotope composition of water in the outlet section. We show that a sharp short-term weighting of the isotopic composition of water in the river at the end of the first phase of the flood may be associated with the influx of autumn soil moisture, displaced from the soils by snowmelt waters.

Nuclear physics with TriSol at Notre Dame’s Nuclear Science Laboratory

The detailed study of radioactive nuclei has resulted in opportunities for addressing many open questions in low-energy nuclear physics. For over three decades, the TwinSol separator at the University of Notre Dame has produced high-quality in-flight radioactive beams at low-energy for light isotopes that have been used in experiments aimed at nuclear structure, astrophysics, and fundamental symmetries studies. We have recently upgraded the TwinSol separator by adding additional elements: a dipole magnet, and a third solenoid. This new TriSol separator will improve the quality and purity of future radioactive beams. This improvement will enable the use of heavier beams and address beam contamination that has hindered past experiments. The current status of TriSol and its science program will be presented along with the role the TriSol program plays in the current landscape of nuclear physics user facilities. The TriSol program includes plans for studies of 11C(p, p)11C reaction for investigating the nature of the first stars, 14O(α, p)17F and its influence on reaction networks in X-ray bursts, the measurement of fusion reactions on Ne isotopes important for pycnonuclear reactions, precision half-life measurements for fundamental symmetries studies, and the use of TriSol as a magnetic spectrometer.

Continental weathering as the source of iron in Jurassic iron oolites from Switzerland

Iron is extremely insoluble in oxic seawater. The lack of a large aqueous reservoir means that sediments rich in authigenic iron are rare in the modern ocean. In the Middle Jurassic, however, condensed iron-rich sedimentary rocks are widely distributed. Their formation coincides with increased volcanic activity and continental weathering related to the breakup of Pangea, suggesting iron supply through one of these processes. We studied three Swiss shallow-marine iron oolites from Herznach, Windgällen and Erzegg, all from condensed sedimentary sequences of Middle to early Late Jurassic age, to constrain the source of iron to these rocks, combining radiogenic neodymium, strontium and stable iron isotope analyses. Leached authigenic neodymium isotope compositions, which appear to preserve the primary signature, serve as a tracer for the potential involvement of hydrothermal fluids in the formation of the iron oolites. The three iron oolite successions yield crustal Nd isotope compositions (εNd between − 9 and − 7), providing no evidence for the involvement of such fluids. It is, thus, more likely that iron in the sediments derived from detrital fluvial inputs. Strontium isotope compositions, which could potentially support these findings, point to metamorphic overprinting associated with Alpine thrusting. The light iron isotope signatures associated with Middle to early Late Jurassic condensed sequences, δ56Fe between − 1.49 and − 0.57‰, suggest that microbially-mediated iron reduction was also involved in generating these sediments.

Carbon and hydrogen dynamic isotope equations are used to describe the dominant processes of waste biodegradation: Effect of aeration in methanogenic phase of the landfill

The sequence of microbiological processes occurring during the decomposition of fresh and old organic wastes from landfills is analyzed using the developed dynamic models, which are verified on the basis of experimental data previously obtained in anaerobic and aerobic laboratory reactors. The models are based on the material balances of the heavy and light isotopes of carbon and hydrogen during the biodegradation of cellulosic waste as a relatively poorly degradable substrate. According to the models, under anaerobic conditions, dissolved carbon dioxide is a substrate for hydrogenotrophic methanogenesis, which leads to an increase in the isotope signature of carbon in carbon dioxide and its subsequent stabilization. After the introduction of aeration, methane production ceases, and from that time on, carbon dioxide remains only a product of cellulose and acetate oxidation, which causes a significant decrease in the isotopic signature of carbon in carbon dioxide. The dynamics of the deuterium content in the leachate water is described as a consequence of the rate of its entry into and exit from the two (upper and lower) compartments of the vertical reactors, as well as the rates of its consumption and formation during microbiological reactions. According to the models, in the anaerobic case, the water is first enriched with deuterium due to acidogenesis and syntrophic acetate oxidation and then diluted with deuterium-depleted water, which is continuously fed to the top of the reactors. In the aerobic case, a similar dynamic is simulated.

Muon Spin Rotation (μSR) for Characterizing Radical Addition to C=S in Xanthene-9-thione and Thioxanthene-9-thione

Abstract Muonium (μ+e−) can be produced by capture of an electron by a spin-polarized muon (μ+) and has been utilized as a light isotope of hydrogen. In this paper, we demonstrate muon spin rotation (μSR) experiments and preliminary computational analyses of the regioselective muonium addition to xanthene-9-thione and thioxanthene-9-thione providing the C-centered radicals. The transverse-field muon spin rotation (TF-μSR) experiments of the cyclic thioketones revealed considerable increase of muon hyperfine coupling constants (muon hfc, Aμ) compared with the muoniated thiobenzophenone, indicating crucial roles of the bridging chalcogen atom promoting the overlap between the S–Mu bond orbital and the radical p orbital.

Antimony isotope fractionation and the key controls in the soil profiles of an antimony smelting area

The controlling factors of antimony migration and transformation in soil profiles are still unclear. Antimony isotopes might be a useful tool to trace it. In this paper, antimony isotopic compositions of plant and smelter-derived samples, and two soil profiles were measured for the first time. The δ123Sb values of the surface and bottom layers of the two soil profiles varied in 0.23‰−1.19‰ and 0.58‰−0.66‰, respectively, while δ123Sb of the smelter-derived samples varied in 0.29‰−0.38‰. The results show that the antimony isotopic compositions in the soil profiles are affected by post-depositional biogeochemical processes. The enrichment and loss of light isotopes at 0–10 cm and 10–40 cm layers of the contrasted soil profile may be controlled by plant uptake process. The loss and enrichment of heavy isotopes in the 0–10 cm and 10–25 cm layers of the antimony from smelting source in the polluted soil profile may be controlled by the adsorption process, while the enrichment of light isotopes in the 25–80 cm layer may be related to the reductive dissolution process. The conclusion emphasizes that the promotion of the Sb isotope fractionation mechanism will play a crucial role in understanding the migration and transformation behaviors of Sb in soil systems.

Effects of Light Shading, Fertilization, and Cultivar Type on the Stable Isotope Distribution of Hybrid Rice.

The effect of fertilizer supply and light intensity on the distribution of elemental contents (%C and %N) and light stable isotopes (C, N, H, and O) in different rice fractions (rice husk, brown rice, and polished rice) of two hybrid rice cultivars (maintainer lines You-1B and Zhong-9B) were investigated. Significant variations were observed for δ13C (-31.3 to -28.3‱), δ15N (2.4 to 2.7‱), δ2H (-125.7 to -84.7‱), and δ18O (15.1‱ to 23.7‱) values in different rice fractions among different cultivars. Fertilizer treatments showed a strong association with %N, δ15N, δ2H, and δ18O values while it did not impart any significant variation for the %C and δ13C values. Light intensity levels also showed a significant influence on the isotopic values of different rice fractions. The δ13C values showed a positive correlation with irradiance. The δ2H and δ15N values decreased with an increase in the irradiance. The light intensity levels did not show any significant change for δ18O values in rice fractions. Multivariate ANOVA showed a significant interaction effect of different factors (light intensity, fertilizer concentration, and rice variety) on the isotopic composition of rice fractions. It is concluded that all environmental and cultivation factors mentioned above significantly influenced the isotopic values and should be considered when addressing the authenticity and origin of rice. Furthermore, care should be taken when selecting rice fractions for traceability and authenticity studies since isotopic signatures vary considerably among different rice fractions.

Cadmium accumulation and isotope fractionation in typical protozoa Tetrahymena: A new perspective on remediation of Cd pollution in wastewater

Cadmium (Cd) pollution threatens water safety and human health, which has raised serious public concern. Tetrahymena is a model protozoan, possessing the potential to remediate Cd contaminated water given the rapid expression of thiols. However, the mechanism of Cd accumulation in Tetrahymena has not been well understood, which hinders its application in environmental remediation. This study elucidated the pathway of Cd accumulation in Tetrahymena using Cd isotope fractionation. Our results showed that Tetrahymena preferentially absorb light Cd isotopes, with Δ114/110CdTetrahymena−solution = −0.20 ± 0.02‰ ∼ − 0.29 ± 0.02‰, which implies that the intracellular Cd is probably in the form of Cd−S. The fractionation generated by Cd complexation with thiols is constant (Δ114/110CdTetrahymena−remaining solution ∼ −0.28 ± 0.02‰), which is not affected by the concentrations of Cd in intracellular and culture medium, nor by the physiological changes in cells. Furthermore, the detoxification process of Tetrahymena results in an increase in cellular Cd accumulation from 11.7% to 23.3% with the elevated Cd concentrations in batch Cd stress culture experiments. This study highlights the promising application of Cd isotope fractionation in Tetrahymena for the remediation of heavy metal pollution in water.

A search for life in Palaeoproterozoic marine sediments using Zn isotopes and geochemistry

Sediments from the 2.1- to 1.9-billion-year-old Francevillian Group in southeastern Gabon include centimeter-sized pyritized structures suggestive of colonial organisms (El Albani et al., 2010), some of which may have been motile (El Albani et al., 2019). However, these interpretations were largely based on morphological and geochemical characteristics that lack metabolic clues and/or can be explained by abiotic processes. To move this work forward, we describe other centimeter-sized specimens, loosely referred to as lenticular forms (LF), from the same area and apply a more holistic approach including morphology, mineralogy, and geochemistry. The objects are 0.2–4 cm in diameter, and most of them are endowed with a regular brim that scales proportionally to external diameter reminiscent of biological order, hence rendering the LF putative biogenic traces. The LF are perfectly delineated in every direction and deflect the sedimentary layers on which they rest. X-ray microtomography further demonstrates that the LF are syn-depositional features and not concretions, while lead isotope systematics indicate that the geochemical imprint of diagenesis is inconsequential. Low sulfur content is largely concentrated in the organic matrix, and scarcity of pyrite and its persistence as micron-sized crystals show that the role of sulfate reduction is minor. Most interestingly, the fillings of the LF cavities show large and correlated excesses of organic carbon and zinc, with the latter being distinctly enriched in its light isotopes. The geochemical anomalies of the fillings relative to the host rock, notably those associated with Zn, clearly were buried with the LF, and further imply biogenicity. In this regard, a ten-fold increase in LF size towards the top of the black shale series hosting the LF might be related to increasing Zn (nutrient) availability. Although we cannot conclude with any certainty what these remnant organisms were, their features all taken together are evocative of very large agglutinate protists that grazed on bacterial biomass either in the water column or as benthic mats.

Gallium isotopic constraints for the origin of the Earth-Moon system

Comparatively heavy isotopic compositions of moderately volatile elements (MVE) in lunar rocks have been advocated to reflect the loss of light isotopes during devolatilization processes from the Moon. In this study we present new gallium (Ga) isotope data for lunar highland rocks, with a focus on the Ferroan Anorthosite Suite (FAS). These are commonly thought to be direct crystallization products from the late lunar magma ocean (LMO) and should contain the majority of the Ga inventory of the Moon. As such, FAS rocks are crucial for identifying the processes that drove Ga isotope fractionation as well as for inferring the Ga isotopic composition of the bulk Moon.Our data reveal that FAS samples have a range in δ71Ga from −0.27 to 0.22‰ and are generally isotopically light in Ga compared to other lunar lithologies, but straddle values typical of terrestrial rocks. Although Ga is defined as an MVE, these Ga isotope variations do not correspond with concentrations of more volatile elements, indicating that Ga isotope variations in the FAS are not primarily controlled by devolatilization processes. Instead, the Ga isotopic compositions of bulk FAS rocks broadly correlate with the composition of plagioclase, with the calcium content of plagioclase decreasing as Ga becomes isotopically heavier. This suggests that fractionation of Ga isotopes in FAS rocks was caused by the preferential incorporation of isotopically light Ga into plagioclase during the later solidification stages of the LMO. The progressive crystallization and extraction of plagioclase forces the residual melt towards increasingly heavier Ga isotope ratios, corroborating similar conclusions derived from correlations between δ71Ga and Eu* in the mare basalt suite.Using Ga isotope partitioning calculations, we demonstrate that an isotope fractionation coefficient between plagioclase and coexisting melt of −0.3 to -0.4‰ could explain the observed range of δ71Ga values in FAS, mare basalt suite rocks, and KREEP. These calculations allow for a first order estimate of the Ga isotopic composition of the bulk silicate Moon prior to plagioclase fractionation and suggest it was close to the composition of the bulk silicate Earth. This would imply that the Moon did not lose a substantial fraction of its Ga inventory during accretion, consistent with new constraints from Rb-Sr isotope systematics that indicate the Moon's volatile deficit was primarily inherited from Theia. In conjunction with the overlap in non-mass-dependent isotope ratios, these collective observations could be reconciled if Theia and the proto-Earth formed in similar regions of the inner Solar System that were already volatile-depleted.