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Samples of the carbonaceous asteroid Ryugu were brought to Earth by the Hayabusa2 spacecraft. We analyzed 17 Ryugu samples measuring 1 to 8 millimeters. Carbon dioxide-bearing water inclusions are present within a pyrrhotite crystal, indicating that Ryugu's parent asteroid formed in the outer Solar System. The samples contain low abundances of materials that formed at high temperatures, such as chondrules and calcium- and aluminum-rich inclusions. The samples are rich in phyllosilicates and carbonates, which formed through aqueous alteration reactions at low temperature, high pH, and water/rock ratios of <1 (by mass). Less altered fragments contain olivine, pyroxene, amorphous silicates, calcite, and phosphide. Numerical simulations, based on the mineralogical and physical properties of the samples, indicate that Ryugu's parent body formed ~2 million years after the beginning of Solar System formation.

We investigated interfacial reactions of U(VI) in the presence of Suwannee River natural organic matter (NOM) at acidic and neutral pH. Laboratory batch experiments show that the adsorption and precipitation of U(VI) in the presence of NOM occur at pH 2 and pH 4, while the aqueous complexation of U by dissolved organic matter is favored at pH 7, preventing its precipitation. Spectroscopic analyses indicate that U(VI) is mainly adsorbed to the particulate organic matter at pH 4. However, U(VI)-bearing ultrafine to nanocrystalline solids were identified at pH 4 by electron microscopy. This study shows the promotion of U(VI) precipitation by NOM at low pH which may be relevant to the formation of mineralized deposits, radioactive waste repositories, wetlands, and other U- and organic-rich environmental systems.

We have performed sound velocity and unit cell volume measurements of three synthetic, ultrafine micro/nanocrystalline grossular samples up to 50 GPa using Brillouin spectroscopy and synchrotron X-ray diffraction. The samples are characterized by average grain sizes of 90 nm, 93 nm and 179 nm (hereinafter referred to as samples Gr90, Gr93, and Gr179, respectively). The experimentally determined sound velocities and elastic properties of Gr179 sample are comparable with previous measurements, but slightly higher than those of Gr90 and Gr93 under ambient conditions. However, the differences diminish with increasing pressure, and the velocity crossover eventually takes place at approximately 20-30 GPa. The X-ray diffraction peaks of the ultrafine micro/nanocrystalline grossular samples significantly broaden between 15-40 GPa, especially for Gr179. The velocity or elasticity crossover observed at pressures over 30 GPa might be explained by different grain size reduction and/or inhomogeneous strain within the individual grains for the three grossular samples, which is supported by both the pressure-induced peak broadening observed in the X-ray diffraction experiments and transmission electron microscopy observations. The elastic behavior of ultrafine micro/nanocrystalline silicates, in this case, grossular, is both grain size and pressure dependent., (© 2021. The Author(s).)

This paper reports the successful synthesis of true two-dimensional silicon carbide using a top-down synthesis approach. Theoretical studies have predicted that 2D SiC has a stable planar structure and is a direct band gap semiconducting material. Experimentally, however, the growth of 2D SiC has challenged scientists for decades because bulk silicon carbide is not a van der Waals layered material. Adjacent atoms of SiC bond together via covalent sp 3 hybridization, which is much stronger than van der Waals bonding in layered materials. Additionally, bulk SiC exists in more than 250 polytypes, further complicating the synthesis process, and making the selection of the SiC precursor polytype extremely important. This work demonstrates, for the first time, the successful isolation of 2D SiC from hexagonal SiC via a wet exfoliation method. Unlike many other 2D materials such as silicene that suffer from environmental instability, the created 2D SiC nanosheets are environmentally stable, and show no sign of degradation. 2D SiC also shows interesting Raman behavior, different from that of the bulk SiC. Our results suggest a strong correlation between the thickness of the nanosheets and the intensity of the longitudinal optical (LO) Raman mode. Furthermore, the created 2D SiC shows visible-light emission, indicating its potential applications for light-emitting devices and integrated microelectronics circuits. We anticipate that this work will cause disruptive impact across various technological fields, ranging from optoelectronics and spintronics to electronics and energy applications.

We investigated the mechanisms of uranium (U) uptake by Tamarix (salt cedars) growing along the Rio Paguate, which flows throughout the Jackpile mine near Pueblo de Laguna, New Mexico. Tamarix were selected for this study due to the detection of U in the roots and shoots of field collected plants (0.6-58.9 mg kg-1), presenting an average bioconcentration factor greater than 1. Synchrotron-based micro X-ray fluorescence analyses of plant roots collected from the field indicate that the accumulation of U occurs in the cortex of the root. The mechanisms for U accumulation in the roots of Tamarix were further investigated in controlled-laboratory experiments where living roots of field plants were macerated for 24 h or 2 weeks in a solution containing 100 μM U. The U concentration in the solution decreased 36-59% after 24 h, and 49-65% in two weeks. Microscopic and spectroscopic analyses detected U precipitation in the root cell walls near the xylems of the roots, confirming the initial results from the field samples. High-resolution TEM was used to study the U fate inside the root cells, and needle-like U-P nanocrystals, with diameter <7 nm, were found entrapped inside vacuoles in cells. EXAFS shell-by-shell fitting suggest that U is associated with carbon functional groups. The preferable binding of U to the root cell walls may explain the U retention in the roots of Tamarix, followed by U-P crystal precipitation, and pinocytotic active transport and cellular entrapment. This process resulted in a limited translocation of U to the shoots in Tamarix plants. This study contributes to better understanding of the physicochemical mechanisms affecting the U uptake and accumulation by plants growing near contaminated sites.

The crystal chemistry of carnotite (prototype formula: K 2 (UO 2 ) 2 (VO 4 ) 2 ·3H 2 O) occurring in mine wastes collected from Northeastern Arizona was investigated by integrating spectroscopy, electron microscopy, and x-ray diffraction analyses. Raman spectroscopy confirms that the uranyl vanadate phase present in the mine waste is carnotite, rather than the rarer polymorph vandermeerscheite. X-ray diffraction patterns of the carnotite occurring in these mine wastes are in agreement with those reported in the literature for a synthetic analog. Carbon detected in this carnotite was identified as organic carbon inclusions using transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses. After excluding C and correcting for K-drift from the electron microprobe analyses, the composition of the carnotite was determined as 8.64% K 2 O, 0.26% CaO, 61.43% UO 3 , 20.26% V 2 O 5 , 0.38% Fe 2 O 3 , and 8.23% H 2 O. The empirical formula, (K 1.66 Ca 0.043 Al(OH) 2+ 0.145 Fe(OH) 2+ 0.044 )((U 0.97 )O 2 ) 2 ((V 1.005 )O 4 ) 2 ·4H 2 O of the studied carnotite, with an atomic ratio 1.9:2:2 for K:U:V, is similar to the that of carnotite (K 2 (UO 2 ) 2 (VO 4 ) 2 ·3H 2 O) reported in the literature. Lattice spacing data determined using selected area electron diffraction (SAED)-TEM suggests: (1) complete amorphization of the carnotite within 120 s of exposure to the electron beam and (2) good agreement of the measured d -spacings for carnotite in the literature. Small Differences between the measured and literature d -spacing values are likely due to the varying degree of hydration between natural and synthetic materials. Such information about the crystal chemistry of carnotite in mine wastes is important for an improved understanding of the occurrence and reactivity of U, V, and other elements in the environment., Competing Interests: Conflicts of Interest: The authors declare no conflict of interest. Any opinions, findings, and conclusions or recommendations expressed in this publication are those of the author(s) and do not necessarily reflect the views of the National Science Foundation or the National Institute of Environmental Health Sciences.

A coordinated mineralogical and oxygen isotopic study of four fine-grained calcium-, aluminum-rich inclusions (CAIs) from the ALHA77307 CO3.0 carbonaceous chondrite was conducted. Three of the inclusions studied, 05, 1-65, and 2-119, all have nodular structures that represent three major groups, melilite-rich, spinel-rich, and hibonite-rich, based on their primary core mineral assemblages. A condensation origin was inferred for these CAIs. However, the difference in their primary core mineralogy reflects unique nebular environments in which multiple gas-solid reactions occurred under disequilibrium conditions to form hibonite, spinel, and melilite with minor perovskite and Al,Ti-rich diopside. A common occurrence of a diopside rim on the CAIs records a widespread event that marks the end of their condensation as a result of isolation from a nebular gas. An exception is a rare inclusion 2-112 that contains euhedral spinel crystals embedded in melilite, suggesting this CAI had been re-melted. All of the fine-grained CAIs analyzed in ALHA77307 are uniformly 16 O-rich with an average Δ 17 O value of ~-22 ± 5‰ (2σ), indicating no apparent correlation between their textures and oxygen isotopic compositions. We therefore conclude that a prevalent 16 O-rich gas reservoir existed in a region of the solar nebula where CO3 fine-grained CAIs formed, initially by condensation and then later, some of them were reprocessed by melting event(s).

The role of calcium (Ca) on the cellular distribution of U(VI) in Brassica juncea roots and root-to-shoot translocation was investigated using hydroponic experiments, microscopy, and spectroscopy. Uranium accumulated mainly in the roots (727-9376 mg kg -1 ) after 30 days of exposure to 80 μ M dissolved U in water containing 1 mM HCO 3 - at different Ca concentrations (0-6 mM) at pH 7.5. However, the concentration of U in the shoots increased 22 times in experiments with 6 mM Ca compared to 0 mM Ca. In the Ca control experiment, transmission electron microscopy-energy-dispersive spectroscopy analyses detected U-P-bearing precipitates in the cortical apoplast of parenchyma cells. In experiments with 0.3 mM Ca, U-P-bearing precipitates were detected in the cortical apoplast and the bordered pits of xylem cells. In experiments with 6 mM Ca, U-P-bearing precipitates aggregated in the xylem with no apoplastic precipitation. These results indicate that Ca in carbonate water inhibits the transport and precipitation of U in the root cortical apoplast and facilitates the symplastic transport and translocation toward shoots. These findings reveal the considerable role of Ca in the presence of carbonate in facilitating the transport of U in plants and present new insights for future assessment and phytoremediation strategies., Competing Interests: The authors declare no competing financial interest.

Dust condensation and coagulation in the early solar system are the first steps toward forming the terrestrial planets, but the time scales of these processes remain poorly constrained. Through isotopic analysis of small Ca-Al-rich inclusions (CAIs) (30 to 100 μm in size) found in one of the most pristine chondrites, Allan Hills A77307 (CO3.0), for the short-lived 26 Al- 26 Mg [ t 1/2 = 0.72 million years (Ma)] system, we have identified two main populations of samples characterized by well-defined 26 Al/ 27 Al = 5.40 (±0.13) × 10 -5 and 4.89 (±0.10) × 10 -5 . The result of the first population suggests a 50,000-year time scale between the condensation of micrometer-sized dust and formation of inclusions tens of micrometers in size. The 100,000-year time gap calculated from the above two 26 Al/ 27 Al ratios could also represent the duration for the Sun being a class I source.

We integrated field measurements, hydroponic experiments, microscopy, and spectroscopy to investigate the effect of Ca(II) on dissolved U(VI) uptake by plants in 1 mM HCO 3 - solutions at circumneutral pH. The accumulation of U in plants (3.1-21.3 mg kg -1 ) from the stream bank of the Rio Paguate, Jackpile Mine, New Mexico served as a motivation for this study. Brassica juncea was the model plant used for the laboratory experiments conducted over a range of U (30-700 μg L -1 ) and Ca (0-240 mg L -1 ) concentrations. The initial U uptake followed pseudo-second-order kinetics. The initial U uptake rate ( V 0 ) ranged from 4.4 to 62 μg g -1 h -1 in experiments with no added Ca and from 0.73 to 2.07 μg g -1 h -1 in experiments with 12 mg L -1 Ca. No measurable U uptake over time was detected for experiments with 240 mg L -1 Ca. Ternary Ca-U-CO 3 complexes may affect the decrease in U bioavailability observed in this study. Elemental X-ray mapping using scanning transmission electron microscopy-energy-dispersive spectrometry detected U-P-bearing precipitates within root cell walls in water free of Ca. These results suggest that root interactions with Ca and carbonate in solution affect the bioavailability of U in plants. This study contributes relevant information to applications related to U transport and remediation of contaminated sites.

We applied spectroscopy, microscopy, diffraction, and aqueous chemistry methods to investigate the persistence of metals in water and sediments from the Animas River 13 days after the Gold King Mine spill (August 5, 2015). The Upper Animas River watershed, located in San Juan Colorado, is heavily mineralized and impacted by acid mine drainage, with low pH water and elevated metal concentrations in sediments (108.4 ± 1.8 mg kg -1 Pb, 32.4 ± 0.5 mg kg -1 Cu, 729.6 ± 5.7 mg kg -1 Zn, and 51 314.6 ± 295.4 mg kg -1 Fe). Phosphate and nitrogen species were detected in water and sediment samples from Farmington, New Mexico, an intensive agricultural area downstream from the Animas River, while metal concentrations were low compared to those observed upstream. Solid-phase analyses of sediments suggest that Pb, Cu, and Zn are associated with metal-bearing jarosite and other minerals (e.g., clays, Fe-(oxy)hydroxides). The solubility of jarosite at near-neutral pH and biogeochemical processes occurring downstream could affect the stability of metal-bearing minerals in river sediments. This study contributes relevant information about the association of metal mixtures in a heavy mineralized semiarid region, providing a foundation to better understand long-term metal release in a public and agricultural water supply.

The chemical interactions of U and co-occurring metals in abandoned mine wastes in a Native American community in northeastern Arizona were investigated using spectroscopy, microscopy and aqueous chemistry. The concentrations of U (67-169 μg L(-1)) in spring water samples exceed the EPA maximum contaminant limit of 30 μg L(-1). Elevated U (6,614 mg kg(-1)), V (15,814 mg kg(-1)), and As (40 mg kg(-1)) concentrations were detected in mine waste solids. Spectroscopy (XPS and XANES) solid analyses identified U (VI), As (-I and III) and Fe (II, III). Linear correlations for the release of U vs V and As vs Fe were observed for batch experiments when reacting mine waste solids with 10 mM ascorbic acid (∼pH 3.8) after 264 h. The release of U, V, As, and Fe was at least 4-fold lower after reaction with 10 mM bicarbonate (∼pH 8.3). These results suggest that U-V mineral phases similar to carnotite [K2(UO2)2V2O8] and As-Fe-bearing phases control the availability of U and As in these abandoned mine wastes. Elevated concentrations of metals are of concern due to human exposure pathways and exposure of livestock currently ingesting water in the area. This study contributes to understanding the occurrence and mobility of metals in communities located close to abandoned mine waste sites.

Chlorine in the Earth is highly depleted relative to carbonaceous chondrites and solar abundances. Knowledge of the Cl concentrations and distribution on Earth is essential for understanding the origin of these depletions. Large differences in the stable chlorine isotope ratios of meteoritic, mantle and crustal materials have been used as evidence for distinct reservoirs in the solar nebula and to calculate the relative proportions of Cl in the mantle and crust. Here we report that large isotopic differences do not exist, and that carbonaceous chondrites, mantle and crust all have the same 37Cl/35Cl ratios. We have further analysed crustal sediments from the early Archaean era to the Recent epoch and find no systematic isotopic variations with age, demonstrating that the mantle and crust have always had the same delta37Cl value. The similarity of mantle, crust and carbonaceous chondrites establishes that there were no nebular reservoirs with distinct isotopic compositions, no isotopic fractionation during differentiation of the Earth and no late (post-core formation) Cl-bearing volatile additions to the crustal veneer with a unique isotopic composition.

Matrix olivines in the Allende carbonaceous chondrite are believed to have formed by condensation processes in the primitive solar nebula. However, transmission electron microscope observations of numerous matrix olivines show that they contain abundant, previously unrecognized, nanometer-sized inclusions of pentlandite and poorly graphitized carbon. Neither of these phases would have been stable at the high-temperature conditions required to condense iron-rich olivine in the solar nebula. The presence of these inclusions is consistent with formation of the olivines by parent body processes that involved overgrowth of fine-grained organic materials and sulfides in the precursor matrix materials.

Transmission electron microscope observations of the Allende carbonaceous chondrite provided evidence of widespread hydrous phases replacing enstatite in chondrules. Calcic amphibole and talc occur in thin (less than 0.3 micrometer) crosscutting veins and as alteration products of primary chondrule glass in contraction cracks within the enstatite. In addition, talc and disordered biopyriboles were found replacing enstatite grains along cracks and fractures. Although rare hydrous phases have been reported in calcium- and aluminum-rich inclusions in the Allende meteorite, these observations suggest that aqueous fluids played a much more significant role in the mineralogical and geochemical evolution of Allende than has previously been thought.

The concentrations of Ni, Cu, Zn, Ga, Ge, and Se in five, fine-grained chondrule rims in the highly unequilibrated CO3 chondrite ALH A77307 (3.0) have been determined for the first time by synchrotron X-ray fluorescence (SXRF) microprobe at Brookhaven National Laboratory. These elements are especially useful for tracing the role of condensation and evaporation processes which occurred at moderate temperatures in the solar nebula. Understanding the distribution of moderately volatile elements between matrix and chondrules is extremely important for evaluating the different models for the volatile depletions in chondritic meteorites. The data show that the trace element chemistry of rims on different chondrules is remarkably similar, consistent with data obtained for the major and minor elements by electron microprobe. These results support the idea that rims are not genetically related to individual chondrules, but all sampled the same reservoir of homogeneously mixed dust. Of the trace elements analyzed, Zn and Ga show depletions relative to CI chondrite values, but in comparison with bulk CO chondrites all the elements are enriched by approximately 1.5 to 3.5 x CO. The abundance patterns for moderately volatile elements in ALH A77307 chondrule rims closely mimic those observed in the bulk chondrite, indicating that matrix is the major reservoir for these elements. The close matching of the patterns for the volatile depleted bulk chondrite and enriched matrix is especially striking for Na, which is anomalously depleted in ALH A77307 in comparison with average CO chondrite abundances. The depletion in Na is probably attributable to the effects of leaching in Antarctica. With the exception of Na, the volatile elements show a relatively smooth decrease in abundance as a function of condensation temperature, indicating that their behavior is largely controlled by their volatility.

Ferromagnesian olivine, one of the most common minerals in the solar system, has been widely regarded as a continuous solid solution, although several thermodynamic analyses have suggested the possibility of a miscibility gap at low temperatures. Natural ferromagnesian olivine from the Divnoe meteorite contains compositionally different exsolution lamellae, providing direct evidence for the existence of a miscibility gap in iron-magnesium olivine solid solutions.

The mechanisms of the phase transformations between the spinel (gamma) and modified spinel (beta) polymorphs of Mg(2)SiO(4) have been studied experimentally between 15 and 20 gigapascals and 800 degrees to 950 degrees C. The gamma to beta transformation occurs by a shear mechanism, whereas the beta to gamma transformation involves grain-boundary nucleation and interface-controlled growth. These contrasting mechanisms are a consequence of the number of independent slip systems that are available in the respective crystal structures. This result leads to the prediction that in subduction zones and perhaps also rising plumes in the Earth's mantle, the gamma to beta transformation should be accompanied by a transient reduction in strength.