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At least 505 records · Page 28

Distribution and speciation of Sb and toxic metal(loid)s near an antimony refinery and their effects on indigenous microorganisms

Although several studies have investigated the effects of Sb contamination on surrounding environments and indigenous microorganisms, little is known about the effect of co-contamination of Sb and toxic metal(loid)s. In this study, the occurrence of Sb and other toxic metal(loid)s near an operating Sb refinery and near-field landfill site were investigated. Topsoil samples near the refinery had high Sb levels (~3250 mg kg -1 ) but relatively low concentrations of other toxic metal(loid)s. However, several soil samples taken at greater depth from the near-field landfill site contained high concentrations of As and Pb, as well as extremely high Sb contents (~21,400 mg kg -1 ). X-ray absorption fine structure analysis showed that Sb in the soils from both sites was present as Sb(V) in the form of tripuhyite (FeSbO 4 ), a stable mineral. Three-dimensional principal coordinate analysis showed that microbial community compositions in samples with high toxic metal(loid)s concentrations were significantly different from other samples and had lower microbial populations (~10 4 MPN g -1 ). Sequential extraction results revealed that Sb is present primarily in the stable residual fraction (~99 %), suggesting low Sb bioavailability. Finally, however, microbial redundancy analysis suggested that the more easily extractable Pb might be the major factor controlling microbial community compositions at the site.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

A Bis(imidazole)-based cysteine labeling tool for metalloprotein assembly

Precise metal-protein coordination by design remains a considerable challenge. Polydentate, high-metal-affinity protein modifications, both chemical and recombinant, can enable metal localization. However, these constructs are often bulky, conformationally and stereochemically ill-defined, or coordinately saturated. Here, we expand the biomolecular metal-coordination toolbox with the irreversible attachment to cysteine of bis(1-methylimidazol-2-yl)ethene (“BMIE”), which generates a compact imidazole-based metal-coordinating ligand. Conjugate additions of small-molecule thiols (thiocresol and N-Boc-Cys) with BMIE confirm general thiol reactivity. The BMIE adducts are shown to complex the divalent metal ions Cu ++ and Zn ++ in bidentate (N 2 ) and tridentate (N 2 S*) coordination geometries. Cysteine-targeted BMIE modification (>90% yield at pH 8.0) of a model protein, the S203C variant of carboxypeptidase G2 (CPG2), measured with ESI-MS, confirms its utility as a site-selective bioconjugation method. ICP-MS analysis confirms mono-metallation of the BMIE-modified CPG2 protein with Zn ++ , Cu ++ , and Co ++ . EPR characterization of the BMIE-modified CPG2 protein reveals the structural details of the site selective 1:1 BMIE-Cu ++ coordination and symmetric tetragonal geometry under physiological conditions and in the presence of various competing and exchangeable ligands (H 2 O/HO – , tris, and phenanthroline). An X-ray protein crystal structure of BMIE-modified CPG2-S203C demonstrates that the BMIE modification is minimally disruptive to the overall protein structure, including the carboxypeptidase active sites, although Zn ++ metalation could not be conclusively discerned at the resolution obtained. The carboxypeptidase catalytic activity of BMIE-modified CPG2-S203C was also assayed and found to be minimally affected. Finally, these features, combined with ease of attachment, define the new BMIE-based ligation as a versatile metalloprotein design tool, and enable future catalytic and structural applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metagenomic strategies identify diverse integron–integrase and antibiotic resistance genes in the Antarctic environment

The objective of this study is to identify and analyze integrons and antibiotic resistance genes (ARGs) in samples collected from diverse sites in terrestrial Antarctica. Integrons were studied using two independent methods. One involved the construction and analysis of intI gene amplicon libraries. In addition, we sequenced 17 metagenomes of microbial mats and soil by high-throughput sequencing and analyzed these data using the IntegronFinder program. As expected, the metagenomic analysis allowed for the identification of novel predicted intI integrases and gene cassettes (GCs), which mostly encode unknown functions. However, some intI genes are similar to sequences previously identified by amplicon library analysis in soil samples collected from non-Antarctic sites. ARGs were analyzed in the metagenomes using ABRIcate with CARD database and verified if these genes could be classified as GCs by IntegronFinder. We identified 53 ARGs in 15 metagenomes, but only four were classified as GCs, one in MTG12 metagenome (Continental Antarctica), encoding an aminoglycoside-modifying enzyme (AAC(6´)acetyltransferase) and the other three in CS1 metagenome (Maritime Antarctica). One of these genes encodes a class D β-lactamase (blaOXA-205) and the other two are located in the same contig. One is part of a gene encoding the first 76 amino acids of aminoglycoside adenyltransferase (aadA6), and the other is a qacG2 gene.

59 BASIC BIOLOGICAL SCIENCES↗

Fixed-Site KAZR b1 Data Processing: Corrections, Calibrations, and Processing Report

The U.S. Department of Energy’s (DOE) Atmospheric Radiation Measurement (ARM) User Facility operates three fixed-site observatories: Eastern North Atlantic (ENA), North Slope of Alaska (NSA), and Southern Great Plains (SGP). Each fixed site has a wide variety of atmospheric instrumentation that has been collecting data for at least 10 years (NSA and SGP over 25 years). Each site is unique because it represents a different climate state. The environment at ENA is characterized by marine stratocumulus clouds and one of the key scientific areas of focus is the interaction of these clouds with aerosols. At NSA the focus is on arctic climate and cloud and radiative processes in a high-latitude environment. SGP represents a mid-latitude, mid-continent climate that experiences environmental cycles on diurnal and seasonal time scales. The ARM observatories are all meant to improve understanding of atmospheric processes that can then be better incorporated into weather and climate models. Another common thread between the fixed sites is the focus on cloud processes. Each site is equipped with at least one radar that provides continuous remote-sensing observations of clouds and precipitation. This report details the analysis of a1-level radar data at the fixed sites and the process for generating b1-level data. While b1-level data have been produced for ARM campaigns at the mobile facilities, this is the first analysis led by ARM radar mentors to correct data at the fixed sites. In particular, we focus on calibrations and corrections of the Ka-band ARM Zenith Radars (KAZRs) at ENA, NSA, and SGP. Ongoing and future work will involve corrections applied to other fixed-site radars.

54 ENVIRONMENTAL SCIENCES↗

Symmetry-mediated quantum coherence of W 5+ spins in an oxygen-deficient double perovskite

Elucidating the factors limiting quantum coherence in real materials is essential to the development of quantum technologies. Here we report a strategic approach to determine the effect of lattice dynamics on spin coherence lifetimes using oxygen deficient double perovskites as host materials. In addition to obtaining millisecond T 1 spin-lattice lifetimes at T ~ 10 K, measurable quantum superpositions were observed up to room temperature. We determine that T 2 enhancement in Sr 2 CaWO 6-δ over previously studied Ba 2 CaWO 6-δ is caused by a dynamically-driven increase in effective site symmetry around the dominant paramagnetic site, assigned as W 5+ via electron paramagnetic resonance spectroscopy. Further, a combination of experimental and computational techniques enabled quantification of the relative strength of spin-phonon coupling of each phonon mode. This analysis demonstrates the effect of thermodynamics and site symmetry on the spin lifetimes of W 5+ paramagnetic defects, an important step in the process of reducing decoherence to produce longer-lived qubits.

36 MATERIALS SCIENCE↗

Updates to Composite Analysis Base Case and Null Space Monte Carlo Sensitivity Based on New Unit Dose Factors

This environmental calculation file (ECF) presents the results of the exposure route-specific and total radiological dose assessments for the groundwater exposure pathway as a part of the updated Composite Analysis for Low-Level Waste Disposal in the Hanford Site Central Plateau (FY 2022), based on revised unit dose factors (UDFs) published in CA Special Studies: Updates to the Groundwater Pathway Radiological Dose. The reason for these radiological dose assessments is to estimate the cumulative radiological impacts from all screened sources of ionizing radiation and exposure routes that could potentially contribute to the projected dose to a hypothetical member of the public. Sources of ionizing radiation can include existing or future disposal facilities and other sources including past-practice discharge sites. Additionally, the results of the exposure route-specific and total radiological dose assessments have been revised for the groundwater pathway based on the null space Monte Carlo (NSMC) groundwater concentrations and the most recent updates to the UDFs as a part an uncertainty analysis for the updated Hanford Site CA.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Compilation of Site Names and Spatial Extents for Sites in the Hanford Site Disposition Database

Several analyses that will be completed as part of the Hanford Composite Analysis (CA) and Cumulative Impact Evaluation (CIE) require the extents of facilities, waste sites, and other locations on the Hanford Site. The purpose of this calculation is to provide spatial extents and consistent naming convention for those locations used as part of the analyses in a single dataset. This calculation documents the process used to develop the dataset.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Stream Chemistry, Synoptic Surveys, East Fork Poplar Creek Watershed, TN, USA; April 2023 to February 2025

Impacts of developed land cover on stream chemistry can be difficult to discern from natural variability, particularly in carbonate watersheds where weathering of urban infrastructure and lithology generate similar signatures. We evaluated how spatial patterns of stream chemistry varied across perennial and non-perennial tributaries spanning an urban-to-forested gradient in a mid-order, carbonate-dominated watershed. This data package contains a processed and compiled summary of stream chemistry and properties obtained from 12 synoptic surveys of 54 stream sites across the East Fork Poplar Creek watershed located near Oak Ridge, TN, United States. The sites include non-perennial tributaries, perennial tributaries, and the main stem and span forested to urban (highly developed) land cover gradients. The data package includes the processed and flagged chemical data (WaDE_SynopticSummary_FinalChemistry), metadata describing data flagging and analysis (WaDE_SynopticSummary_Metadata), information about each site and its contributing subcatchment (WaDE_SynopticSummary_SiteInformation), and a comparison of instrument and field detection limits used to determine method detection limits for the study (WaDE_SynopticSummary_DetectionLimitComparison). Stream chemistry includes stream parameters measured in situ using multiparameter probes (dissolved oxygen, pH, specific conductance, temperature) and solutes including nutrients (nitrate, ammonium, soluble reactive phosphorus), dissolved organic carbon, dissolved inorganic carbon, major cations (calcium, magnesium, potassium, sodium), major anions (chloride, sulfate), and a broad suite of minor and trace elements.

EARTH SCIENCE > TERRESTRIAL HYDROSPHERE > SURFACE ↗

Integrated Experimental and Computational K-Edge X-ray Absorption Near-Edge Structure Analysis of Vanadium Catalysts

X-ray Absorption Near-Edge Structure (XANES) spectroscopy is a powerful tool to reveal key structural and electronic features of isolated catalytic sites, yet insights into molecular structure and more detailed orbital analysis through a combination of experimental and computed XANES analysis are necessary for accurate interpretation of the spectra, especially when significant heterogeneity exits among the catalytic sites. Herein, we present an integrated computational and experimental strategy to determine both primary and secondary bonding interactions within the XANES pre-edge region for organovanadium complexes, which was developed using a series of well-defined molecular vanadium complexes and then applied to the characterization of a supported organovanadium olefin hydrogenation catalyst. Time-dependent density functional theory is used to predict the energy of pre-edge XANES features for a series of vanadium complexes with a variety of oxidation states and local coordination environments. Further, a calibration scheme incorporating different density functionals and basis sets is established, resulting in an optimized scheme that accurately predicts pre-edge energies with a mean absolute error of 0.40 eV. Second-shell coordination (e.g., V---V) effects within XANES are identified through the analysis of the computed dominant orbital contributions for multi-vanadium complexes. Orbital analysis also provided confirmation that the vanadium-hydride formation combined with the heterogeneity of the catalytic active species in ole-fin hydrogenation caused the energy shift and broadening of the pre-edge peak after hydrogen treatment of the silica-supported organovanadium pre-catalyst. This work further elucidates computational XANES simulations and techniques potentially guiding characterization in surface organometallic chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Room temperature polar and weak-ferromagnetic oxide with low dielectric loss

Single-phase materials that are simultaneously ferroelectric and ferromagnetic at room temperature are promising for devices such as non-volatile random-access memory. Perovskite BiFeO 3 which crystallizes in the polar rhombohedral structure (R3c) is ferroelectric and antiferromagnetic at room temperature. Here, we report a family of perovskite oxides in the BiFeO 3 – Bi 2/3 TiO 3 – ATiO 3 (where A 2+ is divalent alkaline earth metal ions e.g., Ca 2+ , Sr 2+ , Ba 2+ ) ternary phase diagram that is polar as well as weak ferromagnetic above room temperature. The composition (Bi 0.9167 A 0.075 )(Fe 0.9 Ti 0.1 )O 3 crystallizes in the polar rhombohedral structure space group R3c as corroborated by powder X-ray and neutron diffraction analysis. The nearly pure A-site perovskite possesses a long-range magnetic ordering above room temperature. Finally, these perovskites show a low dielectric loss, and the electrical response is dominated by grain contributions below 723 K.

42 ENGINEERING↗

Electronic and thermal properties of the phase-change memory material, Ge 2 Sb 2 Te 5 , and results from spatially resolved transport calculations

Here, we report new insights into the electronic, structural, and transport (heat and charge) properties of the phase-change memory material amorphous Ge 2 Sb 2 Te 5 . Using realistic structural models of Konstantinou et al., (2019), we analyze the topology, electronic states, and lattice dynamics with density functional methods, including hybrid-functional calculations and machine-learned interatomic potentials. The Kohn–Sham orbitals near the Fermi level display a strong electron–phonon coupling, and exhibit large energy fluctuations at room temperature. The conduction tail states exhibit larger phonon-induced fluctuations than the valence tail states. To resolve transport at the atomic scale, we employ space-projected electronic conductivity and site-projected thermal conductivity methods. Local analysis of heat transport highlights the role of filamentary networks dominated by Te, with Sb and Ge making progressively smaller contributions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Involvement of TFAP2A in the activation of GSDMD gene promoter in hyperoxia-induced ALI

Highlights: • Hyperoxia exposure increases GSDMD expression in rat lung tissue and A549 cells. • The core promoter region of GSDMD located in −98/-12 bp relative to TSS. • E2F4 and TFAP2A positively regulate the basal transcriptional activity of GSDMD by directly binding to its promoter. • TFAP2A directly drives the expression of GSDMD in hyperoxia-inducedA549 cells. • TFAP2A expression is increased in lung tissues of rats with hyperoxia-induced ALI and linearly correlated with GSDMD. Oxygen therapy is a common treatment in neonatal intensive care units, but long-term continuous hyperoxia ventilation may induce acute lung injury (ALI). Gasdermin D (GSDMD)-mediated pyroptosis participates in various diseases including ALI, but the role of GSDMD in hyperoxia-induced ALI is yet understood. Here, we showed a significant increase in GSDMD after exposure to high oxygen. To elucidate the molecular mechanisms involved in GSDMD regulation, we identified the core promoter of GSDMD, −98 ~ −12 bp relative to the transcriptional start site (TSS). The results of mutational analysis, overexpression or siRNA interference, EMSA and ChIP demonstrated that E2F4 and TFAP2A positively regulate the transcriptional activity of the GSDMD by binding to its promoter. However, only TFAP2A showed a regulatory effect on the expression of GSDMD. Moreover, TFAP2A was increased in the lung tissues of rats exposed to hyperoxia and showed a strong linear correlation with GSDMD. Our results indicated that TFAP2A positively regulates the GSDMD expression via binding to the promoter region of GSDMD.

60 APPLIED LIFE SCIENCES↗

Temperature and Water Levels Collectively Regulate Methane Emissions From Subtropical Freshwater Wetlands

Abstract Wetlands are the largest and most climate‐sensitive natural sources of methane. Accurately estimating wetland methane emissions involves reconciling inversion (“top‐down”) and process‐based (“bottom‐up”) models within the global methane budget. However, estimates from these two model types are inherently interdependent and often reveal substantial discrepancies. To enhance the reliability of both approaches, we need a comprehensive understanding of wetland methane emissions and an independent high‐resolution long‐term flux data set. Here, we employed a data‐driven random forest approach to identify key variables influencing methane emissions from subtropical freshwater wetlands in the Southeastern United States. The model‐estimated monthly mean methane fluxes fit well with measured methane fluxes ( R 2 = 0.67) at four representative FLUXNET‐CH4 wetland sites across the region. Variable importance analysis highlighted the sensitivity of subtropical freshwater wetland methane emissions to variations in both temperature and water levels. High temperatures facilitate methanogenesis by enhancing microbial activities, while elevated water levels maintain anaerobic conditions necessary for methane production. Notably, the response of methane emissions to water level fluctuations is contingent on temperature conditions, and vice versa. Moreover, we constructed the first high‐spatial‐resolution (∼1 km × 1 km) and long‐term (1982–2010) gridded regional wetland methane flux product for the Southeastern United States, estimating annual methane emissions from subtropical freshwater wetlands in the region at 4.93 ± 0.11 Tg CH 4 yr −1 for 1982–2010. This new benchmark product holds promise for validating and parameterizing uncertain wetland methane emission processes in bottom‐up models and provides improved prior information for top‐down models.

He, Keqi [Earth and Climate Sciences Nicholas Scho↗

Structure of pre-miR-31 reveals an active role in Dicer–TRBP complex processing

As an essential posttranscriptional regulator of gene expression, microRNA (miRNA) levels must be strictly maintained. The biogenesis of many miRNAs is mediated by trans-acting protein partners through a variety of mechanisms, including remodeling of the RNA structure. miR-31 functions as an oncogene in numerous cancers, and interestingly, its biogenesis is not known to be regulated by protein-binding partners. Therefore, the intrinsic structural properties of the precursor element of miR-31 (pre-miR-31) can provide a mechanism by which its biogenesis is regulated. We determined the solution structure of pre-miR-31 to investigate the role of distinct structural elements in regulating processing by the Dicer–TRBP complex. We found that the presence or absence of mismatches within the helical stem does not strongly influence Dicer–TRBP processing of the pre-miRNAs. However, both the apical loop size and structure at the Dicing site are key elements for discrimination by the Dicer–TRBP complex. Interestingly, our NMR-derived structure reveals the presence of a triplet of base pairs that link the Dicer cleavage site and the apical loop. Mutational analysis in this region suggests that the stability of the junction region strongly influences processing by the Dicer–TRBP complex. Our results enrich our understanding of the active role that RNA structure plays in regulating miRNA biogenesis, which has direct implications for the control of gene expression.

59 BASIC BIOLOGICAL SCIENCES↗

Critical needs to close monitoring gaps in pan-tropical wetland CH 4 emissions

Global wetlands are the largest and most uncertain natural source of atmospheric methane (CH 4 ). The FLUXNET-CH 4 synthesis initiative has established a global network of flux tower infrastructure, offering valuable data products and fostering a dedicated community for the measurement and analysis of methane flux data. Existing studies using the FLUXNET-CH 4 Community Product v1.0 have provided invaluable insights into the drivers of ecosystem-to-regional spatial patterns and daily-to-decadal temporal dynamics in temperate, boreal, and Arctic climate regions. However, as the wetland CH 4 monitoring network grows, there is a critical knowledge gap about where new monitoring infrastructure ought to be located to improve understanding of the global wetland CH 4 budget. Here we address this gap with a spatial representativeness analysis at existing and hypothetical observation sites, using 16 process-based wetland biogeochemistry models and machine learning. We find that, in addition to eddy covariance monitoring sites, existing chamber sites are important complements, especially over high latitudes and the tropics. Furthermore, expanding the current monitoring network for wetland CH 4 emissions should prioritize, first, tropical and second, sub-tropical semi-arid wetland regions. Considering those new hypothetical wetland sites from tropical and semi-arid climate zones could significantly improve global estimates of wetland CH 4 emissions and reduce bias by 79% (from 76 to 16 TgCH 4 y -1 ), compared with using solely existing monitoring networks. Our study thus demonstrates an approach for long-term strategic expansion of flux observations.

54 ENVIRONMENTAL SCIENCES↗

Single crystal growth, chemical defects, magnetic and transport properties of antiferromagnetic topological insulators ( Ge 1 – δ – x Mn x ) 2 Bi 2 Te 5 ( x ≤ 0.47 , 0.11 ≤ δ ≤ 0.20 )

Magnetic topological insulators provide a platform for emergent phenomena arising from the interplay between magnetism and band topology. Here we report the single crystal growth, crystal structure, magnetic and transport properties, as well as the neutron scattering studies of topological insulator series (Ge 1–δ–x Mn x ) 2 ⁢Bi 2 ⁢Te 5 (x ≤ 0.47, 0.11 ≤ δ ≤ 0.20). Upon doping up to x = 0.47, the lattice parameter c decreases by 0.8%, while the lattice parameter a remains nearly unchanged. Significant Ge vacancies and Ge/Bi site mixing are revealed via elemental analysis as well as refinements of the neutron and x-ray diffraction data, resulting in holes dominating the charge transport. At x = 0.47, below 10.8 K, a bilayer A-type antiferromagnetic ordered state emerges, featuring an ordered moment of 3.0(3) μ B /Mn at 5 K, with the c axis as the easy axis. Magnetization data unveils a much stronger effective interlayer antiferromagnetic exchange interaction and a much smaller uniaxial anisotropy compared to MnBi 2 ⁢Te 4 . We attribute the former to the shorter nearest-neighbor Mn-Mn interlayer superexchange path and the latter to the smaller ligand-field splitting in (Ge 1–δ–x ⁢Mn x ) 2 ⁢Bi 2 ⁢Te 5 . Finally, our study demonstrates that this series of materials holds promise for the investigation of the layer Hall effect and quantum metric nonlinear Hall effect.

36 MATERIALS SCIENCE↗

Cytochrome P450–catalyzed biosynthesis of furanoditerpenoids in the bioenergy crop switchgrass ( Panicum virgatum L.)

Specialized diterpenoid metabolites are important mediators of plant-environment interactions in monocot crops. To understand metabolite functions in plant environmental adaptation that ultimately can enable crop improvement strategies, a deeper knowledge of the underlying species-specific biosynthetic pathways is required. Furthermore, we report the genomics-enabled discovery of five cytochrome P450 monooxygenases (CYP71Z25-CYP71Z29) that form previously unknown furanoditerpenoids in the monocot bioenergy crop Panicum virgatum (switchgrass). Combinatorial pathway reconstruction showed that CYP71Z25-CYP71Z29 catalyze furan ring addition directly to primary diterpene alcohol intermediates derived from distinct class II diterpene synthase products. Transcriptional co-expression patterns and the presence of select diterpenoids in switchgrass roots support the occurrence of P450-derived furanoditerpenoids in planta. Integrating molecular dynamics, structural analysis and targeted mutagenesis identified active site determinants that contribute to the distinct catalytic specificities underlying the broad substrate promiscuity of CYP71Z25-CYP71Z29 for native and non-native diterpenoids.

59 BASIC BIOLOGICAL SCIENCES↗

Dataset for report: Non-Technical Barriers to Geothermal Development in California and Nevada

In California and Nevada, geothermal projects are subject to non-technical barriers, which may create development delays leading to higher project costs and risks and decreased competitiveness with other electricity generation technologies. These non-technical barriers may include federal and state permits, authorizations, environmental reviews, and other regulatory requirements that are applicable throughout different phases of geothermal project development. The 2022 National Renewable Energy Laboratory (NREL) report, "Non-Technical Barriers to Geothermal Development in California and Nevada" presents findings of a study on non-technical barriers that may influence geothermal project development. The set of data resources relied upon for the report includes: 1) interviews conducted with relevant geothermal stakeholders including regulators and project developers, 2) federal and state environmental review documents developed for specific projects, 3) a techno-economic analysis conducted using the NREL Annual Technology Baseline (ATB) framework, and 4) an analysis of the impacts of site-specific land access and permitting considerations on project development readiness conducted using the Geothermal Resource Portfolio Optimization and Reporting Technique (GeoRePORT) Socioeconomic Assessment Tool (SEAT).

15 GEOTHERMAL ENERGY↗