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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 937 records · Page 52

Automated Nanoflow Two-Dimensional Reversed-Phase Liquid Chromatography System Enables In-Depth Proteome and Phosphoproteome Profiling of Nanoscale Samples

Two-dimensional reversed-phase liquid chromatography (2D RPLC) separations have enabled near-comprehensive proteome profiling of biological systems. However, large samples containing milligram amounts of protein are usually required due to the significant sample losses incurred during offline fractionation. The large sample requirements preclude the application of 2D RPLC to biological systems having sample availability in the nanogram to low-microgram range. To achieve in-depth proteomic studies of trace samples, we have developed an automated nanoflow 2D RPLC platform in which the first dimension high-pH fractionation was performed at 300 nL/min on a 75-µm i.d. capillary column.Each fraction was then fully transferred to a second-dimension nanoLC separation using an autosampler equipped with a custom-machined syringe. In addition to optimizing fractionation conditions, we found that the use of a plastic 96-well plate as collection device and the adding of n-Dodecyl ß-D-Maltoside (0.01%) in the collection buffer can significantly improve sample recovery. We have demonstrated the nanoflow 2D RPLC platform can achieve confident identifications of ~37,000–69,000 unique peptides, corresponding to ~5300–6900 protein groups using only 100 to 1000 ng of HeLa tryptic digest. Furthermore, by integrating phosphopeptide enrichment, the platform can identify as many as ~20,000 phosphopeptides from 100 µg of MCF7 protein digest. Because this platform is assembled from commercially available components, our approach can be readily adapted in other proteomics laboratories.

Mass spectrometry, multidimensional separations, n↗

Depth-Dependent Understanding of Cathode Electrolyte Interphase (CEI) on the Layered Li-Ion Cathodes Operated at Extreme High Temperature

The high-temperature operation of Li-ion batteries is highly dependent on the stability of the cathode electrolyte interphase (CEI) formed during lithiation-delithiation reactions. However, knowledge on the nature of the CEI is limited and its stability under extreme temperatures is not well understood. Therefore, herein, we investigate a proof-of-concept study on stabilizing CEI on model LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC333) at extreme operation condition of 100 oC using thermally stable pyrrolidinium based ionic liquid electrolyte. The electrochemical lithiation-delithiation reactions at 100 oC and the CEI evolution upon different cycling conditions are investigated. Further, the depth-dependent CEI chemistry was investigated using energy tunable synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). Overall, the results reveal that the high temperature operation accelerated the CEI formation compared to room temperature, and the surface of the interphase layer is rich in boron-based inorganic moieties than the deeper surface. Further, bulk sensitive X-ray absorption spectroscopy (XAS) was used to investigate the transition metal redox contributors during high temperature electrochemical reactions, similar to room temperature, the Ni2+/4+redox couple is the only charge compensating redox couple during high temperature operation. Finally, the physical nature of the conformal CEI on the cathode particles was visualized with high-resolution transmission electron microscopy, which confirms that the significant degradation of cathode particles without conformal CEI is due to the transformation of layer to spinel formation at extreme temperature. In this study, understanding this high temperature interfacial chemistry of NMC cathodes through advanced spectroscopy and microscopy will shed light on transforming ambient temperature Li-ion chemistry to high temperature applications.

25 ENERGY STORAGE↗

Distribution of Copper States, Phases, and Defects across the Depth of a Cu-Doped CdTe Solar Cell

Copper has been used as a p-type dopant in cadmium telluride (CdTe) for decades. However, the density of Cu atoms in the finished device is much higher than that of holes, which means that most Cu atoms are not activated as acceptors during incorporation. Furthermore, studies have demonstrated that the distribution of copper (Cu) atoms across the device is highly inhomogeneous, with reports citing Cu substitution on Cd sites and segregation to grain boundaries. Fast diffusion along these boundaries and Cu accumulation at the CdTe/CdS interface have also been observed and validated computationally. These levels of inhomogeneity make it difficult to accurately characterize and correlate the performance with the nature of the Cu atomic species present. To address this challenge, we utilize X-ray microscopy and, specifically, nanoscale fluorescence-mode X-ray absorption near-edge structure to resolve the atomic Cu environment throughout the depth of the CdTe layer. Our results suggest that the majority of Cu atoms are in the form of Cu x Te phases (or similar local environments) near the ZnTe|CdTe interface, Cu x O phases in the CdTe absorber, and present in various oxidation states, including Cu 1+ and Cu 2+ , near the CdS/CdTe junction. Here this work also provides experimental evidence for the first time of the presence of CuS around the ZnTe|CdTe interface and the hypothesized Cu Cd -Cl i complex in the CdTe absorber.

14 SOLAR ENERGY↗

Controlling Magnetization Vector Depth Profiles of La 0.7 Sr 0.3 CoO 3 /La 0.7 Sr 0.3 MnO 3 Exchange Spring Bilayers via Interface Reconstruction

The La 0.7 Sr 0.3 CoO 3–δ /La 0.7 Sr 0.3 MnO 3–δ (LSCO/LSMO) bilayer system is an ideal perovskite oxide platform for investigating interface reconstruction and its effect on their magnetic properties. Previous studies have shown that LSCO can separate into magnetic sublayers, which possess distinct trends as the total LSCO thickness increases. Here, we used polarized neutron reflectometry to quantify changes in the magnetic and chemical depth profiles, and it confirms the formation of ~12 Å-thick interfacial LSCO and LSMO layers, characterized by a decreased nuclear scattering length density compared to the bulk of the layers. This decrease is attributed to the combined effects of oxygen vacancy formation and interfacial charge transfer, which lead to magnetically active Co 2+ ions with ionic radii larger than the Co 3+ /Co 4+ ions typically found in bulk LSCO or single-layer films. The interfacial magnetization values, as well as Co 2+ ion and oxygen vacancy concentrations, depend strongly on the LSCO layer thickness. These results highlight the sensitive interplay of the cation valence states, oxygen vacancy concentration, and magnetization at interfaces in perovskite oxide multilayers, demonstrating the potential to tune their functional properties via careful design of their structure.

36 MATERIALS SCIENCE↗

Oxygen Vacancy Evolution at Li x V 2 O 5 /LiPON Solid State Electrochemical Interfaces Using Depth Resolved Cathodoluminescence Spectroscopy

The formation of oxygen vacancies at buried LiPON/ Li x V 2 O 5 interfaces has been observed on a near-nanometer scale and nondestructively using depth-resolved cathodoluminescence spectroscopy (DRCLS) and interfacial markers. Before electrochemical cycling, as-deposited LiPON/Li x V 2 O 5 exhibits a 1.6 eV defect optical emission, which density functional theory calculations identify as originating from oxygen vacancies. This defect appears first within a few nanometers of the buried LiPON/Li x V 2 O 5 interface without cycling, indicating that spontaneous O diffusion from the Li x V 2 O 5 lattice into LiPON may have caused these interface-localized oxygen vacancy defects. DRCLS measured the intensity and spatial distribution of this oxygen vacancy signal as a function of electrochemical cycling in a LiPON/Li x V 2 O 5 half-cell, showing oxygen vacancy signal increasing and moving deeper into the electrode with increased cycle number. Significant electrochemical irreversibility was also observed, with poor Coulombic efficiency and a 15% drop in capacity over 50 cycles. Theoretical simulations predict that the presence of oxygen vacancies increases the energy barrier for lithium diffusion significantly, indicating that this aggregation of oxygen vacancies could be another battery degradation mechanism accompanying lithiation induced phase changes.

36 MATERIALS SCIENCE↗

Depth-Dependent Emission from Silver Dopants in Single CdSe Nanoplatelets

Dopants in semiconductor nanostructures offer tremendous control over electronic, optical, and magnetic properties beyond what is achievable in bulk materials. We demonstrate that the broad dopant emission in semiconductor nanoplatelets effectively maps the electron wave function across the nanoplatelet thickness. Both the emission energy and lifetime of the dopant transition depend strongly on the depth of the dopant within the nanoplatelet. This dependence arises from the electrostatic self-interaction of the charged dopant, which varies with proximity to the dielectric discontinuity at the nanoplatelet surface. Through comprehensive single-particle spectroscopy of silver-doped CdSe nanoplatelets, we verify that acceptors near the center emit at higher energies with shorter lifetimes, while those near the surface emit at lower energies with longer lifetimes. This spatial mapping also reveals unusual two-color emission from individual nanoplatelets, with enhanced Auger recombination yielding exceptional photon antibunching (>90% purity) at room temperature, suggesting potential applications in quantum information technologies.

cadmium selenide↗

Metal affinity enrichment increases the range and depth of proteome identification for extracellular microbial proteins

Many key proteins, such as those involved in cellular signaling or transcription, are difficult to measure in microbial proteomic experiments due to the interfering presence of more abundant, dominant proteins. In an effort to enhance the identification of previously undetected proteins, as well as provide a methodology for selective enrichment, we evaluated and optimized immobilized metal affinity chromatography (IMAC) coupled with mass spectrometric characterization of extracellular proteins from an extremophilic microbial community. Seven different metals were tested for IMAC enrichment. The combined results added 20% greater proteomic depth to the extracellular proteome. Although this IMAC enrichment could not be conducted at the physiological pH of the environmental system, this approach did yield a reproducible and specific enrichment of groups of proteins with functions potentially vital to the community, thereby providing a more extensive biochemical characterization. Notably, 40 unknown proteins previously annotated as hypothetical were enriched and identified for the first time. Examples of identified proteins includes a predicted TonB signal sensing protein homologous to other known TonB proteins and a protein with a COXG domain previously identified in many chemolithoautotrophic microbes as having a function in the oxidation of CO.

Wheeler, Korin↗

Depth‐ and Time‐Resolved Distributions of Snowmelt‐Driven Hillslope Subsurface Flow and Transport and Their Contributions to Surface Waters

Abstract Major components of hydrologic and elemental cycles reside underground, where their complex dynamics and linkages to surface waters are obscure. We delineated seasonal subsurface flow and transport dynamics along a hillslope in the Rocky Mountains (USA), where precipitation occurs primarily as winter snow and drainage discharges into the East River, a tributary of the Gunnison River. Hydraulic and geochemical measurements down to 10 m below ground surface supported application of transmissivity feedback of snowmelt to describe subsurface flow and transport through three zones: soil, weathering shale, and saturated fractured shale. Groundwater flow is predicted to depths of at least 176 m, although a shallower limit exists if hillslope‐scale hydraulic conductivities are higher than our local measurements. Snowmelt during the high snowpack water year 2017 sustained flow along the weathering zone and downslope within the soil, while negligible downslope flow occurred along the soil during the low snowpack water year 2018. We introduce subsurface concentration‐discharge ( C‐Q ) relations for explaining hillslope contributions to C‐Q observed in rivers and demonstrate their calculations based on transmissivity fluxes and measured pore water specific conductance and dissolved organic carbon. The specific conductance data show that major ions in the hillslope pore waters, primarily from the weathering and fractured shale, are about six times more concentrated than in the river, indicating hillslope solute loads are disproportionately high, while flow from this site and similar regions are relatively smaller. This methodology is applicable in different representative environments within snow‐dominated watersheds for linking their subsurface exports to surface waters.

54 ENVIRONMENTAL SCIENCES↗

On the Breakdown of ENSO's Relationship With Thermocline Depth in the Central-Equatorial Pacific

Recent classification of El Nino-Southern Oscillation (ENSO) into two types, Eastern (EP) and Central (CP) events, has highlighted the importance of the central Pacific. We show here that the local correlation between ENSO subsurface temperatures (T sub ) in the upper 100-m and thermocline depth anomalies breaks down in the central equatorial Pacific, whereas T sub remains well correlated with sea surface height anomalies. This observed difference in the central equatorial Pacific is simulated by almost all climate models. It arises from a vertically slanted Tsub anomaly structure that is unique to the central equatorial Pacific. We show that this feature is an adiabatic response to wind-driving that is even present in a linear dynamic model, as long as the model has enough baroclinic modes to adequately represent the observed vertical complexity. Our findings have implications for better understanding the different importance of thermocline feedback in CP and EP events.

58 GEOSCIENCES↗

The Diurnal Variation of the Aerosol Optical Depth at the ARM SGP Site

Abstract This study examines the diurnal variation of the aerosol optical depth (AOD) at 355 nm observed by Raman lidar (RL) at the Atmospheric Radiation Measurement Program Southern Great Plains (SGP) site under both clear and cloudy‐sky conditions. Here only cloudy‐skies when the lidar signal is not fully attenuated are considered. The daytime AOD and its variation from the RL showed an excellent agreement with the Aerosol Robotic Network, demonstrating that the RL‐retrieved AOD is not affected by solar background contamination. The climatological annual‐mean daytime‐mean AOD is only slightly larger than the nighttime‐mean AOD (by 1%–3%). However, day‐to‐day variations are observed such that the daytime‐ and nighttime‐mean AOD difference for a given day can be large (about 95% of days have differences within 0.2). The seasonal AOD diurnal range (i.e., the difference between the maximum and minimum values) relative to the mean was 10%–15% except in the winter when it was 44%. The seasonal‐mean cloudy‐sky AOD diurnal variation is similar to that for clear‐sky, except that the AODs are larger (the annual‐mean cloudy‐sky AOD is larger than the clear‐sky by 24%). The aerosol lidar ratio diurnal variations are also examined, which are 10%–20% for all seasons with a minimum near 9 a.m. to 15 p.m. for all seasons except winter. Also presented is the annual‐mean AOD from the Cloud‐Aerosol Lidar and Infrared Pathfinder Satellite at SGP site: its daytime AOD is about 0.1 smaller than nighttime AOD because of daytime solar background contamination.

54 ENVIRONMENTAL SCIENCES↗

Experimental Whole-Ecosystem Warming Enables Novel Estimation of Snow Cover and Depth Sensitivities to Temperature, and Quantification of the Snow-Albedo Feedback Effect

Climate change is reducing the amount, duration, and extent of snow across high-latitude ecosystems. But, in landscapes where persistent winter snow cover develops, experimental platforms to specifically investigate interactions between warming and changes in snowpack, and impacts on ecosystem processes, have been lacking. We leveraged a whole-ecosystem warming experiment in a boreal peatland forest to quantify how snow duration, depth, and fractional cover vary with warming of up to +9°C. We found that every snow-related quantity we examined declined precipitously as the amount of warming increased. The importance of deep, continuous snow cover for moderating shallow soil temperature is highlighted by an increase in soil temperature variance and the frequency of short-duration freeze-thaw cycles in the warmer plots. We used a paired-plot approach to estimate the magnitude of the snow-albedo feedback effect, and demonstrate that albedo-driven warming linked to reduced snow cover varies between December (+0.4°C increase in maximum air temperature) and March (+1.2°C increase) because of differences in insolation. Overall, results show that even modest future warming will have profound impacts on northern winters and cold-season ecosystem processes. Plot-level data from this warming experiment, and emergent relationships between warming and quantities related to snow cover and duration, could be of enormous value for testing and improving the representation of snow processes in simulation models, especially under future climate scenarios that are outside of the range of historically observed variability.

54 ENVIRONMENTAL SCIENCES↗

Machine Learning Calibration of Groundwater Table Depth in ELM: Impact on Land Surface Hydrology and Land‐Atmosphere Fluxes

Accurate representation of groundwater table depth (GWTD) is crucial for simulating hydrological cycling in Earth system models (ESM). Nevertheless, there is a notable gap in the literature regarding the validation of GWTD simulations in ESMs and their subsequent impact on downstream hydrological components. This study explores the calibration of parameterization of global GWTD using machine learning within the Energy Exascale Earth System Model (E3SM) Land Model (ELM). Despite achieving significant gains in simulating GWTD through calibration, offline ELM simulations unexpectedly show that these improvements do not translate to substantial enhancements in model performance for other key hydrological variables, including soil moisture (SM), runoff, groundwater contribution to runoff or base flow index (BFI), and evapotranspiration and its partitioning. The performance in SM and runoff was even degraded in some regions, while BFI was mostly overestimated. Although there is significant improvement in GWTD within the critical range of 1–5 m, where groundwater traditionally influences land surface energy fluxes, these improvements occurred mostly in humid areas where the impact of GWTD on surface processes is minimal. Although the impacts of model calibration are generally small in offline ELM simulations, coupled land-atmosphere simulations exhibit much stronger responses to GWTD calibration, highlighting the role of land-atmosphere feedbacks in Earth system modeling. These findings underscore the need for integrated calibration strategies that simultaneously optimize multiple hydrological variables. However, if a single-variable approach is necessary, it is crucial to establish clear priorities for calibration, identifying the most critical variables that have the greatest impact on overall model performance.

Fang, Yilin [Pacific Northwest National Laboratory↗

Structural and magnetic depth profiles of magneto-ionic heterostructures beyond the interface limit

Electric field control of magnetism provides a promising route towards ultralow power information storage and sensor technologies. The effects of magneto-ionic motion have been prominently featured in the modification of interface characteristics. Here, we demonstrate magnetoelectric coupling moderated by voltage-driven oxygen migration beyond the interface in relatively thick AlO x /GdO x /Co(15 nm) films. Oxygen migration and Co magnetization are quantitatively mapped with polarized neutron reflectometry under electro-thermal conditioning. The depth-resolved profiles uniquely identify interfacial and bulk behaviours and a semi-reversible control of the magnetization. Magnetometry measurements suggest changes in the microstructure which disrupt long-range ferromagnetic ordering, resulting in an additional magnetically soft phase. X-ray spectroscopy confirms changes in the Co oxidation state, but not in the Gd, suggesting that the GdO x transmits oxygen but does not source or sink it. These results together provide crucial insight into controlling magnetism via magneto-ionic motion, both at interfaces and throughout the bulk of the films.

36 MATERIALS SCIENCE↗

Depth-discrete metagenomics reveals the roles of microbes in biogeochemical cycling in the tropical freshwater Lake Tanganyika

Lake Tanganyika (LT) is the largest tropical freshwater lake, and the largest body of anoxic freshwater on Earth’s surface. LT’s mixed oxygenated surface waters float atop a permanently anoxic layer and host rich animal biodiversity. However, little is known about microorganisms inhabiting LT’s 1470 meter deep water column and their contributions to nutrient cycling, which affect ecosystem-level function and productivity. Here, we applied genome-resolved metagenomics and environmental analyses to link specific taxa to key biogeochemical processes across a vertical depth gradient in LT. We reconstructed 523 unique metagenome-assembled genomes (MAGs) from 34 bacterial and archaeal phyla, including many rarely observed in freshwater lakes. We identified sharp contrasts in community composition and metabolic potential with an abundance of typical freshwater taxa in oxygenated mixed upper layers, and Archaea and uncultured Candidate Phyla in deep anoxic waters. Genomic capacity for nitrogen and sulfur cycling was abundant in MAGs recovered from anoxic waters, highlighting microbial contributions to the productive surface layers via recycling of upwelled nutrients, and greenhouse gases such as nitrous oxide. Overall, our study provides a blueprint for incorporation of aquatic microbial genomics in the representation of tropical freshwater lakes, especially in the context of ongoing climate change, which is predicted to bring increased stratification and anoxia to freshwater lakes.

59 BASIC BIOLOGICAL SCIENCES↗

Global soil profiles indicate depth-dependent soil carbon losses under a warmer climate

Soil organic carbon (SOC) changes under future climate warming are difficult to quantify in situ. Here we apply an innovative approach combining space-for-time substitution with meta-analysis to SOC measurements in 113,013 soil profiles across the globe to estimate the effect of future climate warming on steady-state SOC stocks. We find that SOC stock will reduce by 6.0 ± 1.6% (mean±95% confidence interval), 4.8 ± 2.3% and 1.3 ± 4.0% at 0–0.3, 0.3–1 and 1–2 m soil depths, respectively, under 1 °C air warming, with additional 4.2%, 2.2% and 1.4% losses per every additional 1 °C warming, respectively. The largest proportional SOC losses occur in boreal forests. Existing SOC level is the predominant determinant of the spatial variability of SOC changes with higher percentage losses in SOC-rich soils. Our work demonstrates that warming induces more proportional SOC losses in topsoil than in subsoil, particularly from high-latitudinal SOC-rich systems.

54 ENVIRONMENTAL SCIENCES↗

Mediterranean grassland soil C–N compound turnover is dependent on rainfall and depth, and is mediated by genomically divergent microorganisms

Soil microbial activity drives the carbon and nitrogen cycles and is an important determinant of atmospheric trace gas turnover, yet most soils are dominated by microorganisms with unknown metabolic capacities. Even Acidobacteria, among the most abundant bacteria in soil, remain poorly characterized, and functions across groups such as Verrucomicrobia, Gemmatimonadetes, Chloroflexi and Rokubacteria are understudied. Here, we have resolved 60 metagenomic and 20 proteomic data sets from a Mediterranean grassland soil ecosystem and recovered 793 near-complete microbial genomes from 18 phyla, representing around one-third of all microorganisms detected. Importantly, this enabled extensive genomics-based metabolic predictions for these communities. Acidobacteria from multiple previously unstudied classes have genomes that encode large enzyme complements for complex carbohydrate degradation. In contrast, most microorganisms encode carbohydrate esterases that strip readily accessible methyl and acetyl groups from polymers like pectin and xylan, forming methanol and acetate, the availability of which could explain the high prevalence of C 1 metabolism and acetate utilization in genomes. Microorganism abundances among samples collected at three soil depths and under natural and amended rainfall regimes indicate statistically higher associations of inorganic nitrogen metabolism and carbon degradation in deep and shallow soils, respectively. This partitioning decreased in samples under extended spring rainfall, indicating that long-term climate alteration can affect both carbon and nitrogen cycling. As a whole, by leveraging natural and experimental gradients with genome-resolved metabolic profiles, we link microorganisms lacking prior genomic characterization to specific roles in complex carbon, C 1 , nitrate and ammonia transformations, and constrain factors that impact their distributions in soil.

59 BASIC BIOLOGICAL SCIENCES↗

Harmonized and high-quality datasets of aerosol optical depth at a US continental site, 1997-2018

Aerosol optical depth (AOD) characterizes the aerosol burden in the atmosphere, while its wavelength dependence is a sign of particle size. Long-term records of wavelength-resolved AOD with high quality and suitable continuity are required for climate change assessment. Typically, climate-related studies use AOD products provided by several, and perhaps different, ground-based instruments. The measurements from these instruments often have different accuracy and temporal resolution. To preserve the advantages of these products (high quality) and to reduce their disadvantages (patchy records), we generate a merged dataset obtained from several instruments in which a nearly-continuous AOD record is found at two wavelengths (500 and 870 nm) with high quality and high temporal resolution (1-min) for a 21-yr period (1997-2018). The combined dataset addresses: (1) varying data quality and resolution mismatch of the individual AOD records, and (2) the uncertainty of the merged AOD and its relevance for user-specified needs. The generated dataset will be beneficial for a wide range of applications including aerosol-radiation interactions and their impact in forcing climate change.

54 ENVIRONMENTAL SCIENCES↗

Micro-scale heterogeneity of soil phosphorus depends on soil substrate and depth

Soils comprise various heterogeneously distributed pools of lithogenic, free organic, occluded, adsorbed, and precipitated phosphorus (P) forms, which differ depending on soil forming factors. Small-scale heterogeneity of element distributions recently has received increased attention in soil science due to its influence on soil functions and soil fertility. We investigated the micro-scale distribution of total P and different specific P binding forms in aggregates taken from a high-P clay-rich soil and a low-P sandy soil by combining advanced spectrometric and spectroscopic techniques to introduce new insights on P accessibility and availability in soils. Here we show that soil substrate and soil depth determine micro-scale P heterogeneity in soil aggregates. In P-rich areas of all investigated soil aggregates, P was predominantly co-located with aluminium and iron oxides and hydroxides, which are known to strongly adsorb P. Clay minerals were co-located with P only to a lesser extent. In the low-P topsoil aggregate, the majority of the P was bound organically. Aluminium and iron phosphate predominated in the quartz-rich low-P subsoil aggregate. Sorbed and mineral P phases determined P speciation in the high-P top- and subsoil, and apatite was only detected in the high-P subsoil aggregate. Lastly, our results indicate that micro-scale spatial and chemical heterogeneity of P influences P accessibility and bioavailability.

36 MATERIALS SCIENCE↗