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At least 505 records · Page 28

Simultaneous Determination of Halogens and Metals in Waste Plastic Pyrolysis Oil by Inductively Coupled Plasma Mass Spectrometry

A major barrier to integrating pyrolysis-derived oil into conventional refinery technology is the presence of impurities, particularly halogens and metals, that can deactivate catalysts. This study presents a novel, cost-effective approach for the simultaneous analysis of a subset of halogens, metals, nonmetals, and metalloids in complex, industrially relevant distilled pyrolysis oil samples, this was previously achievable only through multiple techniques. Excellent results were obtained using a widely accessible inductively coupled plasma mass spectrometry (ICP-MS) method with helium gas mode and standard laboratory consumables, enabling high-throughput analysis and efficient evaluation of adsorbent performance. Sample preparation is straightforward, requiring only dilution in a compatible matrix, and provides accurate and precise quantification, with 75%–137% spike recovery for Be, Ti, V, Cr, Fe, Ni, Co, Cu, As, Se, Mo, Cd, Sb, Tl, and Pb, and 62%–65% spike recovery for Cl and 109%–133% spike recovery for Br. Additionally, an enhanced version of the method using ICP-MS/MS and hydrogen gas is described, which has higher accuracy with 69%–112% spike recovery for Be, B, Ti, V, Fe, Co, Ni, Cu, As, Se, Mo, Cd, Sb, Tl, and Pb, with 85%–102% spike recovery for Cl and 63%–93% spike recovery for Br. Helium mode detection limits for industrially relevant elements (V, Fe, Ni, Cu, As, and Pb) are less than 1.7 µg/kg, and less than 0.2 mg/kg for Br and Cl. Furthermore, this methodology facilitates rapid systematic evaluation of adsorption capacities of materials under time-on-stream conditions and supports robust comparisons across diverse operating environments.

Lazarcik, James [University of Wisconsin-Madison, ↗

When can we detect lianas from space? Toward a mechanistic understanding of liana‐infested forest optics

Abstract Lianas, woody vines acting as structural parasites of trees, have profound effects on the composition and structure of tropical forests, impacting tree growth, mortality, and forest succession. Remote sensing could offer a powerful tool for quantifying the scale of liana infestation, provided the availability of robust detection methods. We analyze the consistency and global geographic specificity of spectral signals—reflectance across wavelengths—from liana‐infested tree crowns and forest stands, examining the underlying mechanisms of these signals. We compiled a uniquely comprehensive database, including leaf reflectance spectra from 5424 leaves, fine‐scale airborne reflectance data from 999 liana‐infested canopies, and coarse‐scale satellite reflectance data covering 775 ha of liana‐infested forest stands. To unravel the mechanisms of the liana spectral signal, we applied mechanistic radiative transfer models across scales, establishing a synthesis of the relative importance of different mechanisms, which we corroborate with field data on liana leaf chemistry and canopy structure. We find a consistent liana spectral signal at canopy and stand scales across globally distributed sites. This signature mainly arises at the canopy level due to direct effects of more horizontal leaf angles, resulting in a larger projected leaf area, and indirect effects from increased light scattering in the near and short‐wave infrared regions, linked to lianas' less costly leaf construction compared with trees on average. The existence of a consistent global spectral signal for lianas suggests that large‐scale quantification of liana infestation is feasible. However, because the traits responsible for the liana canopy‐reflectance signal are not exclusive to lianas, accurate large‐scale detection requires rigorously validated remote sensing methods. Our models highlight challenges in automated detection, such as potential misidentification due to leaf phenology, tree life history, topography, and climate, especially where the scale of liana infestation is less than a single remote sensing pixel. The observed cross‐site patterns also prompt ecological questions about lianas' adaptive similarities in optical traits across environments, indicating possible convergent evolution due to shared constraints on leaf biochemical and structural traits.

Environmental Sciences & Ecology↗

An Optothermal Raman Model Accounting for Convection, Radiation, and Substrate Effects for Evaluation of the Thermal Conductivity of Two‐Dimensional Coatings

Thermal conductivity of two‐dimensional (2D) materials is important to characterize as this will govern thermal transport physics in the various thermal and energy applications benefitting from the unique properties of these materials. Here, analytical and numerical techniques are presented to determine the thermal conductivity and interfacial conductance of a 2D material coating using confocal micro‐Raman spectroscopy as a noncontact diagnostic. While several methods have been proposed for calculating the values of thermal conductivity, interfacial conductance, and spatial temperature profile, these models often do not consider effects of radiation, convection, and substrate resistance on the temperature and heat flux profiles. We present a model to calculate the thermal conductivity and interfacial conductance which accounts for convection, radiation, and substrate effects to characterize a variety of 2D material coatings, which is demonstrated using large area graphene transferred onto copper and nickel substrates. Convection and radiation effects are found to have a negligible effect on the temperature profile of supported coatings, while the substrate effects have a considerable effect and therefore impact the quantification of thermal conductivity and interfacial conductance in addition to limiting the spatial resolution of the technique. These findings will allow for more accurate and reproducible extraction of the thermal conductivity of graphene and other 2D material coatings when employing noncontact optothermal Raman spectroscopy methods.

2D coatings↗

In situ aerobic methane oxidation rates in a stratified lake

Abstract Microbial aerobic methane oxidation is an important sink for aquatic methane worldwide. Despite its importance to global methane fluxes, few aerobic methane oxidation rates have been obtained in freshwater or marine environments without imposing changes to the microbial community through use of ex situ methods. A novel in situ incubation method for continuous time‐series measurements was used in Jordan Lake, North Carolina, during 2020–2021, to determine reaction kinetics for aerobic methane oxidation rates across a wide range of naturally varying methane (55–1833 nM) and dissolved oxygen (DO; 28–366 μM) concentrations and temperatures (17–30°C). Methane oxidation began immediately at the start of each of 21 incubations and methane oxidation rates were 1 st order with respect to methane. The data density allowed for accurate calculation of 1 st ‐order rate constants,k, that ranged from 0.018 to 0.462 h −1 (R 2 > 0.967). Addition of ammonium (20–45 μM) to natural concentrations ranging from 0.057 to 2.4 μM did not change aerobic methane oxidation rate kinetics, suggesting that the natural population of aerobic methane oxidizers in this eutrophic lake was not nitrogen limited. Values ofkinversely correlated most strongly with initial DO concentrations (R 2 = 0.82) rather than temperature. Values forkincreased with Julian day throughout our sampling period, suggesting seasonal influences on methane oxidation via responses to geochemical changes or shifts in microbial community abundance and composition. These experiments demonstrate a high variability in the enzymatic capacity for 1 st ‐order methane oxidation rates in this eutrophic lake that is tightly and inversely coupled to oxygen concentrations. Measurements of in situ aerobic methane oxidation rate constants allow for the direct quantification and modeling of the microbial community's capacity for methane oxidation over a wide range of natural methane concentrations.

Marine & Freshwater Biology↗

A semi–automatic analytical methodology for characterizing the energy consumption of MRI systems using load duration curves

Background and purpose: Magnetic resonance imaging (MRI) scanners are a major contributor to greenhouse gas emissions from the healthcare sector, and efforts to improve energy efficiency and reduce energy consumption rely on quantification of the characteristics of energy consumption. The purpose of this work was to develop a semi-automatic analytical methodology for the characterization of the energy consumption of MRI systems using only the load duration curve (LDC). LDCs are a fundamental tool used across various fields to analyze and understand the behavior of loads over time. Methods: An electric current transformer sensor and data logger were installed on two 3T MRI scanners from two vendors, termed M1 (outpatient scanner) and M2 (inpatient/emergency scanner). Data was collected for 1 month (7/11/2023 to 8/11/2023). Active power was calculated, assuming a balanced three-phase system, using the average current measured across all three phases, a 480 V reference voltage for both machines, and vendor-provided power factors. An LDC was constructed for each system by sorting the active power values in descending order and computing the cumulative time (in units of percentage) for each data point. The first derivative of the LDC was then computed (LDC’), smoothed by convolution with a window function (sLDC’), and used to detect transitions between different system modes including (in descending power levels): scan, prepared-to-scan, idle, low-power, and off. The final, segmented LDC was used to measure time (% total time), total energy (kWh), and mean power (kW) for each system mode on both scanners. The method was validated by comparing mean power values, computed using the segmented 1-month LDC, for each nonproductive system mode (i.e., prepared-to-scan, idle, lower-power, and off) against power levels measured after a deliberate system shutdown was performed for each scanner (1 day worth of data). Results: The validation revealed differences in mean power values <1.4% for all nonproductive modes and both scanners. In the scan system mode, the mean power values ranged from 29.8 to 37.2 kW and the total energy consumed for 1 month ranged from 11 106 to 14 466 kWh depending on the scanner. Over the course of 1 month, the portion of time the scanners were in nonproductive modes ranged from 76% to 80% across scanners and the nonproductive energy consumption ranged from 8010 to 6722 kWh depending on the scanner. The M1 (outpatient) scanner consumed 99.9 and 183.9 kWh/day in idle mode for weekdays and weekends, respectively, because the scanner spent 23% more time proportionally in idle mode on the weekends. Conclusions: A semi-automatic method for quantifying energy consumption characteristics of MRI scanners was introduced and validated. This method is relatively simple to implement as it requires only power data from the scanners and avoids the technical challenges associated with extracting and processing scanner log files. Finally, the methodology enables quantitative evaluation of the power, time, and energy characteristics of MRI scanners in scan and nonproductive system modes, providing baseline data and the capability of identifying potential opportunities for enhancing the energy efficiency of MRI scanners.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Accurate data-driven surrogates of dynamical systems for forward propagation of uncertainty

Stochastic collocation (SC) is a well-known non-intrusive method of constructing surrogate models for uncertainty quantification. In dynamical systems, SC is especially suited for full-field uncertainty propagation that characterizes the distributions of the high-dimensional solution fields of a model with stochastic input parameters. However, due to the highly nonlinear nature of the parameter-to-solution map in even the simplest dynamical systems, the constructed SC surrogates are often inaccurate. Here, this work presents an alternative approach, where we apply the SC approximation over the dynamics of the model, rather than the solution. By combining the data-driven sparse identification of nonlinear dynamics framework with SC, we construct dynamics surrogates and integrate them through time to construct the surrogate solutions. We demonstrate that the SC-over-dynamics framework leads to smaller errors, both in terms of the approximated system trajectories as well as the model state distributions, when compared against full-field SC applied to the solutions directly. We present numerical evidence of this improvement using three test problems: a chaotic ordinary differential equation, and two partial differential equations from solid mechanics.

42 ENGINEERING↗

Challenges and Opportunities in State‐of‐the‐Art Proteomics Analysis for Biomarker Development From Plasma Extracellular Vesicles

Extracellular vesicles (EVs) are membrane-bound particles secreted by cells, playing crucial roles in intercellular communication. The composition of EVs can undergo changes in response to stress and disease conditions, making them excellent biomarker candidates. However, extracting protein information from EVs can be challenging due to their low abundance in complex biofluids and copurification with contaminant proteins and particles. Techniques to enrich EVs have their strengths and limitations, without one being able to purify EVs to complete homogeneity. This can lead to compromised recovery rates and increased complexity, making data interpretation difficult. In this viewpoint article, we explore the concept that better characterization of EV composition, followed by quantification of EV proteins in complex samples, might be a more viable route for biomarker development. Mass spectrometers can provide reproducible deep coverage of the EV proteome, despite sample impurities. This paradigm shift presents opportunities to integrate advanced bioinformatics tools to refine the EV proteome landscape, identify novel biomarkers, and streamline validation processes in biomarker development. By focusing on leveraging technology rather than achieving absolute purity, this approach can transform current practices and open opportunities for robust biomarker discovery. Herein, we highlight not only such opportunities but also challenges to implement this concept.

Dakup, Panshak P. [Pacific Northwest National Labo↗

Quantifying leaf symptoms of sorghum charcoal rot in images of field‐grown plants using deep neural networks

Abstract Charcoal rot of sorghum (CRS) is a significant disease affecting sorghum crops, with limited genetic resistance available. The causative agent, Macrophomina phaseolina (Tassi) Goid, is a highly destructive fungal pathogen that targets over 500 plant species globally, including essential staple crops. Utilizing field image data for precise detection and quantification of CRS could greatly assist in the prompt identification and management of affected fields and thereby reduce yield losses. The objective of this work was to implement various machine learning algorithms to evaluate their ability to accurately detect and quantify CRS in red‐green‐blue images of sorghum plants exhibiting symptoms of infection. EfficientNet‐B3 and a fully convolutional network emerged as the top‐performing models for image classification and segmentation tasks, respectively. Among the classification models evaluated, EfficientNet‐B3 demonstrated superior performance, achieving an accuracy of 86.97%, a recall rate of 0.71, and an F1 score of 0.73. Of the segmentation models tested, FCN proved to be the most effective, exhibiting a validation accuracy of 97.76%, a recall rate of 0.68, and an F1 score of 0.66. As the size of the image patches increased, both models’ validation scores increased linearly, and their inference time decreased exponentially. This trend could be attributed to larger patches containing more information, improving model performance, and fewer patches reducing the computational load, thus decreasing inference time. The models, in addition to being immediately useful for breeders and growers of sorghum, advance the domain of automated plant phenotyping and may serve as a foundation for drone‐based or other automated field phenotyping efforts. Additionally, the models presented herein can be accessed through a web‐based application where users can easily analyze their own images.

Gonzalez, Emmanuel M.↗

Surface science insight note: A linear algebraic approach to elucidate native films on Fe 3 O 4 surface

Standard materials are often used to obtain spectra that can be compared to those from unknown samples. Spectra measured from these known substances are also used as a means of computing sensitivity factors to allow quantification by X-ray photoelectron spectroscopy (XPS) of less well-defined materials. Spectra from known materials also provide line shapes suitable for inclusion in spectral models which, when fitted to spectra, permit the chemical state for a sample to be assessed. Both types of information depend on isolating photoemission signals from the inelastically scattered signal. In this Insight note, technical issues associated with the use of XPS of as received Fe 3 O 4 powder sample surface are discussed. The Insight note is designed to show how linear algebraic techniques applied to data collected from a sample marketed as pure Fe 3 O 4 powder are used to verify that XPS has been performed on chemistry representative of the sample. The methods described in this Insight note can further be utilized in elucidating complex XPS data obtained from thin films formed or evolved during cyclic/non-steady use of complex (electro)catalyst surfaces, especially in the presence of contaminants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identifying preferential flow from soil moisture time series: Review of methodologies

Abstract Identifying and quantifying preferential flow (PF) through soil—the rapid movement of water through spatially distinct pathways in the subsurface—is vital to understanding how the hydrologic cycle responds to climate, land cover, and anthropogenic changes. In recent decades, methods have been developed that use measured soil moisture time series to identify PF. Because they allow for continuous monitoring and are relatively easy to implement, these methods have become an important tool for recognizing when, where, and under what conditions PF occurs. The methods seek to identify a pattern or quantification that indicates the occurrence of PF. Most commonly, the chosen signature is either (1) a nonsequential response to infiltrated water, in which soil moisture responses do not occur in order of shallowest to deepest, or (2) a velocity criterion, in which newly infiltrated water is detected at depth earlier than is possible by nonpreferential flow processes. Alternative signatures have also been developed that have certain advantages but are less commonly utilized. Choosing among these possible signatures requires attention to their pertinent characteristics, including susceptibility to errors, possible bias toward false negatives or false positives, reliance on subjective judgments, and possible requirements for additional types of data. We review 77 studies that have applied such methods to highlight important information for readers who want to identify PF from soil moisture data and to inform those who aim to develop new methods or improve existing ones. Core Ideas Soil moisture data can be used to identify the occurrence of preferential flow (PF) and its initiating conditions. Various data‐analysis methods to identify PF differ in susceptibility to error, bias, and subjectivity. These methods can utilize vast amounts of data from soil moisture monitoring networks to develop understanding of when, where, and under what conditions PF occurs. Newly developed methods may lead to better accuracy and reliability, and reduce the need for subjective judgments. Plain Language Summary Preferential flow through soil occurs when a large amount of water is suddenly available, as during an intense storm. This type of flow moves rapidly through the soil in distinct narrow pathways rather than moving evenly throughout the body of soil, with major consequences for groundwater resources, ecosystems, spreading of contaminants, and other vital concerns. Methods of detecting preferential flow have been developed that utilize measurements of soil water content made by sensors installed at various depths. This measurement technology has been widely implemented, many locations now having datasets years in length, and various methods have been developed for using these to identify preferential flow. The various methods are based on different features in the soil moisture records and vary in their advantages and shortcomings. In this review, we explain and evaluate these methods, highlighting important information for their implementation to identify preferential flow from soil moisture data and for efforts to develop new methods or improve existing ones.

Nimmo, John R↗

Robust calibration of non-perturbative models with history matching

We apply, for the first time, Bayes Linear Emulation and History Matching to the calibration of non-perturbative models in Monte Carlo event generators. In contrast to the usual approach of "Monte Carlo tuning", History Matching does not result in best-fit plus ellipsoidal parameter uncertainty estimates but instead identifies all parameter space regions that are consistent with data. This approach leads to a systematic and robust quantification of parametric uncertainties in the models, especially in those challenging cases where different, possibly disjoint, regions of parameter space deliver similar results, which are usually not properly treated with current methodology. We highlight the power of this method with the hadronisation models available through Sherpa : the built-in cluster fragmentation Ahadic and string fragmentation through an interface to Pythia .

Iskauskas, Andrew [Durham U. (main)] (ORCID:000000↗

Increased inflammation as well as decreased endoplasmic reticulum stress and translation differentiate pancreatic islets from donors with pre-symptomatic stage 1 type 1 diabetes and non-diabetic donors

Aims/hypothesis Progression to type 1 diabetes is associated with genetic factors, the presence of autoantibodies and a decline in beta cell insulin secretion in response to glucose. Very little is known regarding the molecular changes that occur in human insulin-secreting beta cells prior to the onset of type 1 diabetes. Herein, we applied an unbiased proteomics approach to identify changes in proteins and potential mechanisms of islet dysfunction in islet-autoantibody-positive organ donors with pre-symptomatic stage 1 type 1 diabetes (HbA1c ≤42 mmol/mol [6.0%]). We aimed to identify pathways in islets that are indicative of beta cell dysfunction. Methods Multiple islet sections were collected through laser microdissection of frozen pancreatic tissues from organ donors positive for single or multiple islet autoantibodies (AAb + , n=5), and age (±2 years)- and sex-matched non-diabetic (ND) control donors (n=5) obtained from the Network for Pancreatic Organ donors with Diabetes (nPOD). Islet sections were subjected to MS-based proteomics and analysed with label-free quantification followed by pathway and functional annotations. Results Analyses resulted in ~4500 proteins identified with low false discovery rate (<1%), with 2165 proteins reliably quantified in every islet sample. We observed large inter-donor variations that presented a challenge for statistical analysis of proteome changes between donor groups. We therefore focused on only the donors with stage 1 type 1 diabetes who were positive for multiple autoantibodies (mAAb + , n=3) and genetic risk compared with their matched ND controls (n=3) for the final statistical analysis. Approximately 10% of the proteins (n=202) were significantly different (unadjusted p<0.025, q<0.15) for mAAb + vs ND donor islets. The significant alterations clustered around major functions for upregulation in the immune response and glycolysis, and downregulation in endoplasmic reticulum (ER) stress response as well as protein translation and synthesis. The observed proteome changes were further supported by several independent published datasets, including a proteomics dataset from in vitro proinflammatory cytokine-treated human islets and single-cell RNA-seq datasets from AAb + individuals. Conclusions/interpretation In situ human islet proteome alterations in stage 1 type 1 diabetes centred around several major functional categories, including an expected increase in immune response genes (elevated antigen presentation/HLA), with decreases in protein synthesis and ER stress response, as well as compensatory metabolic response. The dataset serves as a proteomics resource for future studies on beta cell changes during type 1 diabetes progression and pathogenesis. Data availability The LC-MS raw datasets that support the findings of this study have been deposited in the online repository: MassIVE (https://massive.ucsd.edu/ProteoSAFe/static/massive.jsp) with accession no. MSV000090212.

Autoantibody-positive↗

Out-of-Distribution Detection and Radiological Data Monitoring Using Statistical Process Control

Abstract Machine learning (ML) models often fail with data that deviates from their training distribution. This is a significant concern for ML-enabled devices as data drift may lead to unexpected performance. This work introduces a new framework for out of distribution (OOD) detection and data drift monitoring that combines ML and geometric methods with statistical process control (SPC). We investigated different design choices, including methods for extracting feature representations and drift quantification for OOD detection in individual images and as an approach for input data monitoring. We evaluated the framework for both identifying OOD images and demonstrating the ability to detect shifts in data streams over time. We demonstrated a proof-of-concept via the following tasks: 1) differentiating axial vs. non-axial CT images, 2) differentiating CXR vs. other radiographic imaging modalities, and 3) differentiating adult CXR vs. pediatric CXR. For the identification of individual OOD images, our framework achieved high sensitivity in detecting OOD inputs: 0.980 in CT, 0.984 in CXR, and 0.854 in pediatric CXR. Our framework is also adept at monitoring data streams and identifying the time a drift occurred. In our simulations tracking drift over time, it effectively detected a shift from CXR to non-CXR instantly, a transition from axial to non-axial CT within few days, and a drift from adult to pediatric CXRs within a day—all while maintaining a low false positive rate. Through additional experiments, we demonstrate the framework is modality-agnostic and independent from the underlying model structure, making it highly customizable for specific applications and broadly applicable across different imaging modalities and deployed ML models.

Zamzmi, Ghada↗

Adaptive anomaly detection for identifying attacks in cyber-physical systems: A systematic literature review

Modern cyberattacks in cyber-physical systems (CPS) rapidly evolve and cannot be deterred effectively with most current methods, which focus on characterizing past threats. Adaptive anomaly detection (AAD) is among the most promising techniques to detect evolving cyberattacks, with an emphasis on fast data processing and model adaptation. AAD has been researched extensively; however, to the best of our knowledge, our work is the first systematic literature review (SLR) on current research in this field. We present a comprehensive SLR, gathering 397 relevant papers and systematically analyzing 65 of them (47 research and 18 survey papers) on AAD in CPS from 2013 to November 2023. We introduce a novel taxonomy considering attack types, CPS application, learning paradigm, data management, and algorithms. Our findings show that most studies addressed either model adaptation or data processing, but rarely both simultaneously. This indicates a research gap in fully adaptive solutions. We also categorize algorithms, datasets, and attack characteristics, and summarize strengths and weaknesses across the literature. Our review provides a structured and accessible reference for researchers and practitioners, offering insights into key trends and highlighting limitations in current approaches. Finally, we outline several future research directions, including the need for integrated real-time processing and adaptive learning, explainability, and uncertainty quantification in AAD for CPS.

Adaptation↗

Transition in ICF Capsule Implosions

Longstanding design and reproducibility challenges in inertial confinement fusion (ICF) capsule implosion experiments involve recognizing the need for appropriately characterized and modeled three-dimensional initial conditions and high-fidelity simulation capabilities to predict transitional flow approaching turbulence, material mixing characteristics, and late-time quantities of interest—e.g., fusion yield. We build on previous coarse graining simulations of the indirect-drive national ignition facility (NIF) cryogenic capsule N170601 experiment-a precursor of N221205 which resulted in net energy gain. We apply effectively combined initialization aspects and multiphysics coupling in conjunction with newly available hydrodynamics simulation methods, including directional unsplit algorithms and low Mach-number correction-key advances enabling high fidelity coarse grained simulations of radiation-hydrodynamics driven transition. Our presentation includes discussion of the capsule initialization and implosion dynamics, analysis of the vorticity production budget, transition signatures, quantities of interest—late-time ion temperature and fusion-neutron yield, numerical uncertainty quantification, and comparisons with NIF data.

42 ENGINEERING↗

Field deployable trace radioisotope analysis through combined electrochemical and alpha spectroscopy methods

A method for depositing actinides directly onto a 4H-SiC Schottky barrier diode (SBD) detector as a field deployable actinides sensor was developed to enable off-site analysis, shortening the time to obtain critical information such as elements, concentration, and/or isotopic ratio related to the radiological situation. A thin film of Hg was first electrodeposited onto the Pt contact of the SiC diode, followed by chronoamperometric deposition of microgram levels of actinides under conventional control conditions. The 4H-SiC diode maintained consistent functionality through the electrodeposition process and showed resolved alpha-energy spectra that contained accurate isotopic information demonstrating the feasibility of a combined chemical and radiological sensor for field actinide detection and quantification.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

LandScan HD: a high-resolution gridded ambient population methodology for the world

Unwarned population distributions accounting for routine human activities are needed to address many global human security challenges, including disasters, conflict, and infrastructure demand. LandScan High Definition (LSHD) supports this need through gridded ambient population estimates that measure average human presence between daytime and nighttime at a high spatial resolution of 3 arcseconds (approximately 90 m). Although LSHD has traditionally been produced on a country-specific basis, advances in global foundational data and computational resources now enable scaling its methodology to the world. Combining aspects of top-down and bottom-up gridded population methods, LSHD allocates subnational population totals from authoritative statistics to built-up areas based on occupancy estimates for multiple facility types (e.g., residential, commercial) and then reaggregates these estimates to a global population grid. We scale this approach by organizing the LSHD data stack into a 1° resolution tileset of vector analytic features, enabling an efficient and repeatable workflow for all countries worldwide. Examining the Philippines as an output of the global LSHD baseline dataset, we contrast unwarned and residential (WorldPop) population distributions by (1) exploring a practical application of flood risk assessment and (2) evaluating their congruence with outcomes of collective human activities (subnational CO 2 emissions). Finally, we discuss plans to address current LSHD limitations through data/modeling and uncertainty quantification improvements and provide outlook for workflow automation and extending the model to social, demographic and economic population characteristics.

Building morphology↗

Stabilization of Catalytically Active Surface Defects on Ga-doped La–Sr–Mn Perovskites for Improved Solar Thermochemical Generation of Hydrogen

Solar thermochemical hydrogen (STCH) production from water splitting typically requires performing redox cycles at temperatures above 1200 °C to reduce and re-oxidize the bulk of a reversible material. Bulk processes such as oxygen vacancy formation and oxygen diffusion energies dictate the viability of a material for STCH. The surface plays an important role in the formation and destruction of vacancies and interacts with gas phase water and surface adsorbed species. These surface processes can lead to surface reconfigurations and even the formation of surface phases with stoichiometry and oxygen content very different from the bulk composition. Understanding in-situ the surface chemical state and its evolution under water splitting is important to design nonstoichiometric oxides capable of longer-lasting STCH generation at lower temperatures. In this work, we describe the water splitting active defect sites in LSM ((La 0.65 Sr 0.35 ) 0.95 MnO 3–δ ) and Ga-doped LSM ((La 0.6 Sr 0.4 ) 0.95 (Mn 0.8 Ga 0.2 )O 3–δ ) perovskites during Operando thermochemical water splitting conditions using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) experiments at 800 °C under steam. We show that sub-stoichiometric La +3 in the oxygen-vacancy rich surface at operating conditions can be used to correlate surface water splitting activity and the creation of surface hydroxide intermediates. The addition of Ga in LSM is shown to drastically stabilize the surface chemical composition by preventing Sr segregation and stabilizing catalytically active surface defects that promote the binding of adsorbed hydroxides. Here, we use Operando AP-XPS quantification of metastable surface hydroxide intermediates (La(OH) 3 ) to determine the amount of catalytically active surface sites in LSM (2.9%) and in LSMG (7.8–8.1%, depending on the bulk oxidation state).

08 HYDROGEN↗