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At least 1,441 records · Page 80

Predicting 3D moisture sorption behavior of materials from 1D investigations

Abstract Moisture in materials can be a source of future outgassing and exacerbate unwanted changes in physical and chemical properties. Here, we investigate the effect of sample size and shape on the moisture transport phenomena through a combined experimental and modeling approach. Several different materials varying in size and shape were investigated over a wide range of relative humidities (0–90%) and temperatures ( $$30{-}70^{\,\circ } \hbox {C}$$ 30 - 70 ∘ C ) using gravimetric type dynamic vapor sorption (DVS). A dynamic triple-mode sorption model, developed previously, was employed to describe the experimental results with good success; the model includes absorption, adsorption, pooling (clustering) of species, and molecular diffusion. Here we show that the full triple-mode sorption model is robust enough to predict the dynamic uptake and outgassing of 3-dimensional (3D) samples using parameters derived from quasi-1D samples. This successful demonstration on three different materials (filled polydimethylsiloxane (PDMS), unfilled PDMS, and ceramic inorganic composite) illustrates that the model is robust at describing the scale-independent physics and chemistry of moisture sorption and diffusion materials. This work demonstrates that while sorption mechanisms manifest in testing of all sample sizes, some of these mechanisms were so subtle that they were overlooked in our initial modeling and assessment, illustrating the importance of multi-scale experiments in the development of robust predictive capabilities. Our study also outlines the challenges and viable solutions for global optimization of a multi-parameter model. The ability to quantify moisture sorption and diffusion, independent of scale, using 1D lab-scale experiments enables prediction of long-term bulk materials behavior in real applications.

36 MATERIALS SCIENCE↗

Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy

Metal organic frameworks (MOFs) that incorporate metal oxide cluster nodes, exemplified by UiO-66, have been widely studied, especially in terms of their deviations from the ideal, defect-free crystalline structures. Although defects such as missing linkers, missing nodes, and the presence of adventitious synthesis-derived node ligands (such as acetates and formates) have been proposed, their exact structures remain unknown. Previously, it was demonstrated that defects are correlated and span multiple unit cells. The highly specialized techniques used in these studies are not easily applicable to other MOFs. Thus, there is a need to develop new experimental and computational approaches to understand the structure and properties of defects in a wider variety of MOFs. Here, we show how low-frequency phonon modes measured by inelastic neutron scattering (INS) spectroscopy can be combined with density functional theory (DFT) simulations to provide unprecedented insights into the defect structure of UiO-66. We are able to identify and assign peaks in the fingerprint region (<100 cm –1 ) which correspond to phonon modes only present in certain defective topologies. Specifically, this analysis suggests that our sample of UiO-66 consists of predominantly defect-free fcu regions with smaller domains corresponding to a defective bcu topology with 4 and 2 acetate ligands bound to the Zr 6 O 8 nodes. Importantly, the INS/DFT approach provides detailed structural insights (e.g., relative positions and numbers of acetate ligands) that are not accessible with microscopy-based techniques. Furthermore, the quantitative agreement between DFT simulations and the experimental INS spectrum combined with the relative simplicity of sample preparation, suggests that this methodology may become part of the standard and preferred protocol for the characterization of MOFs, and, in particular, for elucidating the structure defects in these materials.

36 MATERIALS SCIENCE↗

In-Situ and Remote-Sensing Data Fusion Using Machine Learning Techniques to Infer Urban and Fire Related Pollution Plumes

Airmass type characterization is key in understanding the relative contribution of various emission sources to atmospheric composition and air quality and can be useful in bottom-up model validation and emission inventories. However, classification of pollution plumes from space is often not trivial. Sub-orbital campaigns, such as SEAC4RS (Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys) give us a unique opportunity to study atmospheric composition in detail, by using a vast suite of in-situ instruments for the detection of trace gases and aerosols. These measurements allow identification of spatial and temporal atmospheric composition changes due to various pollution plumes resulting from urban, biogenic and smoke emissions. Nevertheless, to transfer the knowledge gathered from such campaigns into a global spatial and temporal context, there is a need to develop workflow that can be applicable to measurements from space. In this work we rely on sub-orbital in-situ and total column remote sensing measurements of various pollution plumes taken aboard the NASA DC-8 during 2013 SEAC4RS campaign, linking them through a neural-network (NN) algorithm to allow inference of pollution plume types by input of columnar aerosol and trace-gas measurements. In particular, we use the 4STAR (Spectrometer for Sky-Scanning, Sun-Tracking Atmospheric Research) airborne measurements of wavelength dependent aerosol optical depth (AOD), particle size proxies, O3, NO2 and water vapor to classify different pollution plumes. Our method relies on assigning a-priori ground-truth labeling to the various plumes, which include urban pollution, different fire types (i.e. forest and agriculture) and fire stage (i.e. fresh and aged) using cluster analysis of aerosol and trace-gases in-situ and auxiliary (e.g. trajectory) data and the training of a NN scheme to fit the best prediction parameters using 4STAR measurements as input. We explore our misclassification rates as related to our ground-truth labels, and with multi-layered pollution plume cases. The next step in our analysis is to optimize parameter selection for a scheme that can be applied to space-borne aerosol and trace-gas observation platforms such as OMI, and future geostationary satellites such as TEMPO and GEO-CAPE.

Neural-network↗

Hydrogen–Deuterium Exchange Mass Spectrometry Identifies Local and Long-Distance Interactions within the Multicomponent Radical SAM Enzyme, PqqE

Interactions among proteins and peptides are essential for many biological activities including the tailoring of peptide substrates to produce natural products. The first step in the production of the bacterial redox cofactor pyrroloquinoline quinone (PQQ) from its peptide precursor is catalyzed by a radical SAM (rSAM) enzyme, PqqE. We describe the use of hydrogen–deuterium exchange mass spectrometry (HDX-MS) to characterize the structure and conformational dynamics in the protein–protein and protein–peptide complexes necessary for PqqE function. HDX-MS-identified hotspots can be discerned in binary and ternary complex structures composed of the peptide PqqA, the peptide-binding chaperone PqqD, and PqqE. Structural conclusions are supported by size-exclusion chromatography coupled to small-angle X-ray scattering (SEC-SAXS). HDX-MS further identifies reciprocal changes upon the binding of substrate peptide and S-adenosylmethionine (SAM) to the PqqE/PqqD complex: long-range conformational alterations have been detected upon the formation of a quaternary complex composed of PqqA/PqqD/PqqE and SAM, spanning nearly 40 Å, from the PqqA binding site in PqqD to the PqqE active site Fe 4 S 4 . Interactions among the various regions are concluded to arise from both direct contact and distal communication. The described experimental approach can be readily applied to the investigation of protein conformational communication among a large family of peptide-modifying rSAM enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monitoring Airspace Complexity and Determining Contributing Factors

The national airspace has evolved over many years to accommodate increased traffic demand [1] while simultaneously maintaining one of the safest forms of transportation [2], [3]. One of the reasons for this success is the ability of the system and the operators to adapt and accommodate to situations that routinely disrupt optimal operations. These situations may include: adverse weather, delays, early arrivals, equipment outages, and other factors that are outside the operators ability to control. These factors can lead to states where automation is unable to properly handle these issues and therefore air traffic controllers and pilots have to intervene, ultimately increasing communication between operators resulting in higher workload. As controller workload increases to handle sub-optimal operating conditions this can be viewed as an increase in complexity. The reasoning for this is because humans are now required to make tactical decisions in response to external factors, resulting in a departure from the strategic plan where operations would be more efficiently managed. Human operators control airspace complexity under rigid regulations that are constantly changing. The airspace is divided into sectors and the number of aircraft assigned to each controller is limited for safe handling. There has been past work that devised airspace complexity metrics in commercial aviation and related these metrics to controller workload (e.g., [4],[5]). The upper bounds on the system load are pre-determined. Such bounds on complexity make for a safe system, but the system cannot scale and adapt to autonomous, dense, and heterogeneous traffic, including the many types of Unmanned Aerial Vehicles (UAVs) envisioned to be added to the operations. We hypothesize that, as traffic density and heterogeneity grow, and other key metrics change, there will be phase transitions at which the way traffic should be managed changes significantly [6]. We offer a method for in-time detection of contributing factors that lead to phase transitions, characterized by increased complexity. To the best of our knowledge, there is no tool similar to our proposed effort that identifies such contributing factors or precursor patterns. To define the scope we are proposing to measure complexity from the viewpoint of the Terminal Radar Approach Control Facilities (TRACON) controller’s perspective. In particular we are analyzing arrivals into KSFO. With safety as the top concern for airspace operators, it is important to recognize that as density and heterogeneity grow, the focus of the system will change. Times of the day when the airspace has low density and heterogeneity, the flights will follow more efficient paths where the aircraft move on established routes that are more or less directly to the destination. However, when density and heterogeneity increases, the system will begin changing focus to avoiding conflicts and collisions and route the flights in a more flexible way. Higher flexibility requires more communication and coordination between controllers and pilots which the current automation is unable to handle. This paper proposes a novel approach that monitors airspace complexity at multiple scales, uses a Machine Learning-based tool that predicts when operations will transition to a regime of greater complexity, and identifies actions that can reduce the complexity while still maintaining efficient and safe operations. We demonstrate our proposed approach using data from multiple complementary sources. This includes, but is not limited to: historical aircraft surveillance data from NASA’s Sherlock Data Warehouse [7], METAR weather data, and airport configuration data from Aviation System Performance Metrics (ASPM). The surveillance data flight paths are sampled at a variable sample rate — increasing as the aircraft approaches the airport. This is due to how Sherlock manages flight track stitching between different radar facilities which have different sampling rates. The weather and performance data are logged at defined intervals throughout the day at a courser refresh rate. In addition to the logged data and metrics, we leverage pre-defined Standard Terminal Arrival Routes (STARs) procedures to characterize the path of each flight. Each flight files for one of these routes in the flight plan well before entering the terminal airspace, and approximately follows the route until it leaves the STAR, typically on the final fix of a runway transition. However, most flights do not always fly the full STAR procedure to completion [8], but the majority do adhere to the fixes within the common route of the procedure. Our approach leverages fixes in the common route of each of the STARs to build a reference path to the airport. This allows us to characterize the flight paths in what we are defining as the “maneuvering area” (the airspace between the STAR and before the flight is lined up on the runway’s final approach) to determine how off nominal the flights are to calculate its complexity score. Determining airspace complexity is a concept that does not have a concrete answer. In designing this metric, we consider what increases the workload for the air traffic controllers. Consequently more specialized vectoring maneuvers results in higher workload. Accordingly, we start with a theory: each flight has a direct path it takes from the STAR’s common route to the final approach’s outer marker fix for the flight’s landing runway. It is important to note that the direct path is only used as a reference. If the majority of the flights have a large consistent offset as compared to other routes it does not necessarily mean that those flights have higher complexity. We are merely building a distribution based on this direct path for that particular STAR and runway pair to determine the normal mode of operations for that route. Flights that are in the upper tail of these distributions will result in higher complexity scores and flights that fly in the median will represent the normal mode of operations and therefore will have lower complexity scores. Since flights following each STAR route take different paths to the airport, we have a different distribution for each STAR route and therefore can model these distributions to compute a complexity score from their respective normalized distributions. To evaluate the effectiveness of our proposed airspace complexity metric we will compare against an established approach based on trajectory clustering [9]. This unsupervised learning technique consists of the following steps: (1) identify the general maneuvering areas (waypoints) by performing $\kappa$-means or DBSCAN clustering on locations where aircraft frequently turn based on the surveillance radar track data, (2) map flight trajectories onto sequences of waypoints, and (3) cluster the sequences based on their common subsequences. From a high-level perspective, this baseline model learns nominal operations in the airspace through the sequence of waypoints that are representative of where aircraft change direction and defines deviations from the nominal operations as “complex.” Therefore, more deviations from the nominal operations correspond to higher complexity values. For our validation, we re-implemented this technique and tune model hyper-parameters to correctly detect waypoints for the arrival traffic into the San Francisco bay area. We will compute the complexity measure over a one-year period using our proposed technique as well as the baseline. Our validation will be based on each technique’s ability to detect a set of undesirable outcomes (e.g., go-arounds, holding patterns, average time in the airspace, etc.). Since our current complexity metric is derived from the offset from the direct reference path, it’s important to understand what causes these offsets. In many of the flights with high offset distance, flights performing holding patterns and S turns can be observed. These maneuvering tactics are utilized to add distance between the aircraft and the destination runway to prevent multiple flights from having conflicting arrival times. In order to predict a rise in complexity (or the precursor to complexity), it’s necessary to be able to identify these potential conflicts (which in turn, result in higher offsets). To do this, we define a “representative flight” for each STAR route and runway pair. This flight is approximately the path the flight would take if there was a clear path with no other flights in the airspace — including the time remaining to the airport. We first identify the flights for a given STAR runway pair using the offset to the reference path distributions that fall between the 44-55 percentiles. This yields the flights that conform to the most normal mode of operation. Each of these flights is partitioned based on the percent complete from the entry point into the maneuvering areas from 0\% – 100\% complete. Then for each percent “bin”, we take the median value of the flight’s latitude/longitude coordinates, airspeed, and (non causal) time remaining to the airport to construct a lookup table for each percent complete bin on a given route. As a flight enters the maneuvering area, we can find the estimated arrival time of a flight to the airport by finding the closest point to the representative path’s percent complete bin (relative to the flight’s current position at any snapshot in the airspace) and therefore retrieve the corresponding remaining time left on the “representative path”. We assume that the flight will follow the representative path to completion when deriving these estimates. We can then compare these estimated arrival times against other flights for the same snapshot in time to identify potential conflicts. If more flights are estimated to arrive within a tolerance window than there are runways available, then we have a potential conflict. We can use this derived measure along with other factors expected to add disruption to the operation such as weather and runway configuration changes as an input to machine learning tools to detect precursors that increases in our complexity measure. This novel method will assist in uncovering insights into the contributing factors that lead to increased complexity that may allow for in-time responses to avoid reaching a high complexity state in the airspace.

complexity↗

Measurement of Kinetic-Scale Current Filamentation Dynamics and Associated Magnetic Fields in Interpenetrating Plasmas

Here, we present the first local, quantitative measurements of ion current filamentation and magnetic field amplification in interpenetrating plasmas, characterizing the dynamics of the ion Weibel instability. The interaction of a pair of laser-generated, counterpropagating, collisionless, supersonic plasma flows is probed using optical Thomson scattering (TS). Analysis of the TS ion-feature revealed anticorrelated modulations in the density of the two ion streams at the spatial scale of the ion skin depth c/ω pi = 120 μm, and a correlated modulation in the plasma current. The inferred current profile implies a magnetic field amplitude ~30 ± 6 T , corresponding to ~1% of the flow kinetic energy, indicating that magnetic trapping is the dominant saturation mechanism.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Parametrizing the detector response with neural networks

In high energy physics, characterizing the response of a detector to radiation is one of the most important and fundamental experimental tasks. In many cases, this task is accomplished by parameterizing summary statistics of the full detector response probability density. The parameterized detector response can then be used for calibration as well as for directly improving physics analysis sensitivity. This paper reports on how to parameterize summary statistics of the detector response using neural networks. Specifically, neural networks are powerful tools for incorporating multidimensional data and the loss function used during training determines which summary statistic is learned. One common summary statistic that has not been combined with deep learning (as far as the authors are aware) is the mode. A neural network-based approach to mode learning is proposed and empirically demonstrated in the context of high energy jet calibrations. Altogether, the neural network-based toolkit for detector response parameterization can enhance the utility of data collected at high energy physics experiments and beyond.

47 OTHER INSTRUMENTATION↗

Utilization of Machine Learning Techniques for Managing the Tracking and Data Relay Satellite Constellation

National Aeronautics and Space Administration’s (NASA) Goddard Space Flight Center (GSFC) operates a constellation of ten geosynchronous Tracking and Data Relay Satellites (TDRS). The TDRS constellation consists of multiple geosynchronous communication relay satellites located around the equator so they can provide continual coverage of any mission in low earth orbit. The TDRS are located primarily in three oceanic regions around the earth. NASA’s White Sands Complex provides the ground communication support for TDRS located over the Atlantic and Pacific Oceans. Another TDRS ground station in Guam supports the TDRS over the Indian Ocean. With these satellites the TDRS network can provide continuous coverage of satellites in low-earth orbit. The NASA Space Network (SN) project office at GSFC manages the constellation of spacecraft. Major customers of the TDRS constellation include, but are not limited to, the International Space Station and the Hubble Space Telescope. The TDRS constellation has three generations of satellites and has been active for over 30 years providing reliable communication links between customer satellites and corresponding ground stations. However, one of the major concerns for TDRS, and in any space mission, is to ensure the health and safety of the spacecraft. Generally, engineers use telemetry data to monitor and analyze the performance and state of health of the spacecraft. Telemetry data contains hundreds of parameters that monitor each important component in the spacecraft, which can be utilized to recognize and characterize the behavior of the spacecraft. Each parameter contains considerable information to represent time-dependent properties of each spacecraft subsystem and component. During the entire life of a TDRS spacecraft, thousands of gigabytes of telemetry data are transmitted in real-time from the spacecraft to the ground station at the White Sands Complex in Las Cruces, New Mexico, and recorded as historical data sets for engineers to process and analyze the events that occurred on-orbit. These parameters contain the function of multiple spacecraft subsystems, such as the attitude control system (ACS), Thermal, Electrical Power Subsystem (EPS), etc. . The first and second generations have exceeded their required lifetime and NASA is keen to manage these spacecrafts carefully in order to maximize the remaining life using the spacecraft telemetry. The challenge is to know when the risk of losing a spacecraft in geosynchronous orbit exceeds the benefit of continued operations for customer support. In the TDRS fleet, the EPS is the most critical subsystem related to spacecraft operations. Failure of the EPS would strand a spacecraft in geosynchronous orbit. Since EPS provides power to the spacecraft, component failures ultimately lead to the inability to support the spacecraft loads and the communications payload. For instance, TDRS-8 has several anomalies in EPS including the Bus Voltage Limiter (BVL) shunt current, solar array loss of circuits, and failed battery cells. Any of these anomalies can cause critical issues to the spacecraft. Therefore, developing a system to analyze and perform early detection of a potential anomaly is an important issue in telemetry data analysis. In recent years, Telemetry Mining (TM) has been proposed to process telemetry data by using Data Mining (DM) techniques such as classification, clustering, regression and anomaly detection. Anomaly detection, also known as outlier detection, has been widely used in many data mining areas such as remote sensing, medical data processing and digital image processing. The goal of anomaly detection is to detect abnormal data, which contains a relatively low probability of occurrence among the entire data set. Early detection of anomalies is one of the most significant issues in managing the spacecraft configuration. If anomalies can be detected early enough, then the redundant resources can be used to extend the life of the operational spacecraft. We present an unsupervised anomaly detection method to process the EPS data extracted from TDRS-8. This is different from traditional analytical methods, which use telemetry data to illustrate behavior and physical meaning of each spacecraft component. TM connects multiple parameters as a vector and then conducts data analysis on this high dimension telemetry vector. This method is looking at the properties of a high dimensional vector that is able to consider the relationship between different parameters in the anomaly detection problem. This kind of method performs much better than the traditional limit checking method. In addition, we propose a new approach of real-time anomaly detection to process telemetry data in real-time, which can then be applied to spacecraft monitoring with high reliability, low cost and high accuracy.

Machine Learning (ML)↗

Excited States of Crystalline Point Defects with Multireference Density Matrix Embedding Theory

Accurate and affordable methods to characterize the electronic structure of solids are important for targeted materials design. Embedding-based methods provide an appealing balance in the trade-off between cost and accuracy-particularly when studying localized phenomena. Here, we use the density matrix embedding theory (DMET) algorithm to study the electronic excitations in solid-state defects with a restricted open-shell Hartree-Fock (ROHF) bath and multireference impurity solvers, specifically, complete active space self-consistent field (CASSCF) and n-electron valence state second-order perturbation theory (NEVPT2). In this work, we apply the method to investigate the electronic excitations in an oxygen vacancy (OV) on a MgO(100) surface and find absolute deviations within 0.05 eV between DMET using the CASSCF/NEVPT2 solver, denoted as CAS-DMET/NEVPT2-DMET, and the nonembedded CASSCF/NEVPT2 approach. Next, we establish the practicality of DMET by extending it to larger supercells for the OV defect and a neutral silicon vacancy in diamond where the use of nonembedded CASSCF/NEVPT2 is extremely expensive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Young Stellar Objects, Accretion Disks, and Their Variability with Rubin Observatory LSST

Vera C. Rubin Observatory, through the Legacy Survey of Space and Time (LSST), will allow us to derive a panchromatic view of variability in young stellar objects (YSOs) across all relevant timescales. Indeed, both short-term variability (on timescales of hours to days) and long-term variability (months to years), predominantly driven by the dynamics of accretion processes in disk-hosting YSOs, can be explored by taking advantage of the multiband filters option available in Rubin LSST, in particular the u, g, r, i filters that enable us to discriminate between photospheric stellar properties and accretion signatures. The homogeneity and depth of sky coverage that will be achieved with LSST will provide us with a unique opportunity to characterize the time evolution of disk accretion as a function of age and varying environmental conditions (e.g., field crowdedness, massive neighbors, metallicity) by targeting different star-forming regions. In this contribution to the Rubin LSST Survey Strategy Optimization Focus Issue, we discuss how implementing a dense observing cadence to explore short-term variability in YSOs represents a key complementary effort to the Wide–Fast–Deep observing mode that will be used to survey the sky over the full duration of the main survey (≈10 yr). The combination of these two modes will be vital to investigate the connection between the inner-disk dynamics and longer-term eruptive variability behaviors, such as those observed on EX Lupi–type objects.

79 ASTRONOMY AND ASTROPHYSICS↗

Mapping causal patterns in crystalline solids

The evolution of the atomic structures of the combinatorial library of Sm-substituted thin film BiFeO 3 along the phase transition boundary from the ferroelectric rhombohedral phase to the non-ferroelectric orthorhombic phase is explored using scanning transmission electron microscopy. Localized properties, including polarization, lattice parameter, and chemical composition, are parameterized from atomic-scale imaging, and their causal relationships are reconstructed using a linear non-Gaussian acyclic model. This approach is further extended to explore the spatial variability of the causal coupling using the sliding window transform method, which revealed that new causal relationships emerged at both the expected locations, such as domain walls and interfaces, and at additional regions forming clusters in the vicinity of the walls or spatially distributed features. While the exact physical origins of these relationships are unclear, they likely represent nanophase-separated regions in the morphotropic phase boundaries. Overall, we posit that an in-depth understanding of complex disordered materials away from thermodynamic equilibrium necessitates understanding not only the generative processes that can lead to observed microscopic states but also the causal links between multiple interacting subsystems.

Causal inference↗

Charge Transport in Zirconium-Based Metal–Organic Frameworks

Metal–organic frameworks (MOFs) are a class of crystalline porous materials characterized by inorganic nodes and multitopic organic linkers. Because of their molecular-scale porosity and periodic intraframework chemical functionality, MOFs are attractive scaffolds for supporting and/or organizing catalysts, photocatalysts, chemical-sensing elements, small enzymes, and numerous other functional-property-imparting, nanometer-scale objects. Notably, these objects can be installed after the synthesis of the MOF, eliminating the need for chemical and thermal compatibility of the objects with the synthesis milieu. Thus, postsynthetically functionalized MOFs can present three-dimensional arrays of high-density, yet well-separated, active sites. Depending on the application and corresponding morphological requirements, MOF materials can be prepared in thin-film form, pelletized form, isolated single-crystal form, polycrystalline powder form, mixed-matrix membrane form, or other forms. For certain applications, most obviously catalytic hydrolysis and electro- or photocatalytic water splitting, but also many others, an additional requirement is water stability. MOFs featuring hexa-zirconium(IV)-oxy nodes satisfy this requirement. For applications involving electrocatalysis, charge storage, photoelectrochemical energy conversion, and chemiresistive sensing, a further requirement is electrical conductivity, as embodied in electron or hole transport. As most MOFs, under most conditions, are electrically insulating, imparting controllable charge-transport behavior is both a chemically intriguing and chemically compelling challenge. Herein, we describe three strategies to render zirconium-based metal–organic frameworks (MOFs) tunably electrically conductive and, therefore, capable of transporting charge on the few nanometers (i.e., several molecular units) to few micrometers (i.e., typical dimensions for MOF microcrystallites) scale. The first strategy centers on redox-hopping between periodically arranged, chemically equivalent sites, essentially repetitive electron (or hole) self-exchange. Zirconium nodes are electrically insulating, but they can function as grafting sites for (a) redox-active inorganic clusters or (b) molecular redox couples. Alternatively, charge hopping based on linker redox properties can be exploited. Marcus’s theory of electron transfer has proven useful for understanding/predicting trends in redox-hopping based conductivity, most notably, in accounting for variations as great as 3000-fold depending on the direction of charge propagation through structurally anisotropic MOFs. In MOF environments, propagation of electronic charge via redox hopping is necessarily accompanied by movement of charge-compensating ions. Consequently, rates of redox hopping can depend on both the identity and concentration of ions permeating the MOF. In the context of electrocatalysis, an important goal is to transport electronic charge fast enough to match or exceed the inherent activity of MOF-based or MOF-immobilized catalysts. Bandlike electronic conductivity is the focus of an alternative strategy: one based on the introduction of molecular guests capable of forming donor–acceptor charge transfer complexes with the host framework. Theory again can be applied predictively to alter conductivity. A third strategy similarly emphasizes electronic conductivity, but it makes use of added bridges in the form of molecular oligomers or inorganic clusters that can then be linked to span the length of a MOF crystallite. For all strategies, retention of molecular-scale porosity is emphasized, as this property is key to many applications. Lastly, while our focus is on Zr-MOFs, the described approaches clearly are extendable to other MOF compositions, as has already been demonstrated, in part, in studies by others.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Whole-Genome Comparisons of Ergot Fungi Reveals the Divergence and Evolution of Species within the Genus Claviceps Are the Result of Varying Mechanisms Driving Genome Evolution and Host Range Expansion

The genus Claviceps has been known for centuries as an economically important fungal genus for pharmacology and agricultural research. Only recently have researchers begun to unravel the evolutionary history of the genus, with origins in South America and classification of four distinct sections through ecological, morphological, and metabolic features (Claviceps sects. Citrinae, Paspalorum, Pusillae, and Claviceps). The first three sections are additionally characterized by narrow host range, whereas section Claviceps is considered evolutionarily more successful and adaptable as it has the largest host range and biogeographical distribution. However, the reasons for this success and adaptability remain unclear. Our study elucidates factors influencing adaptability by sequencing and annotating 50 Claviceps genomes, representing 21 species, for a comprehensive comparison of genome architecture and plasticity in relation to host range potential. Our results show the trajectory from specialized genomes (sects. Citrinae and Paspalorum) toward adaptive genomes (sects. Pusillae and Claviceps) through colocalization of transposable elements around predicted effectors and a putative loss of repeat-induced point mutation resulting in unconstrained tandem gene duplication coinciding with increased host range potential and speciation. Alterations of genomic architecture and plasticity can substantially influence and shape the evolutionary trajectory of fungal pathogens and their adaptability. Furthermore, our study provides a large increase in available genomic resources to propel future studies of Claviceps in pharmacology and agricultural research, as well as, research into deeper understanding of the evolution of adaptable plant pathogens.

59 BASIC BIOLOGICAL SCIENCES↗

Intense windstorms in the northeastern United States

Abstract. Windstorms are a major natural hazard in many countries. The objective of this study is to identify and characterize intense windstorms during the last 4 decades in the US Northeast and determine both the sources of cyclones responsible for these events and the manner in which those cyclones differ from the cyclone climatology. The windstorm detection is based on the spatial extent of locally extreme wind speeds at 100 m height from the ERA5 reanalysis database. During the top 10 windstorms, wind speeds exceed their local 99.9th percentile over at least one-third of land-based ERA5 grid cells in this high-population-density region of the USA. Maximum sustained wind speeds at 100 m during these windstorms range from 26 to over 43 ms−1, with wind speed return periods exceeding 6.5 to 106 years (considering the top 5 % of grid cells during each storm). Property damage associated with these storms, with inflation adjusted to January 2020, ranges from USD 24 million to over USD 29 billion. Two of these windstorms are linked to decaying tropical cyclones, three are Alberta clippers, and the remaining storms are Colorado lows. Two of the 10 re-intensified off the east coast, leading to development of nor'easters. These windstorms followed frequently observed cyclone tracks but exhibit maximum intensities as measured using 700 hPa relative vorticity and mean sea level pressure that is 5–10 times the mean values for cyclones that followed similar tracks over this 40-year period. The time evolution of wind speeds and concurrent precipitation for those windstorms that occurred after the year 2000 exhibit good agreement with in situ ground-based and remote sensing observations, plus storm damage reports, indicating that the ERA5 reanalysis data have a high degree of fidelity for large, damaging windstorms such as these. A larger pool of the top 50 largest windstorms exhibit evidence of only weak serial clustering, which is in contrast to the relatively strong serial clustering of windstorms in Europe.

58 GEOSCIENCES↗

Microbial Characterization During the Early Habitation of the International Space Station

An evaluation of the microbiota from air, water, and surface samples provided a baseline of microbial characterization onboard the International Space Station (ISS) to gain insight into bacterial and fungal contamination during the initial stages of construction and habitation. Using 16S genetic sequencing and rep-PCR, 63 bacterial strains were isolated for identification and fingerprinted for microbial tracking. Of the bacterial strains that were isolated and fingerprinted, 19 displayed similarity to each other. The use of these molecular tools allowed for the identification of bacteria not previously identified using automated biochemical analysis and provided a clear indication of the source of several ISS contaminants. Strains of Bradyrhizobium and Sphingomonas unable to be identified using sequencing were identified by comparison of rep-PCR DNA fingerprints. Distinct DNA fingerprints for several strains of Methylobacterium provided a clear indication of the source of an ISS water supply contaminant. Fungal and bacterial data acquired during monitoring do not suggest there is a current microbial hazard to the spacecraft, nor does any trend indicate a potential health risk. Previous spacecraft environmental analysis indicated that microbial contamination will increase with time and will require continued surveillance. Copyright 2004 Springer-Verlag.

Fungi/genetics↗

Developing Upscaling Approach for Swarming Hydraulic Fractures Observed at Hydraulic Fracturing Test Site through Multiscale Simulations

We show that this work aims to address a challenge posed by recent observations of tightly spaced hydraulic fractures in core samples from the hydraulic fracturing test site (HFTS) in the Middle Wolfcamp Formation. Many fractures in retrieved cores have subfoot spacing, which is at odds with conventional models in which usually one hydraulic fracture is initiated per cluster. Models assuming a single fracture at each cluster, although a common practice, often predict excessive fracture propagation that is inconsistent with microseismic observation. Here, we aim to develop a numerical approach to effectively account for densely spaced hydraulic fractures in field-scale simulations. Because it is impractical to explicitly model all aforementioned fractures, we develop a new upscaling law that enables existing simulation tools to predict reservoir response to fracture swarms. The upscaling law is derived based on an energy equivalence argument and validated through multiscale simulations using a high-fidelity code, GEOS. The swarming fractures are first modeled with a spacing that is much smaller than the cluster spacing; these fractures are then approximated by an upscaled, single fracture based on the proposed upscaling law. The upscaled fracture is shown to successfully match the energy input rate and produce the total fracture aperture and average propagation length of the explicitly simulated swarm. Afterward, the upscaling approach is further implemented in 3D field-scale simulations and validated against the HFTS microseismic data of a horizontal well. Our results show that hydraulic fracture swarming can significantly affect fracture propagation behaviors compared with the propagation of single fractures as assumed by conventional modeling approaches. Under the considered situations, the conventional treatment yields fast propagation speed that far exceeds that indicated by the microseismic data. We also illustrate that this discrepancy can be reduced readily through the implementation of the upscaling law. Our results demonstrate the importance of accounting for the fracture swarming effect in field-scale simulations and the efficacy of this approach to enable realistic predictions of reservoir responses to fracture swarms, without the need to model tightly spaced fractures individually.

02 PETROLEUM↗

GCR Transport in the Brain: Assessment of Self-Shielding, Columnar Damage, and Nuclear Reactions on Cell Inactivation Rates

Radiation shield design is driven by the need to limit radiation risks while optimizing risk reduction with launch mass/expense penalties. Both limitation and optimization objectives require the development of accurate and complete means for evaluating the effectiveness of various shield materials and body-self shielding. For galactic cosmic rays (GCR), biophysical response models indicate that track structure effects lead to substantially different assessments of shielding effectiveness relative to assessments based on LET-dependent quality factors. Methods for assessing risk to the central nervous system (CNS) from heavy ions are poorly understood at this time. High-energy and charge (HZE) ion can produce tissue events resulting in damage to clusters of cells in a columnar fashion, especially for stopping heavy ions. Grahn (1973) and Todd (1986) have discussed a microlesion concept or model of stochastic tissue events in analyzing damage from HZE's. Some tissues, including the CNS, maybe sensitive to microlesion's or stochastic tissue events in a manner not illuminated by either conventional dosimetry or fluence-based risk factors. HZE ions may also produce important lateral damage to adjacent cells. Fluences of high-energy proton and alpha particles in the GCR are many times higher than HZE ions. Behind spacecraft and body self-shielding the ratio of protons, alpha particles, and neutrons to HZE ions increases several-fold from free-space values. Models of GCR damage behind shielding have placed large concern on the role of target fragments produced from tissue atoms. The self-shielding of the brain reduces the number of heavy ions reaching the interior regions by a large amount and the remaining light particle environment (protons, neutrons, deuterons. and alpha particles) may be the greatest concern. Tracks of high-energy proton produce nuclear reactions in tissue, which can deposit doses of more than 1 Gv within 5 - 10 cell layers. Information on rates of cell killing from GCR, including patterns of cell killing from single particle tracks. can provide useful information on expected differences between proton and HZE tracks and clinical experiences with photon irradiation. To model effects on cells in the brain, it is important that transport models accurately describe changes in the GCR due to interactions in the cranium and proximate tissues. We describe calculations of the attenuated GCR particle fluxes at three dose-points in the brain and associated patterns of cell killing using biophysical models. The effects of the brain self-shielding and bone-tissue interface of the skull in modulating the GCR environment are considered. For each brain dose-point, the mass distribution in the surrounding 4(pi) solid angle is characterized using the CAM model to trace 512 rays. The CAM model describes the self-shielding by converting the tissue distribution to mass-equivalent aluminum, and nominal values of spacecraft shielding is considered. Particle transport is performed with the proton, neutron, and heavy-ion transport code HZETRN with the nuclear fragmentation model QMSFRG. The distribution of cells killed along the path of individual GCR ions is modeled using in vitro cell inactivation data for cells with varying sensitivity. Monte Carlo simulations of arrays of inactivated cells are considered for protons and heavy ions and used to describe the absolute number of cell killing events of various magnitude in the brain from the GCR. Included are simulations of positions of inactivated cells from stopping heavy ions and nuclear stars produced by high-energy ions most importantly, protons and neutrons.

Shavers, M. R.↗

Thermal Weight Determination and Interstate Coupling in State-Averaged ADAPT-VQE

Characterizing electronic thermal states at low temperatures is an important but challenging task in quantum chemistry and condensed matter physics, making it a prime candidate for a useful application in quantum computing. One of the most successful methods for state preparation on quantum computers is the Adaptive, Problem-Tailored (ADAPT) Variational Quantum Eigensolver (VQE), which has recently been generalized to treat excited states within a state-averaged framework as well as Gibbs states. In this work, we introduce Helmholtz-Optimized Thermal (HOT) ADAPT-VQE, an ancilla-free strategy for preparing Gibbs states that directly minimizes the Helmholtz free energy by targeting the dominant eigenstates of the thermal ensemble. We demonstrate the usefulness of HOT-ADAPT-VQE by predicting the free energy of two model systems with strongly correlated ground states: (1) the Fe 2+ cation in a magnetic field and (2) a [Cu 2 O 7 ] 10– fragment of the Mott insulator La 2 CuO 4 . Our results demonstrate that HOT-ADAPT-VQE significantly improves upon Gibbs-state estimates from multistate variants of ADAPT-VQE, often with substantially shallower quantum circuits, making it a promising candidate for thermal-state calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗