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Early Failure of Lithium–Sulfur Batteries at Practical Conditions: Crosstalk between Sulfur Cathode and Lithium Anode

Lithium–sulfur (Li–S) batteries are one of the most promising next-generation energy storage technologies due to their high theoretical energy and low cost. However, Li–S cells with practically high energy still suffer from a very limited cycle life with reasons which remain unclear. Here, through cell study under practical conditions, it is proved that an internal short circuit (ISC) is a root cause of early cell failure and is ascribed to the crosstalk between the S cathode and Li anode. The cathode topography affects S reactions through influencing the local resistance and electrolyte distribution, particularly under lean electrolyte conditions. The inhomogeneous reactions of S cathodes are easily mirrored by the Li anodes, resulting in exaggerated localized Li plating/stripping, Li filament formation, and eventually cell ISC. Manipulating cathode topography is proven effective to extend the cell cycle life under practical conditions. The findings of this work shed new light on the electrode design for extending cycle life of high-energy Li–S cells, which are also applicable for other rechargeable Li or metal batteries.

25 ENERGY STORAGE↗

Global Geo-processed Data of Aquifer Properties by 0.5° Grid, Country and Water Basins

This repository of global hydrogeologic datasets contains aquifer properties on 0.5° scale, including depth to groundwater (Fan et al., 2013), aquifer thickness (de Graaf et al., 2015), WHYMap aquifer classes (Richts et al., 2011), porosity and permeability (Gleeson et al., 2014), digitized and geo-processed from their respective sources. Globally gridded aquifer properties could be used independently to estimate global groundwater availability or used as critical inputs to the superwell model to simulate groundwater extraction and provide estimates of pumped volumes and unit costs under user-specific scenarios. Key resources related to this data are: Niazi, H., Ferencz, S., Graham, N., Yoon, J., Wild, T., Hejazi, M., Watson, D., & Vernon, C. (2024; In-prep). Long-term Hydro-economic Assessment Tool for Evaluating Global Groundwater Cost and Supply: Superwell v1. Geoscientific Model Development. superwell model repository which uses this data to simulate groundwater extraction and provides estimates of the global extractable volumes and unit-costs ($/km3) of accessible groundwater production under user-specified extraction scenarios. Repository Overview Main output: aquifer_properties.csv contains all processed outputs, including aquifer properties like porosity, permeability, aquifer thickness, and depth to groundwater. shapefiles.zip: contains all digitized GIS databases and shapefile for all aquifer properties prep_inputs.R: R script that processes the shapefiles to produce the aquifer_properties file plot_inputs.R: R script for plotting the maps and conducting preliminary analysis on the available groundwater volume basin_to_country_mapping.csv, basin_country_region_mapping.csv and continent_county_mapping.csv provide the mapping between continents, 32 energy-economic macro regions, countries, and water basins for post-processing aquifer_properties.csv Maps: Each map visualizes the spatial distribution of one of the aquifer properties across the globe map_in_Porosity.png map_in_Permeability.png map_in_Aquifer_thickness.png map_in_Depth_to_water.png map_in_Grid_area_km.png map_in_WHYClass.png Sample inputs sample_inputs.py: this script samples inputs from the aquifer_properties dataset, ensuring the sampled and original inputs maintain the same distributions sampled_data_100.csv contains 100 sampled data points and sampled_data_100.png compares their distributions Dataset Overview The main outputs are consolidated in a comprehensive aquifer_properties.csv file and include the following fields: GridCellID: Unique identifier for each (roughly 0.5°) grid cell Continent: Continent name Country: Country name GCAM_basin_ID: Identifier for GCAM hydrologic basin Basin_long_name: Full name of the basin WHYClass: Hydrogeologic classification based on WHYMap aquifer classes (Richts et al., 2011) Porosity: Soil porosity (%) (Gleeson et al., 2014) Permeability: Soil permeability (in square meters; Gleeson et al., 2014) Aquifer_thickness: Thickness of the aquifer (in meters; de Graaf et al., 2015) Depth_to_water: Depth to groundwater (in meters; Fan et al., 2013) Grid_area: Area of the grid cell (in square meters) Key References The datasets are digitized versions of global hydrogeologic properties from the following key literature sources: Depth to Groundwater: Fan, Y., Li, H., & Miguez-Macho, G. (2013). Global Patterns of Groundwater Table Depth. Science, 339(6122), 940-943. https://doi.org/10.1126/science.1229881 Aquifer Thickness: de Graaf, I. E. M., Sutanudjaja, E. H., van Beek, L. P. H., & Bierkens, M. F. P. (2015). A high-resolution global-scale groundwater model. Hydrol. Earth Syst. Sci., 19(2), 823-837. https://doi.org/10.5194/hess-19-823-2015 Porosity and Permeability: Gleeson, T., Moosdorf, N., Hartmann, J., & van Beek, L. P. H. (2014). A glimpse beneath earth's surface: GLobal HYdrogeology MaPS (GLHYMPS) of permeability and porosity. Geophysical Research Letters, 41(11), 3891-3898. https://doi.org/10.1002/2014GL059856 Aquifer classes: Richts, A., Struckmeier, W. F., & Zaepke, M. (2011). WHYMAP and the Groundwater Resources Map of the World 1:25,000,000. In J. A. A. Jones (Ed.), Sustaining Groundwater Resources: A Critical Element in the Global Water Crisis (pp. 159-173). Springer Netherlands. https://doi.org/10.1007/978-90-481-3426-7_10 Cite as Niazi, H., Watson, D., Hejazi, M., Yonkofski, C., Ferencz, S., Vernon, C., Graham, N., Wild, T., & Yoon, J. (2024). Global Geo-processed Data of Aquifer Properties by 0.5° Grid, Country and Water Basins. MSD-LIVE Data Repository. https://doi.org/10.57931/2307831 Contact Reach out to Hassan Niazi or open an issue in superwell repository for questions or suggestions.

aquifer thickness↗

Stability of the Early Mars Atmosphere to Collapse into Permanent Polarcaps

The presence of a permanent CO2 polar ice cap on Mars has important consequences for the planet's climate system. The heat balance of such a cap, which is determined mainly by atmospheric heat transport, and the downward solar in infrared radiative fluxes, determines its surface temperature, which through the vapor pressure relation sets the mean annual surface pressure. On Mars today, for example, the south residual CO2 cap is present year-round with a mean annual temperature of approximately 145 K which corresponds to a mean annual CO2 vapor pressure of approximately 600 Pa. On early Mars, permanent polar caps are also possible especially since the sun was less luminous 3.5-4.0 Gya. Thus, the existence of permanent polar caps on early Mars is central to understanding the nature of the planets climate system in those ancient times and whether or not the atmosphere might have been capable of sustaining conditions suitable for liquid water flowing over the surface as is indicated in the geological record. Forget et al [1] showed that for present orbital properties atmospheric collapse into permanent polar caps could only be prevented for surface pressures roughly between 500 - 3000 hPa. Though follow-on studies confirm and extend the Forget et al. results [2], the full sensitivity of this "window" of stability has not been explored. There are many factors to consider such the albedo of the caps, dust content of the atmosphere, and the presence of water ice clouds. However, we begin our exploration of the stability of the early Martian atmosphere by focusing on the role of CO2 ice clouds. In some preliminary simulations with the Ames Mars General Circulation Model (GCM) we found that atmospheric collapse depends on assumptions regarding the fate of CO2 ice clouds. If, for example, we assume the clouds immediately fall to the surface, then in some cases collapse is favored. On the other hand if the clouds are allowed to fall and evaporate, collapse can be averted. This implies that CO2 ice cloud microphysics is important to the overall stability of the atmosphere. Though the Ames GCM has a sophisticated CO2 cloud microphysics package that includes nucleation, growth, and sedimentation (see accompanying poster by Kahre et al. [3]), we have implemented a simpler scheme based on the Forget et al. [1] approach to CO2 ice clouds. Our goal is to reproduce and expand their study. The key parameter in this approach is the concentration and vertical distribution of cloud condensation nuclei (CCN), i.e., dust particles. Fewer CCN lead to larger particles which fall faster, while higher CCN concentrations lead to smaller particles and thicker clouds that remain suspended for longer periods of time. We plan to explore the stability of the atmosphere to CCN concentrations and distributions and then assess the capability of thick early atmospheres to loft and distribute dust particles (CCN) around the planet. Thus, our work will shed light on the nature of the coupling between the dust and CO2 cycles and the implications it has for the early Mars climate system.

ice cap↗

Swept-Wing Receptivity Studies Using Distributed Roughness

Transition to turbulence in swept-wing flows has resisted correlation with linear theory because of its sensitivity to freestream conditions and 3-D roughness and because one of the principal instability modes quickly 'becomes nonlinear. In the face of such a formidable problem, two rather long-term fundamental efforts have been underway at DLR Gottinberg and Arizona State University that address swept-wing transition. These efforts have been recently reviewed by Bippes (1997) and Reibert and Saric (1997). Thus, the present work is a continuation of a series of studies on swept-wing boundary layers which have led to a better understanding of the transition process. In particular, we have taken advantage of the sensitivity to 3-D roughness and the modal nature of the instability in order to propose a particular control strategy. Complementing the two aforementioned reviews, general reviews of the swept-wing transition problem are found in Arnal (1997) and Kachanov (1996). Other recent reviews include Reshotko (t997), Crouch (1997), and Herbert (1997a,b). The failure of linear theory is discussed in Reed et al. (1996). The historical work is found in Reed and Sar-ic (1989). The basic idea is that the combination of sweep and chordwise pressure gradient within the boundary layer creates a velocity component perpendicular to the inviscid streamline. This crossflow profile is inflectional and exhibits both traveling and stationary unstable waves called crossflow vortices that are (approximately) aligned along the inviscid streamlines. Under conditions of low freestream turbulence levels, the dominant crossflow wave is stationary (Reibert and Saric t997) while moderate to high turbulence levels initiate dominant traveling waves (Dehle and Bippes 1996; Bippes 1997). 'Me mechanism is relatively insensitive to sound and 2-D surface roughness (Radeztsky et al. 1993) but very sensitive to 3-D roughness near the attachment line. We concentrate our work on low-turbulence freestream flows and stationary crossflow waves. Although the v' and w' components of the disturbances are very small, by convecting streamwise momentum in the wall-normal direction, they produce 0(l) changes inu'.Thus the mean flow is highly distorted with localized inflection points. Transition is then triggered by a high-frequency secondary instability of the distorted mean profile.

Saric, William S.↗

Towards Quantifying and Correlating RTV Intumescence to Entry-Relevant Conditions

Room Temperature Vulcanizing silicone (RTV) is a high-temperature adhesive used as a gap-filler between Thermal Protection System (TPS) tiles for heatshields on numerous missions. It is also adopted to bond instrumentation plugs of temperature and pressure sensors into heatshield’s tiles. While RTV has been traditionally assumed to be a non-porous and non-ablating material, numerous experiments have shown that RTV pyrolyzes and becomes highly porous as it is heated. Experimental data has also shown heating rate-dependent swelling (or intumescence) and shrinking of RTV, these volume changes may cause roughness-induced boundary layer transition. Outgassing and surface oxide formation of RTV upon decomposition also occur, which can be sources of contamination of heat shield sensors. This combination of detrimental effects motivates a critical need to develop a high-fidelity model for RTV ablation. As a first critical step in RTV modeling, a comprehensive material properties database for RTV was collected that account for the lack of data in properties such as pyrolysis char yield, shape change, virgin and char porosity. The next step is to quantify the volume change of RTV as a function of temperature. While this was done in previous campaigns, limited data was collected which showed a possible heating rate dependent intumescent behavior. To further understand the intumescence phenomenon of RTV, numerous dedicated experiments were performed at Beamline 8.3.2 of the Advanced Light Source, where RTV samples were heated while X-ray scans were taken in situ. Micro-Computed Tomography scans were taken in situ for low heating rates (≤ 60 °C/min), whereas continuous radiography scans were taken for higher heating rates (≤ 1500 ºC/min). Unconstrained samples and samples constrained in different holders (quartz, graphite, FiberForm and PICA) were tested to determine the change in intumescence due to confinement. Using deep learning techniques, the tomographies and radiographies are segmented to obtain volume change, porosity, pore size distributions and connectivity. From the results obtained, modifications to the previous RTV intumescence model are proposed, along with preliminary comparisons to testing RTV at high-enthalpy facilities.

RTV↗

Geologic Mapping of Ejecta Deposits in Oppia Quadrangle, Asteroid (4) Vesta

Oppia Quadrangle Av-10 (288-360 deg E, +/- 22 deg) is a junction of key geologic features that preserve a rough history of Asteroid (4) Vesta and serves as a case study of using geologic mapping to define a relative geologic timescale. Clear filter images, stereo-derived topography, slope maps, and multispectral color-ratio images from the Framing Camera on NASA's Dawn spacecraft served as basemaps to create a geologic map and investigate the spatial and temporal relationships of the local stratigraphy. Geologic mapping reveals the oldest map unit within Av-10 is the cratered highlands terrain which possibly represents original crustal material on Vesta that was then excavated by one or more impacts to form the basin Feralia Planitia. Saturnalia Fossae and Divalia Fossae ridge and trough terrains intersect the wall of Feralia Planitia indicating that this impact basin is older than both the Veneneia and Rheasilvia impact structures, representing Pre-Veneneian crustal material. Two of the youngest geologic features in Av-10 are Lepida (approximately 45 km diameter) and Oppia (approximately 40 km diameter) impact craters that formed on the northern and southern wall of Feralia Planitia and each cross-cuts a trough terrain. The ejecta blanket of Oppia is mapped as 'dark mantle' material because it appears dark orange in the Framing Camera 'Clementine-type' colorratio image and has a diffuse, gradational contact distributed to the south across the rim of Rheasilvia. Mapping of surface material that appears light orange in color in the Framing Camera 'Clementine-type' color-ratio image as 'light mantle material' supports previous interpretations of an impact ejecta origin. Some light mantle deposits are easily traced to nearby source craters, but other deposits may represent distal ejecta deposits (emplaced greater than 5 crater radii away) in a microgravity environment.

Asteroids↗

Atmospheric Soundings from AIRS/AMSU in Partial Cloud Cover

Simultaneous use of AIRS/AMSU-A observations allow for the determination of accurate atmospheric soundings under partial cloud cover conditions. The methodology involves the determination of the radiances AIRS would have seen if the AIRS fields of view were clear, called clear column radiances, and use of these radiances to infer the atmospheric and surface conditions giving rise to these clear column radiances. Susskind et al. demonstrate via simulation that accurate temperature soundings and clear column radiances can be derived from AIRS/AMSU-A observations in cases of up to 80% partial cloud cover, with only a small degradation in accuracy compared to that obtained in clear scenes. Susskind and Atlas show that these findings hold for real AIRS/AMSU-A soundings as well. For data assimilation purposes, this small degradation in accuracy is more than offset by a significant increase in spatial coverage (roughly 50% of global cases were accepted, compared to 3.6% of the global cases being diagnosed as clear), and assimilation of AIRS temperature soundings in partially cloudy conditions resulted in a larger improvement in forecast skill than when AIRS soundings were assimilated only under clear conditions. Alternatively, derived AIRS clear column radiances under partial cloud cover could also be used for data assimilation purposes. Further improvements in AIRS sounding methodology have been made since the results shown in Susskind and Atlas . A new version of the AIRS/AMSU-A retrieval algorithm, Version 4.0, was delivered to the Goddard DAAC in February 2005 for production of AIRS derived products, including clear column radiances. The major improvement in the Version 4.0 retrieval algorithm is with regard to a more flexible, parameter dependent, quality control. Results are shown of the accuracy and spatial distribution of temperature-moisture profiles and clear column radiances derived from AIRS/AMSU-A as a function of fractional cloud cover using the Version 4.0 algorithm. Use of the Version 4.0 AIRS temperature profiles increased the positive forecast impact arising from AIRS retrievals relative to what was shown in Susskind and Atlas .

Susskind, Joel↗

Dust extinction and molecular gas in the dark cloud IC 5146

In this paper we describe a powerful method for mapping the distribution of dust through a molecular cloud using data obtained in large-scale, multiwavelength, infrared imaging surveys. This method combines direct measurements of near-infrared color excess and certain techniques of star counting to derive mean extinctions and map the dust column density distribution through a cloud at higher angular resolutions and greater optical depths than those achieved previously by optical star counting. We report the initial results of the application of this method to a dark cloud complex near the cluster IC 5146, where we have performed coordinated, near-infrared, JHK imaging and (13)CO, C(18)O, and CS millimeter-wave, molecular-line surveys of a large portion of the complex. More than 4000 stars were detected in our JHK survey of the cloud. Of these, all but about a dozen appear to be field stars not associated with the cloud. Star count maps at J band show a striking and detailed anticorrelation between the surface density of J-band sources and CO and CS molecular-line emission. We used the (H-K) colors and positions of nearly 1300 sources to directly measure and map the extinction and thus trace the dust column density through the cloud at an effective angular resolution of 1 min .5. We report an interesting correlation between the measured dispersion in our extinction determinations and the extinction. Modeling this relation indicates that effects of small-scale cloud structure dominate the uncertainties in our measurements. Moreover, we demonstrate that such observations can be used to place constraints on the nature of the spatial distribution of extinction on scales smaller than our resolution. In particular, we show that models in which the dust is distributed uniformly or in discrete high-extinction clumps on scales smaller than (1 min .5) are inconsistent with the observations. We have derived extinctions at the same positions and at the same angular resolution (1 min .7) as our molecular-line observations. This enabled a direct comparison of (13)CO, C(18)O, and CS integrated intensities and column densities with A(sub V) for more than 500 positions in the cloud, corresponding to a range in A(sub V) between 0 to 32 mag of extinction. We found the integrated intensities of (13)CO, C(18)O, and CS to be roughly linearly correlated with extinction over different ranges of extinction. However, for all three molecules we find the scatter in the observed relations to be larger than can be accounted for by instrumental error, suggesting that there are large intrinsic variations in the abundances or excitation of the molecules through the cloud. Mean abundances for all the molecules relative to hydrogen were directly derived from the data. The ratio of (13)CO to C(18)O abundances was found to be significantly higher than the terrestrial ratio in regions where extinction is less than 10 mag. In the same region, the dispersion in the abundance ratio is also found to be very large, suggesting that the abundances of one or both molecules are very unstable even at relatively large cloud optical depths. Beyond 10 mag of extinction the abundances of both species appear very stable with their ratio close to the terrestrial value.

Lada, Charles J.↗

Soot Aerosol Properties in Laminar Soot-Emitting Microgravity Nonpremixed Flames

The spatial distributions and morphological properties of the soot aerosol are examined experimentally in a series of 0-g laminar gas-jet nonpremixed flames. The methodology deploys round jet diffusion flames of nitrogen-diluted acetylene fuel burning in quiescent air at atmospheric pressure. Full-field laser-light extinction is utilized to determine transient soot spatial distributions within the flames. Thermophoretic sampling is employed in conjunction with transmission electron microscopy to define soot microstructure within the soot-emitting 0-g flames. The microgravity tests indicate that the 0-g flames attain a quasi-steady state roughly 0.7 s after ignition, and sustain their annular structure even beyond their luminous flame tip. The measured peak soot volume fractions show a complex dependence on burner exit conditions, and decrease in a nonlinear fashion with decreasing characteristic flow residence times. Fuel preheat by approximately 140 K appears to accelerate the formation of soot near the flame axis via enhanced fuel pyrolysis rates. The increased soot presence caused by the elevated fuel injection temperatures triggers higher flame radiative losses, which may account for the premature suppression of soot growth observed along the annular region of preheated-fuel flames. Electron micrographs of soot aggregates collected in 0-g reveal the presence of soot precursor particles near the symmetry axis at midflame height, The observations also verify that soot primary particle sizes are nearly uniform among aggregates present at the same flame location, but vary considerably with radius at a fixed distance from the burner. The maximum primary size in 0-g is found to be by 40% larger than in 1-g, under the same burner exit conditions. Estimates of the number concentration of primary particles and surface area of soot particulate phase per unit volume of the combustion gases are also made for selected in-flame locations.

Konsur, Bogdan↗

Maximum entropy modeling to identify physical drivers of shallow snowpack heterogeneity using unpiloted aerial system (UAS) lidar

Understanding the spatial variability of the snowpack is valuable for hydrologists and ecologists seeking to predict hydrological processes in a cold region. Snow distribution is a function of interactions among static variables, such as terrain, vegetation, and soil properties, and dynamic meteorological variables, such as solar radiation, wind speed and direction, and soil moisture. However, identifying the dominant physical drivers responsible for spatial patterns of the snowpack, particularly for ephemeral, shallow snowpacks, has been challenging due to the lack of the high-resolution snowpack and physical variables with high vertical accuracy as well as inherent limitations in traditional approaches. This study uses an Unpiloted Aerial System (UAS) lidar-based snow depth and static variables (1-m spatial resolution) to analyze field-scale spatial structures of snow depth and apply the Maximum Entropy (MaxEnt) model to identify primary controls over open terrain and forests at the University of New Hampshire Thompson Farm Research Observatory, New Hampshire, United States. We found that, among nine topographic and soil variables, plant functional type and terrain roughness contribute up to 80% and 76% of relative importance in the MaxEnt framework to predict locations of deeper or shallower snowpacks, respectively, across a mixed temperate forested and field landscape. Soil variables, such as organic matter and saturated hydraulic conductivity, were also important controls (up to 70% and 81%) on snow depth spatial variations for both open and forested landscapes suggesting spatial variations in soil variables under snow can control thermal transfer among soil, snowpack, and surface-atmosphere. This work contributes to improving land surface and snow models by informing parameterization of the sub-grid scale snow depths, down-scaling remotely sensed snow products, and understanding field scale snow states.

Eunsang Cho↗

A Decision Support System for Extravehicular Operations Under Significant Communication Latency

Within the next few decades, humanity hopes to perform extravehicular activities (EVAs) on the surface of Mars; however, several technical and operational challenges must first be overcome. Foremost among these challenges is managing a significant two-way communication latency between Earth and Mars. Current and historical paradigms of EVA operations have required near-real-time communication between the crewmember(s) performing an EVA and an Earth-based mission control. Next-generation operational paradigms for supporting deep space exploration will necessitate a distributed decision authority system, including delayed Earth-based mission control, the on-planet extravehicular crewmember(s), and intermediate mission support from intravehicular crewmember(s) within real-time communication range. This latter group is of particular interest: they must provide operations support without the plentiful resources available to mission control on Earth. For this purpose, NASA is developing the Personalized EVA Informatics and Decision Support (PersEIDS) software platform. PersEIDS is designed to bolster operator situational awareness and offload operator workload by automating the tracking and projection of consumables usage over an EVA timeline, providing real-time probabilistic safety assessments of an EVA timeline given consumables constraints, and recommending alternative EVA timeline(s) when the active timeline is not expected to be completed under consumables limits. The PersEIDS concept of operations, use cases, and models will be presented. A limited version of PersEIDS was demonstrated during a three-day-long study where each day a roughly four-hour-long simulated Martian EVA was performed in virtual reality at the NASA Johnson Space Center. The first day was a control trial without PersEIDS support; the second and third days represented different levels of decision support provided by PersEIDS to the intravehicular crewmember acting as mission control. With PersEIDS support, the IV crewmember was able to manage the mission to completion faster and with more remaining consumables; however, additional testing is required to understand confounding factors, e.g. training bias.

Mars↗

In-situ Characterizations of Microstructural Degradation of Perovskite Solar Cells

Rapid progress has been achieved in perovskite solar cells (PSCs), and their efficiencies have improved from 3.8 % to 24.2 % in less than a decade. With low-cost processing, PSCs have shown exciting photovoltaic (PV) properties, such as effective optical absorption, a long carrier lifetime, and unique defect tolerance. While recent studies demonstrated improved stability up to 100 days, PSC technology is still challenged to meet the stringent industry requirements for commercialization. Despite considerable efforts, the underlying physical mechanisms for the inferior stability of PSCs are not well understood. One reason for this divergence is that many established measurement techniques (e.g., quantum efficiency, photoluminescence) probe the properties on length scales far greater than that of electronic and/or structural inhomogeneity (i.e., < 1 μm near grain boundaries) and therefore characterize convoluted and/or averaged properties. Ion/electron beam-based techniques have been extensively used to access the microstructures of PSCs, enabling atomic/nanoscale structural, chemical, optical, and electrical characterizations. For example, focused ion beam (FIB) milling produces an atomically smooth surface that minimizes the artifacts attributed to the surface roughness. FIB techniques can also create a well-defined cross-section of PSCs without mechanical damage in a physical cleaving sample preparation. While powerful, there are some concerns about possible beam damage of inorganic-organic perovskites via chemical-bond breakage and local heating. This project aims to comprehensively understand how the microstructural/interfacial properties of PSCs (e.g., Methylammonium Lead Iodide [MAPbI 3 ]) are modified under the irradiating ion beams. Specifically, we investigate the sub-surface properties of PSCs before and after Ar-ion beam injections. Kelvin probe force microscopy (KPFM) measures the contact potential differences (CPDs). Photoluminescence (PL) microscopy in conjunction with Finite-Difference Time-Domain (FDTD) simulations infers the formation of a “dead layer” (< 15 nm) on the subsurface of MAPbI 3 during Ar+ milling processes while preserving the initial bulk properties. The x-ray photoemission spectroscopy (XPS) confirms this modified surface is a lead-rich and iodine-deficient surface. We initiate customizing in-situ measurement setup while measuring the local optical and electrical properties of PSC under thermal (cooling, heating) and light stressors. Our results provide in-depth knowledge of the ion-beam impact on metal-halide perovskites and how this modified sub-surface impacts their properties under accelerated stressors of light and heat. Intensive Monte Carlo simulations of an electron beam interacting with PSCs provide the beam energy distribution in PSCs, proposing possible measurement conditions of using e-beam with minimizing beam damage. Our in-situ measurement platform can accommodate the diverse architecture of PSC devices for studying deterioration mechanisms under mixed environmental stressors.

14 SOLAR ENERGY↗

Accounting for hydrological and microbial processes on greenhouse gas budgets from river systems (Final Report)

River systems have a disproportionately large impact on carbon and nitrogen cycling on this planet. For instance, despite their much smaller size in area, it is estimated that global carbon dioxide emission from river systems exceed the emission from lakes and reservoirs, and are on par with the estimated oceanic and land carbon sinks. Closing carbon and nitrogen budgets in river systems requires knowledge of end member greenhouse gas (GHG) products (e.g. carbon dioxide, nitrous oxide, methane), which typically have not been measured in river systems. Moreover, while the production of these gasses is thought to be microbially derived, little is known about microbial activities in sediments of large rivers, despite their potentially high influence on biogeochemical budgets. Typically, when we think of rivers we visualize the channels that carve through the earth, but this only represents a small part of the hydrologic exchange that a river participates in. Rivers are more than conduits; they are dynamically exchanging water and materials with surrounding terrestrial and subsurface environments. In fact, 96% of the carbon dioxide produced within river systems occurs in hyporheic zones, or sediment regions beneath and alongside a river where groundwater and river water mix. In fact, it is widely recognized that microbial processes in hyporheic zones, also known as the river’s liver, strongly influence the fate of carbon, nutrients, and contaminants transported through watersheds. Despite this general knowledge, observational studies linking nitrogen and carbon gas production to microbial activity, and studies of overall gas emissions, are limited across river systems, but especially absent from larger rivers. To identify microbial processes responsible for GHG emissions from large rivers, and to quantify their environmental drivers and dependencies, we selected the Columbia River as a representative field site. This is the largest river west of the North American Continental Divide, and produces a drainage and discharge roughly double of the Nile in Egypt. This river is also an important source for agricultural irrigation and generates more hydroelectric power than any other North American river. Dams manage the release of water in the river, with these changes in river discharge patterns strongly impacting microbial activities in hyporheic zones. Specifically, we target a region down-river from the Priest Rapids Dam (WA) associated with the PNNL SFA, where water discharge from the dam is highly controlled, resulting in 1.5 m fluctuations in river stage daily. This dynamic river stage creates an ideal research opportunity for investigating hydrological perturbations in GHG production, uptake, and emission from large river systems. In this exploratory 1-year project, we conducted data-driven field research to provide observations needed to support predictions about GHG flux from river ecosystems. Using porewater dialysis and surface flux measurements, we observed where and when GHGs were produced and is the emission impacted by river stage. Using meta-omics tools, we determined what microbial processes control production and consumption of GHG in these systems. Finally, we provided key observations to parameterize models that could predict the effect of environmental conditions on GHG emission in the Columbia River near shore environment, at the scale that the modeled processes operate. Closing knowledge gaps in the linkages between river stage, microbial processes, and GHG production and emission, as well as the spatial distribution and ecosystem dependencies of these processes, is necessary to better parameterize land surface models. We provide some of the first, detailed GHG measurements paired microbial activity from large river systems. Our findings have direct relevance to many other large rivers with flows altered by hydroelectric energy, reservoirs, snowmelt, tides, or agriculture.

54 ENVIRONMENTAL SCIENCES↗

Microwave Signatures of Snow on Sea Ice: Modeling

Accurate knowledge of snow-depth distribution over sea ice is critical for polar climate studies. Current snow-depth-over-sea-ice retrieval algorithms do not sufficiently account for variations in snow and ice physical properties that can affect the accuracy of retrievals. For this reason, airborne microwave observations were coordinated with ground-based measurements of snow depth and snow properties in the vicinity of Barrow, AK, in March 2003. In this paper, the effects of snowpack properties and ice conditions on microwave signatures are examined using detailed surface-based measurements and airborne observations in conjunction with a thermal microwave-emission model. A comparison of the Microwave Emission Model of Layered Snowpacks (MEMLS) simulations with detailed snowpack and ice data from stakes along the Elson Lagoon and the Beaufort Sea and ra- 'diometer data taken from low-level flights using a Polarimetric Scanning Radiometer (PSR-A) shows that MEMLS can be used to simulate snow on sea ice and is a useful tool for understanding the limitations of the snow-depth algorithm. Analysis of radiance data taken over the Elson Lagoon and the Beaufort Sea using MEMLS suggests that the radiometric differences between the two locations are due to the differences in sea-ice emissivity. Furthermore, measured brightness temperatures suggest that the current snow-depth retrieval algorithm is sufficient for areas of smooth first-year sea ice, whereas new algorithm coefficients are needed for rough first-year sea ice. Snowpack grain size and density remain an unresolved issue for snow-depth retrievals using passive-microwave radiances.

Powell, D. C.↗

Improved Calibration of Reflectance Data from the LRO Lunar Orbiter Laser Altimeter (LOLA) and Implications for Space Weathering

The Lunar Orbiter Laser Altimeter (LOLA) experiment on Lunar Reconnaissance Orbiter (LRO) is a laser altimeter that also measures the strength of the return pulse from the lunar surface. These data have been used to estimate the reflectance of the lunar surface, including regions lacking direct solar illumination. A new calibration of these data is presented that features lower uncertainties overall and more consistent results in the polar regions. We use these data, along with newly available maps of the distribution of lunar maria, also derived from LRO instrument data, to investigate a newly discovered dependence of the albedo of the lunar maria on latitude (Hemingway et al., [2015]). We confirm that there is an increase in albedo with latitude in the lunar maria, and confirm that this variation is not an artifact arising from the distribution of compositions within the lunar maria, using data from the Lunar Prospector Neutron Spectrometer. Radiative transfer modeling of the albedo dependence within the lunar maria is consistent with the very weak to absent dependence of albedo on latitude in the lunar highlands; the lower abundance of the iron source for space weathering products in the lunar highlands weakens the latitude dependence to the extent that it is only weakly detectable in current data. In addition, photometric mod- els and normalization may take into account the fact that the lunar albedo is latitude dependent, but this dependence can cause errors in normalized reflectance of at most 2% for the majority of near-nadir geometries. We also investigate whether the latitude dependent albedo may have obscured detection of small mare deposits at high latitudes. We find that small regions at high latitudes with low roughness similar to the lunar maria are not mare deposits that may have been misclassified owing to high albedos imposed by the latitude dependence. Finally, we suggest that the only modest correlations among space weathering indicators defined for the lunar samples may be due to mixing of soils from distinct latitudes.

Lemelin, M.↗

Experimental Investigation of Roughness Effects on Transition on Blunt Spherical Capsule Shapes

The present contribution reviews recent experimental results of roughness effects on boundary layer transition on capsule geometries with spherical windward geometries. Experiments in three wind tunnel facilities are considered. The ACE Tunnel of Texas AM University, USA, provided Mach 6 experiments with distributed roughness at relatively low Reynolds numbers, 2.5 · 10(exp 5) < Re(sub d) < 5 · 10(exp 5), with d denoting the capsule diameter. The observed boundary layer transition compared well with correlations based on transient growth theory, even though the roughness heights were in the order of boundary layer thickness. Larger Reynolds numbers, 1 · 10(exp 6) < Re(sub d) < 3·10(exp 6), could be assessed in the hypersonic Ludwieg tube, HLB, of TU Braunschweig, Germany. Transition is observed at rather low, subcritical roughness values in the order of 20 μm for a roughness patch placed about the geometric center of the capsule model. These experiments varied fluctuation levels of the freestream. The authors assume that the observed transitions that occur downstream of the subcritical roughness patch are due to freestream disturbances in the tunnel, which interact with small roughness heights. Additional experiments in the HLB facility with patches of larger roughness height support the relevance of transient growth theory for low-to-medium roughness heights, relative to boundary layer thickness. The effects of Reynolds numbers and total flow enthalpy on transition with isolated roughness were investigated in the HIEST facility of JAXA, Japan. Here, a model insert with roughness elements of varying height for tripping transition to turbulence was employed. The results are compared to known trip effectiveness correlations for isolated roughness. Overall, the transient growth correlation seems to represent roughness-induced transition behavior on the ACE and HLB entry capsule shapes with roughness over the entire capsule surface. These experiment are however for perfect gases. Comparable experiments on roughness induced transition in a high-enthalpy facility are still needed to confirm the validity of transient-growth correlation for vehicle design.

Radespiel, Rolf↗

The complex optical to soft x-ray spectrum of the low-redshift radio-quiet quasars

Eight high signal-to-noise ROSAT Position Sensitive Proportional Counter (PSPC) observations of six low-redshift (o.048 less than z less than 0.155) radio-quiet quasars have been analyzed to study ant soft excess. All the spectra can, at least roughly, be described int eh 0.1-2.5 keV band by simple power laws reduced at low energies by Galactic absorption. The strong oxygen edges seen in the PSPC spectra of several Seyfert galaxies and quasars are not observed in this sample. The limits implied for the abount of absorbing gas intrinsic to the quasars are particularly tight: of the order of approximately 10(exp 20)/sq cm. THe range of energy indices is broad: 1.3 less than alpha(sub E) less than 2.3. The energy indices are systematically steeper than those found in the same sources at higher energies (by DELTA alpha(sub E) approximately 0.5-1 with respect to Ginga or EXOSAT (2-10 keV) measurements, and by DELTA alpha(sub E) approximately 0.5 with respect to IPC (0.2-3.5 keV) measurements). This suggests a break between the hard and soft components in the keV region and, therefore, that the PSPC spectra are strongly dominated by the soft compnents. In fact, a fit tot he composite, high signal-to-noise spectrum reveals a significant excess above approximately 1 keV withrespect to the simple power-law model. No evidence for strong emission lines is found in any of the quasars. This argues against emission from an ionized plasma as the main contributor to the soft X-ray compnentunless there is a distribution of te mperatures. If the soft X-ray spectrum of thee quasars is dominated by radiation reflected by the photoinonized surface of an accretion disk, the absence of strong emissionlines suggests high ionization parameters and therefore high accretion rates. We include in two Appendices a comarison of the two official PSPC resolution matrices, those released on1992 March and on 1993 January, a discussion of the amplitude of the residual systematic uncertainties in 1993 January matrix, and a compaison between the PSPC and IPC spectra of a sample of sources.

Fiore, Fabrizio↗

(abstract) A Polarimetric Model for Effects of Brine Infiltrated Snow Cover and Frost Flowers on Sea Ice Backscatter

A polarimetric scattering model is developed to study effects of snow cover and frost flowers with brine infiltration on thin sea ice. Leads containing thin sea ice in the Artic icepack are important to heat exchange with the atmosphere and salt flux into the upper ocean. Surface characteristics of thin sea ice in leads are dominated by the formation of frost flowers with high salinity. In many cases, the thin sea ice layer is covered by snow, which wicks up brine from sea ice due to capillary force. Snow and frost flowers have a significant impact on polarimetric signatures of thin ice, which needs to be studied for accessing the retrieval of geophysical parameters such as ice thickness. Frost flowers or snow layer is modeled with a heterogeneous mixture consisting of randomly oriented ellipsoids and brine infiltration in an air background. Ice crystals are characterized with three different axial lengths to depict the nonspherical shape. Under the covering multispecies medium, the columinar sea-ice layer is an inhomogeneous anisotropic medium composed of ellipsoidal brine inclusions preferentially oriented in the vertical direction in an ice background. The underlying medium is homogeneous sea water. This configuration is described with layered inhomogeneous media containing multiple species of scatterers. The species are allowed to have different size, shape, and permittivity. The strong permittivity fluctuation theory is extended to account for the multispecies in the derivation of effective permittivities with distributions of scatterer orientations characterized by Eulerian rotation angles. Polarimetric backscattering coefficients are obtained consistently with the same physical description used in the effective permittivity calculation. The mulitspecies model allows the inclusion of high-permittivity species to study effects of brine infiltrated snow cover and frost flowers on thin ice. The results suggest that the frost cover with a rough interface significantly increases the backscatter from thin saline ice and the polarimetric signature becomes closer to the isotropic characteristics. The snow cover also modifies polarimetric signatures of thin sea ice depending on the snow mixture and the interface condition.

thin sea ice radar backscatter frost flowers snow ↗