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At least 649 records · Page 36

Chemical Heterogeneity on Mercury's Surface Revealed by the MESSENGER X-ray Spectrometer

We present the analysis of 205 spatially resolved measurements of the surfacecomposition of Mercury from MESSENGERs X-Ray Spectrometer. The surfacefootprints of these measurements are categorized according to geological terrain. Northernsmooth plains deposits and the plains interior to the Caloris basin differ compositionallyfrom older terrain on Mercury. The older terrain generally has higher MgSi, SSi, andCaSi ratios, and a lower AlSi ratio than the smooth plains. Mercurys surface mineralogyis likely dominated by high-Mg mafic minerals (e.g., enstatite), plagioclase feldspar, andlesser amounts of Ca, Mg, andor Fe sulfides (e.g., oldhamite). The compositionaldifference between the volcanic smooth plains and the older terrain reflects differentabundances of these minerals and points to the crystallization of the smooth plains from amore chemically evolved magma source. High-degree partial melts of enstatite chondritematerial provide a generally good compositional and mineralogical match for much ofthe surface of Mercury. An exception is Fe, for which the low surface abundance onMercury is still higher than that of melts from enstatite chondrites and may indicate anexogenous contribution from meteoroid impacts.

Chemical heterogeneity↗

PyXAS – an open-source package for 2D X-ray near-edge spectroscopy analysis

In the synchrotron X-ray community, X-ray absorption near-edge spectroscopy (XANES) is a widely used technique to probe the local coordination environment and the oxidation states of specific elements within a sample. Although this technique is usually applied to bulk samples, the advent of new synchrotron sources has enabled spatially resolved versions of this technique (2D XANES). This development has been extremely powerful for the study of heterogeneous systems, which is the case for nearly all real applications. However, associated with the development of 2D XANES comes the challenge of analyzing very large volumes of data. As an example, a single 2D XANES measurement at a synchrotron can easily produce ~106 spatially resolved XANES spectra. Conventional manual analysis of an individual XANES spectrum is no longer feasible. Here, a software package is described that has been developed for high-throughput 2D XANES analysis. A detailed description of the software as well as example applications are provided.

25 ENERGY STORAGE↗

Impact of solar geoengineering on temperatures over the Indonesian Maritime Continent

Climate change has been projected to increase the intensity and magnitude of extreme temperature in Indonesia. Solar radiation management (SRM) has been proposed as a strategy to temporarily combat global warming, buying time for negative emissions. Though the global impacts of SRM have been extensively studied in recent years, regional impacts, especially in the tropics, have received much less attention. This paper investigates the potential stratospheric sulfate aerosol geoengineering to modify mean and extreme temperature, as well as the relative humidity and wet bulb temperature (WBT) change over Indonesian Maritime Continent (IMC) based on simulations from three different earth system models. We applied statistical downscaling and corrected the bias of model output to reproduce historical temperatures and relative humidity over IMC. We compared SRM as specified by the Geoengineering Model Intercomparison Project (GeoMIP) G4 experiment – 5 Tg of SO 2 into the lower stratosphere between 2020 and 2069 – concurrent with the RCP4.5 emissions scenario. SRM is able to significantly reduce the temperature means and extremes, and although differences in magnitude of response and spatial pattern occur, there is a generally consistent response. Additionally, the spatial response of changes forced by RCP4.5 scenario and SRM impact is notably heterogeneous in the archipelago, highlighting uncertainties that would be critical in assessing socio-economic consequences of both doing, and not doing SRM. In general, SRM has bigger impacts in reducing temperatures over land than oceans, and the southern monsoon region shows more variability. SRM is also effective at reducing the likelihood of WBT > 27OC events compared to RCP4.5 after some years of SRM deployment as well as during the post-termination period of SRM. Regional downscaling may be an effective tool in obtaining policy-relevant information about local effects of different future scenarios involving SRM.

54 ENVIRONMENTAL SCIENCES↗

High-Density, Low-Hysteresis Storage Using Hydrated Salts in Surface-Functionalized Hydrogels (Final Technical Report)

Nearly 70 years ago, Glauber’s salt was identified as a leading phase change material (PCM) in terms of its heat storage density (~2x paraffin), thermal conductivity (~1W/m·K), safety, availability and cost (~$\$$100/ton). However, the complex issues of supercooling and incongruent melting due to phase separation have prevented realization of the promise. The addition of thickeners and nucleating agents such as borax solve these issues but only over few cycles. This work aims to (a) resolve long-standing challenges with Glauber’s salt as a thermal storage material through a unique materials approach, (b) to characterize the new material’s properties that are relevant to performance and (c) to explore its incorporation into commercial water heaters. The materials concept involves encapsulating the salt in custom-designed, large-mesh hydrogels that enable breakthrough advances. Specifically, (1) the choice of mesh size and polymer chemistry control diffusion of salt/water and help to eliminate phase segregation. With the hydrogel itself occupying <10% volume, there is little loss in storage density compared to another encapsulation. (2) Specific nucleation centers that covalently tether to the hydrogel trigger heterogeneous nucleation, eliminating supercooling-associated hysteresis losses. The fact that they are spatially tethered, prevents the loss in performance over multiple freeze/thaw cycles (>100). We report extensive characterization of the hydrogel complex in terms of its storage density, freezing/melting temperature, cycling losses, rheological properties, aging and thermal conductivity. The novel material developed in this work is a significant advancement over the state-of-art. Finally, we investigate its potential as a thermal storage material for commercial/residential water heating and identify scenarios in which its deployment is advantageous.

25 ENERGY STORAGE↗

Tree canopy radiance measurement system

A system is described for obtaining both an estimate of the spatial mean bidirectional reflectance factor (BRF) for a tree canopy (displaying a horizontally heterogeneous foliage distribution) and the statistical significance of that estimate. The system includes a manlift supporting a horizontal beam 7 m long on which are mounted four radiometers. These radiometers may be pointed, and radiance data acquired, in any of 11 view directions in the principal plane of the sun. A total of 80 data points, acquired in 3 min, were used to estimate the BRF of a walnut orchard 5 m tall and detect true differences of 12 percent of the mean approximately 90 percent of the time.

Caldwell, William↗

A Proposed Extension to the Soil Moisture and Ocean Salinity Level 2 Algorithm for Mixed Forest and Moderate Vegetation Pixels

The Soil Moisture and Ocean Salinity (SMOS)mission, launched in November 2009, provides global maps of soil moisture and ocean salinity by measuring the L-band (1.4 GHz) emission of the Earth's surface with a spatial resolution of 40-50 km.Uncertainty in the retrieval of soilmoisture over large heterogeneous areas such as SMOS pixels is expected, due to the non-linearity of the relationship between soil moisture and the microwave emission. The current baseline soilmoisture retrieval algorithm adopted by SMOS and implemented in the SMOS Level 2 (SMOS L2) processor partially accounts for the sub-pixel heterogeneity of the land surface, by modelling the individual contributions of different pixel fractions to the overall pixel emission. This retrieval approach is tested in this study using airborne L-band data over an area the size of a SMOS pixel characterised by a mix Eucalypt forest and moderate vegetation types (grassland and crops),with the objective of assessing its ability to correct for the soil moisture retrieval error induced by the land surface heterogeneity. A preliminary analysis using a traditional uniform pixel retrieval approach shows that the sub-pixel heterogeneity of land cover type causes significant errors in soil moisture retrieval (7.7%v/v RMSE, 2%v/v bias) in pixels characterised by a significant amount of forest (40-60%). Although the retrieval approach adopted by SMOS partially reduces this error, it is affected by errors beyond the SMOS target accuracy, presenting in particular a strong dry bias when a fraction of the pixel is occupied by forest (4.1%v/v RMSE,-3.1%v/v bias). An extension to the SMOS approach is proposed that accounts for the heterogeneity of vegetation optical depth within the SMOS pixel. The proposed approach is shown to significantly reduce the error in retrieved soil moisture (2.8%v/v RMSE, -0.3%v/v bias) in pixels characterised by a critical amount of forest (40-60%), at the limited cost of only a crude estimate of the optical depth of the forested area (better than 35% uncertainty). This study makes use of an unprecedented data set of airborne L-band observations and ground supporting data from the National Airborne Field Experiment 2005 (NAFE'05), which allowed accurate characterisation of the land surface heterogeneity over an area equivalent in size to a SMOS pixel.

Panciera, Rocco↗

Mapping of Texture and Phase Fractions in Heterogeneous Stress States during Multiaxial Loading of Biomedical Superelastic NiTi

Thermoelastic deformation mechanisms in polycrystalline biomedical-grade superelastic NiTi are spatially mapped using in situ neutron diffraction during multiaxial loading and heating. The trigonal R-phase is formed from the cubic phase during cooling to room temperature and subsequently deforms in compression, tension, and torsion. The resulting R-phase variant microstructure from the variant reorientation and detwinning processes are equivalent for the corresponding strain in tension and compression, and the variant microstructure is reversible by isothermal loading. The R-phase variant microstructure is consistent between uniaxial and torsional loading when the principal stress directions of the stress state are considered (for the crystallographic directions observed here). The variant microstructure evolution is tracked and the similarity in general behavior between uniaxial and torsional loading, in spite of the implicit heterogeneous stress state associated with torsional loading, pointed to the ability of the reversible thermoelastic transformation in NiTi to accommodate stress and strain mismatch with deformation. This ability of the R-phase, despite its limited variants, to accommodate stress and strain and satisfy strain incompatibility in addition to the existing internal stresses has significance for reducing irrecoverable deformation mechanisms during loading and cycling through the phase transformation.

36 MATERIALS SCIENCE↗

The Radiative Consistency of Atmospheric Infrared Sounder and Moderate Resolution Imaging Spectroradiometer Cloud Retrievals

The consistency of cloud top temperature (Tc) and effective cloud fraction (f) retrieved by the Atmospheric Infrared Sounder (AIRS)/Advanced Microwave Sounding Unit (AMSU) observation suite and the Moderate Resolution Imaging Spectroradiometer (MODIS) on the EOS-Aqua platform are investigated. Collocated AIRS and MODIS TC and f are compared via an 'effective scene brightness temperature' (Tb,e). Tb,e is calculated with partial field of view (FOV) contributions from TC and surface temperature (TS), weighted by f and 1-f, respectively. AIRS reports up to two cloud layers while MODIS reports up to one. However, MODIS reports TC, TS, and f at a higher spatial resolution than AIRS. As a result, pixel-scale comparisons of TC and f are difficult to interpret, demonstrating the need for alternatives such as Tb,e. AIRS-MODIS Tb,e differences ((Delta)Tb,e) for identical observing scenes are useful as a diagnostic for cloud quantity comparisons. The smallest values of DTb,e are for high and opaque clouds, with increasing scatter in (Delta)Tb,e for clouds of smaller opacity and lower altitude. A persistent positive bias in DTb,e is observed in warmer and low-latitude scenes, characterized by a mixture of MODIS CO2 slicing and 11-mm window retrievals. These scenes contain heterogeneous cloud cover, including mixtures of multilayered cloudiness and misplaced MODIS cloud top pressure. The spatial patterns of (Delta)Tb,e are systematic and do not correlate well with collocated AIRS-MODIS radiance differences, which are more random in nature and smaller in magnitude than (Delta)Tb,e. This suggests that the observed inconsistencies in AIRS and MODIS cloud fields are dominated by retrieval algorithm differences, instead of differences in the observed radiances. The results presented here have implications for the validation of cloudy satellite retrieval algorithms, and use of cloud products in quantitative analyses.

clouds↗

The rigorous upscaling of advection-dominated transport in heterogeneous porous media via the Method of Finite Averages

Systems involving advection-dominated transport through heterogeneous porous and fractured media are ubiquitous in subsurface engineering applications. However, upscaling such systems continues to challenge rigorous modeling efforts, particularly when advection is stronger than diffusion at fine spatial scales (i.e., when the Péclet number is greater than one at length scales that characterize a system’s unit-cells, representative elementary volumes, or averaging regions). Here, in this work, we propose and validate a strategy for extending the Method of Finite Averages (MoFA), a rigorous upscaling methodology for heterogeneous porous media, to upscale transport systems experiencing stronger advection than diffusion at fine scales (i.e., fine-scale Péclet numbers greater than one). We detail the strategy, the physical conditions under which it can be applied while retaining a priori modeling error guarantees, and implement the strategy to obtain a MoFA model for advective-diffusive transport that accommodates advective physics at fine spatial scales. We then perform two numerical experiments considering systems with system-scale Péclet numbers of 300 and 1000 — which correspond to fine-scale Péclet numbers of 30 and 100, respectively — to verify that the error guarantees are met under the strategy. After, we conduct a numerical study to demonstrate the strategy’s advantages over the original MoFA methodology. The results suggest that rigorously-upscaled transport models for heterogeneous porous media experiencing advective physics at finer spatial scales can be derived through MoFA and resolved orders of magnitude faster than their pore-scale counterparts. The results also suggest that the presented strategy is limited to modeling shallow concentration gradients when there are large differences between the time scales related to advection and a system’s temporally-varying boundary conditions. This limitation hinders the strategy’s practicality in modeling more advective systems, and as such, opportunity exists for developing additional strategies that accommodate rapidly-varying boundary conditions — and consequentially, steeper concentration gradients — while modeling advective systems with MoFA.

36 MATERIALS SCIENCE↗

Spatial Variations in the Spectral Properties of Bright Regions on Mars

Much of the surface of Mars is covered by material that is bright and reddish at visible wavelengths and which is interpreted as chemically altered soil. High spatial resolution data from the ISM near-infrared imaging spectrometer on the Phobos 2 spacecraft have provided new information about the composition and compositional heterogeneity of this soil. Most bright soil exhibits a weak, narrow absorption feature near 2.2 micron, suggesting the presence of poorly crystalline phyllosilicate. The strength of the 3.0-micron H2O absorption exhibits spatially coherent variations, with stronger absorptions occurring in specific geologic units. These variations may result from differences in the content of molecular water in soils developed on different deposits. Additionally, the position and shape of the 0.9-micron Fe(3+) absorption indicate hematite to be present in bright soils covering many areas, including Tharsis. However, other large areas covered by bright soil, including much of Arabia, exhibit a deeper absorption at a longer wavelength, suggesting occurrence of ferric minerals other than hematite. These spectral heterogeneities indicate that bright martian soil is compositionally diverse and not completely homogenized by eolian activity. The compositional differences may result from different histories of chemical alteration of parent materials and their resulting soils, possibly including local effects of liquid water.

Murchie, Scott↗

Towards POI-based large-scale land use modeling: spatial scale, semantic granularity, and geographic context

The combination of spatial distribution, semantic characteristics, and sometimes temporal dynamics of POIs inside a geographic region can capture its unique land use characteristics. Most previous studies on POI-based land use modeling research focused on one geographic region and select one spatial scale and semantic granularity for land use characterization. There is a lack of understanding on the impact of spatial scale, semantic granularity, and geographic context on POI-based land use modeling, particularly large-scale land use modeling. In this study, we developed a scalable POI-based land use modeling framework and examined the impact of these three factors on POI-based land use characterization using data from three geographic regions. We developed a unified semantic representation framework for POI semantics that can help fuse heterogeneous POI data sources. Then, by combining POIs with a neural network language model, we developed a spatially explicit approach to learn the embedding representation of POIs and AOIs. We trained multiple supervised classifiers using AOI embeddings as input features to predict AOI land use at different semantic granularities. The classification performance of different land use classes was analyzed and compared across three geographic regions to identify the semantic representativeness of POI-based AOI embedding and the impact of geographic context.

58 GEOSCIENCES↗

ARJUNA: An Electrochemical Interface Mapping Probe for Solid-State Batteries

Solid-state batteries (SSBs) are promising candidates for next-generation energy storage, although their performance can be compromised by interfacial heterogeneity within the electrolyte. Furthermore, ensuring the quality of large form-factors electrolyte film is crucial for establishing a robust manufacturing platform for solid-state batteries. Herein, we report on the use of ARJUNA, an electrochemical interface mapping system, to characterize heterogeneities at solid electrolyte interfaces and to serve as a quality control system for SSB manufacturing. In addition to spatial mapping, the proposed system can also probe the interface behavior as a function of pressure and temperature. We present the operating principle, design, instrumentation, and evaluation of the system alongside a typical hybrid solid electrolyte produced using two common manufacturing processes. This report showcases the capability of ARJUNA to probe the heterogeneity and quality of processed solid electrolyte films.

25 ENERGY STORAGE↗

Bright soil units on Mars determined from ISM imaging spectrometer data

The lithology of bright Martian soil provides evidence for chemical and physical processes that have modified the planet's surface. Data from the ISM imaging spectrometer, which observed much of the equatorial region at a spatial resolution of approximately 22 km, cover the NIR wavelength range critical to ascertaining the presence and abundance of Fe-containing phases, hydroxylated silicates, and H2O in the bright soil. ISM data previously have revealed spatial variations in depth of the 3.0-microns H2O absorption suggesting differences in water content, a weak absorption at 2.2 microns indicative of metal-OH in phyllosilicate, and variations in the 1-micron Fe absorption indicative of differences in Fe mineralogy. This paper summarizes first results of a systematic investigation of spectral heterogeneity in bright soils observed by ISM. At least seven 'units' with distinctive properties were discriminated. Comparison of their spatial distributions with Viking data shows that they generally correspond with previously recognized morphologic, color, and thermal features. These correspondences and the units' spectral attributes provide evidence for lithologic differences between the soils in different geologic settings.

Murchie, Scott↗

Detecting multi‐scale riverine topographic variability and its influence on Chinook salmon habitat selection

Abstract Quantifying geomorphic conditions that impact riverine ecosystems is critical in river management due to degraded riverine habitat, changing flow and thermal conditions, and increasing anthropogenic pressure. Geomorphic complexity at different scales directly impacts habitat heterogeneity and affects aquatic biodiversity resilience. Here we showed that the combination of continuous spatial survey at high resolution, topobathymetric light detection and ranging (LiDAR), and continuous wavelet analysis can help identify and characterize that complexity. We used a continuous wavelet analysis on 1‐m resolution topobathymetry in three rivers in the Salmon River Basin, Idaho (USA), to identify different scales of topographic variability and the potential effects of this variability on salmonid redd site selection. On each river, wavelet scales characterized the topographic variability by portraying repeating patterns in the longitudinal profile. We found three major representative spatial wavelet scales of topographic variability in each river: a small wavelet scale associated with local morphology such as pools and riffles, a mid‐wavelet scale that identified larger channel unit features, and a large wavelet scale related to valley‐scale controls. The small wavelet scale was used to identify pools and riffles along the entire lengths of each river as well as areas with differing riffle‐pool development. Areas along the rivers with high local topographic variability (high wavelet power) at all wavelet scales contained the largest features (i.e., deepest or longest pools) in the systems. By comparing the wavelet power for each wavelet scale to Chinook salmon redd locations, we found that higher small‐scale wavelet power, which is related to pool‐riffle topography, is important for redd site selection. The continuous wavelet methodology objectively identified scales of topographic variability present in these rivers, performed efficient channel‐unit identification, and provided geomorphic assessment without laborious field surveys.

Duffin, Jenna↗

Mapping Competitive Reduction upon Charging in LiNi 0.8 Co 0.15 Al 0.05 O 2 Primary Particles

Side reactions involving surface reduction play a critical role in the failure of LiNi 0.8 Co 0.15 Al 0.05 O 2 to reach its theoretical capacity as a cathode material for Li-ion batteries. While macroscopic consequences are known, the underlying nanoscopic mechanisms are not fully elucidated. By coupling X-ray spectroscopy with several X-ray microscopy modalities, we have spatially resolved the extent of Ni oxidation at several states of charge and uncovered heterogeneity that is hidden when considering ensemble measurements alone. The use of morphologically controlled particles enabled high-resolution imaging of these materials, uncovering gradients of Ni oxidation states within individual primary particles. At high states of charge, these gradients revealed regions of possible oxygen deficiency extending deeper into the particle than previously observed. Surface-sensitive X-ray coupled scanning tunneling microscopy allows oxidation states to be measured at the material's surface, showing predominantly Ni II in the first atomic layer and mixtures of Ni II with Ni III /Ni IV already appearing 1.5 nm into the particle. These results reveal the subtle interplay between irreversible surface transformations and the bulk reactions that ultimately define function, which will refine strategies of surface passivation that are key to overcoming current performance limitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fracture Intensity Impacts on Reaction Front Propagation and Mineral Weathering in Three‐Dimensional Fractured Media

Abstract Studying reaction front propagation in heterogeneous natural settings is challenging, but numerical simulations can provide insight into the varying spatial and temporal scales of reaction front propagation. Here, the impact of increasing fracture intensity on mineral dissolution rates, and the extent of reaction front propagation is investigated using reactive transport simulations in upscaled discrete fracture network domains with varied fracture intensity. Domain‐averaged dissolution rates vary less than 0.5 log units regardless of the fracture intensity, but the spatial distribution of reactions is controlled by the location and number of dead‐end fractures and the number of connected flowpaths through the domain. Higher fracture intensities lead to more weathering in the domain because of more available mineral for water‐rock interactions. We find that reaction fronts propagate through the primary flowpaths in the first 10,000 years of the simulation for a 10‐m length domain, then propagate into secondary flowpaths and dead‐end fractures between 10,000 and 100,000 years, and finally into the matrix over timescales of hundreds of thousands of years. The domain‐averaged reaction rates decrease through time corresponding to a transition from dissolution in advection‐dominated, fast‐flowing pathways, to dissolution in transport‐limited zones of disconnected fractures and matrix. Matrix dissolution, or dissolution under transport‐limited conditions, is the dominant process at late times in these simulations. The results of these simulations recreate the observed paradox found in nature where highly fractured hillslopes tend to be more weathered but have slower weathering rates, while hillslopes with fewer fractures, are less weathered but have higher dissolution rates.

58 GEOSCIENCES↗

Viromes outperform total metagenomes in revealing the spatiotemporal patterns of agricultural soil viral communities

Abstract Viruses are abundant yet understudied members of soil environments that influence terrestrial biogeochemical cycles. Here, we characterized the dsDNA viral diversity in biochar-amended agricultural soils at the preplanting and harvesting stages of a tomato growing season via paired total metagenomes and viral size fraction metagenomes (viromes). Size fractionation prior to DNA extraction reduced sources of nonviral DNA in viromes, enabling the recovery of a vaster richness of viral populations (vOTUs), greater viral taxonomic diversity, broader range of predicted hosts, and better access to the rare virosphere, relative to total metagenomes, which tended to recover only the most persistent and abundant vOTUs. Of 2961 detected vOTUs, 2684 were recovered exclusively from viromes, while only three were recovered from total metagenomes alone. Both viral and microbial communities differed significantly over time, suggesting a coupled response to rhizosphere recruitment processes and/or nitrogen amendments. Viral communities alone were also structured along an 18 m spatial gradient. Overall, our results highlight the utility of soil viromics and reveal similarities between viral and microbial community dynamics throughout the tomato growing season yet suggest a partial decoupling of the processes driving their spatial distributions, potentially due to differences in dispersal, decay rates, and/or sensitivities to soil heterogeneity.

59 BASIC BIOLOGICAL SCIENCES↗