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At least 289 records · Page 16

Instrument for Measuring Temperature of Water

A pseudo-Brewster angle infrared radiometer has been proposed for use in noncontact measurement of the surface temperature of a large body of water (e.g., a lake or ocean). This radiometer could be situated on a waterborne, airborne, or spaceborne platform. The design of the pseudo-Brewster angle radiometer would exploit the spectral emissivity and polarization characteristics of water to minimize errors attributable to the emissivity of water and to the reflection of downwelling (e.g., Solar and cloud-reflected) infrared radiation.

Ryan, Robert↗

Optical vibrational spectra of β -U 3 O 8

Technogenic uranium oxides are ubiquitous in the nuclear fuel cycle. Identifying the chemical composition of these oxides is frequently done with optical vibrational spectroscopy (infrared and Raman spectroscopy). The α phase of U 3 O 8 is the most stable and common uranium oxide, but a β phase of U 3 O 8 can be produced via very slow cooling of the α phase from elevated temperatures or the application of small shear forces. However, optical spectra of this compound have not been reported. In this work, we use high-resolution attenuated total reflection infrared spectroscopy and Raman spectroscopy to collect the optical vibrational spectra. Despite similarities in the crystal structure of α and β – U 3 O 8 , the optical spectra of these compounds differ substantially, with additional Raman active modes in β – U 3 O 8 that are likely originating from differences in the U–O coordination units. Measurements presented here provide spectral characterization that can be used for chemical identification in future studies of uranium oxides.

36 MATERIALS SCIENCE↗

Paintable Heat-Reflective Coatings for Low-Cost Energy Efficient Windows

The major objective of this effort is to manufacture a paintable coating to inexpensively retrofit energy-inefficient windows with a heat-reflective, visibly transparent film. This coating will drastically reduce cooling costs for millions of homes and buildings and lower the Nation’s greenhouse gas emissions. Widespread implementation could reduce the national consumption of electricity for cooling by billions of kWh, saving billions of dollars per year. This improved energy efficiency would decrease CO2 emissions by billions kg per year, the equivalent to removing millions of cars from the road. Although near-IR reflective adhesive films are commercially available products and have demonstrated significant energy efficiency enhancement, high upfront costs largely deter potential consumers across all sectors. The technology developed under this award was proposed to disrupt the building envelope market, by providing an inexpensive coating that can be directly applied by consumers to improve the energy efficiency of virtually all window types. The proof of concept for a paintable, DIY applicable, visibly transparent, and infrared reflective coating was achieved, laying the foundation for future technology development in this area.

14 SOLAR ENERGY↗

Evaluation of thermal data for geologic applications

Sensitivity studies using thermal models indicated sources of errors in the determination of thermal inertia from HCMM data. Apparent thermal inertia, with only simple atmospheric radiance corrections to the measured surface temperature, would be sufficient for most operational requirements for surface thermal inertia. Thermal data does have additional information about the nature of surface material that is not available in visible and near infrared reflectance data. Color composites of daytime temperature, nighttime temperature, and albedo were often more useful than thermal inertia images alone for discrimination of lithologic boundaries. A modeling study, using the annual heating cycle, indicated the feasibility of looking for geologic features buried under as much as a meter of alluvial material. The spatial resolution of HCMM data is a major limiting factor in the usefulness of the data for geologic applications. Future thermal infrared satellite sensors should provide spatial resolution comparable to that of the LANDSAT data.

Kahle, A. B.↗

CO as a Probe Molecule to Study Surface Adsorbates during Electrochemical Oxidation of Propene

A major challenge in the electrochemical oxidation of hydrocarbons is understanding the formation of intermediate species, some of which continue to react, while others are non-reactive or poisonous species that block adsorption of further reactants. Herein we investigate the identity and behavior of adsorbates formed during partial oxidation of propene. We employ two techniques: Electrochemistry-Mass Spectrometry (EC-MS) and Attenuated Total Reflection Infrared Spectroscopy (ATR-FTIR). In both cases, we use CO as a probe molecule, to perturb the ad-layer of propene intermediates. In the EC-MS experiments, propene and its intermediates were quantified by triggering their desorption via displacement with CO. We show evidence for at least two distinct classes of propene adsorbates, via CO displacement and electrochemical stripping. A redshift in the ν(C–O) mode was observed, during IR spectroscopy, reflecting the chemical environment arising from strongly bound propene intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Infrared observations of small solar system bodies

Infrared reflectance spectra were measured of dark primitive asteroids in the 2 to 5 micron wavelength region. The search was for organic complexes such and CN, CH, and NH in dark material on small bodies in the solar system. A search and study was made of volatiles such as nitrogen, methane, ammonia, and carbon monoxide, both as free ices and hydrates/clathrates, on icy surfaces in the outer solar system, using high resolution spectra obtained with a multichannel cooled grating, infrared spectrometer. An absorption that can be attributed to X-C (triple bond) N in the matrix of dark materials on the primitive asteroids.

Brown, R. H.↗

Two-stream theory of spectral reflectance of snow

Spectral reflectance of snow under diffuse illumination is studied using the two-stream approximation of the radiative transfer equation. The scattering and absorption within the snowcover due to the randomly distributed ice grains are characterized by the single scattering albedo and anisotropic phase function. Geometric optics calculations are used to relate the scattering and absorption parameters to grain size and density of snow. Analytical expressions for the intensity within the snowpack and the asymptotic flux extinction coefficient are also obtained. Good agreement is shown between the theory and available experimental data on visible and near-infrared reflectance and asymptotic flux extinction coefficient. The theory also may be used to explain the observed effect of aging on the snow reflectance.

Choudhury, B. J.↗

Characterizing Vegetation Cover in Global Savannas with an Annual Foliage Clumping Index Derived from the MODIS BRDF Product

The global savanna biome is characterized by enormous diversity in the physiognomy and spatial structure of the vegetation. The foliage clumping index can be calculated from bidirectional reflectance distribution function (BRDF) data. It measures the response of the darkspot reflectance to increased shadow associated with clumped vegetation and is related to leaf area index. Clumping index theoretically declines with increasing woody cover until the tree canopy begins to become uniform. In this study, clumping index is calculated for Moderate Resolution Imaging Spectroradiometer BRDF data for the Australian tropical savanna, the tropical savannas of South America, and the tropical savannas of east, west and southern Africa and compared with site-based measurements of tree canopy cover, and with area-based classifications of land cover. There were differences in sensitivity of clumping index between red and near-infrared reflectance channels, and between savanna systems with markedly different woody vegetation physiognomy. Clumping index was broadly related to foliage cover from historical site data in Australia and in West Africa and Kenya, but not in Southern Africa nor with detailed site-based demographic data in the cerrado of Brazil. However, clumping index decreased with proportion of woody cover in land cover datasets for east Africa, Australia and the Colombian Llanos. There was overlap in the range of clumping index values for forest, cerrado and campo land covers in Brazil. Clumping index was generally negatively correlated with percentage tree cover from the MODIS Vegetation Continuous Fields product, but regional differences in the relationship were evident. There were large differences in the frequency distributions of clumping index from savanna, woody savanna and grassland land cover classes between global ecoregions. The clumping index shows differing sensitivity to savanna woody cover for red and NIR reflectance, and requires regional calibration for application as a universal indicator.

Hill, Michael J.↗

Using Neural Networks to Identify Mixture Components in Hyperspectral Reflectance Data

Neural networks have been employed to identify materials of interest from hyperspectral data (generally imagery) based on their unique spectral signatures. This approach assumes that there is a single material that is standing out from the rest of the spectrum to be identified. However, pixels often contain more than one material, or a material of interest may itself be a mixture of multiple materials. Neural networks are only as good as the data used to train them, and it takes a great deal of work in the laboratory to identify, make, and measure all potential mixtures of interest. Thus, researchers often calculate synthetic spectra using algorithms with varying degrees of fidelity to the physics that govern the interactions between light and multiple materials. In this work, we have (1) adapted a neural network designed to identify mixture components from Raman spectroscopy to work with visible to near‐infrared reflectance data and (2) tested three common mixture algorithms to determine the most accurate and least computationally expensive method to build synthetic training datasets. With our initial test dataset, we have achieved accuracies of > 90% and found that the synthetic training dataset produced using the Hapke mixture model provides the best results.

99 GENERAL AND MISCELLANEOUS↗

Mineralogical and Geochemical Analyses of Antarctic Lake Sediments: A Reflectance and Moessbauer Spectroscopy Study with Applications for Remote Sensing on Mars

Lakebottom sediments from the Dry Valleys region of Antarctica have been analyzed here in order to study the influence of water chemistry on the mineralogy and geochemistry of these sediments, as well as to evaluate techniques for remote spectral identification of potential biomarker minerals on Mars. Lakes from the Dry Valleys region of Antarctica have been investigated as possible analogs for extinct lake environments on early Mars. Sediment cores were collected in the present study from perennially ice-covered Lake Hoare in the Taylor Valley. These sediments were taken from a core in an oxic region of the lake and another core in an anoxic zone. Differences between the two cores were observed in the sediment color, Fe(II)/Fe(III) ratio, the presence of pyrite, the abundance of Fe, S and some trace elements, and the C, N and S isotope fractionation patterns. The results of visible-infrared reflectance spectroscopy (0.3-25 microns) Mossbauer spectroscopy (77 and 4 K) and X-ray diffraction are combined to determine the mineralogy and composition of these samples. The sediments are dominated by plagioclase, K-feldspar, quartz and pyroxene. Algal mats grow on the bottom of the lake and organic material has been found throughout the cores. Calcite is abundant in some layers of the aerobic core (shallow region) and pyrite is abundant in some layers of the anaerobic core (deep region). Analysis of the spectroscopic features due to organics and carbonates with respect to the abundance of organic C and carbonate contents was performed in order to select optimal spectral bands for remote identification of these components in planetary regoliths. Carbonate bands near 4 and 6.8 microns (approx.2500 and 1500/cm) were detected for carbonate abundances as low as 0.1 wt.% CO2. Organic features at 3.38, 3.42 and 3.51 microns (2960, 2925 and 2850/cm) were detected for organic C abundances as low as 0.06 wt.% C. The d13C trends show a more complex organic history for the anaerobic sediments than for the aerobic sediments. The biogenic pyrite found in the anaerobic core is associated with lighter d34S values and high organic C levels and could be used as a biomarker mineral for paleolakes on Mars.

Froeschl, Heinz↗

Application of High-Resolution Thermal Infrared Remote Sensing and GIS to Assess the Urban Heat Island Effect

Day and night airborne thermal infrared image data at 5 m spatial resolution acquired with the 15-channel (0.45 micron - 12.2 micron) Advanced Thermal and Land Applications Sensor (ATLAS) over Alabama, Huntsville on 7 September, 1994 were used to study changes in the thermal signatures of urban land cover types between day and night. Thermal channel number 13 (9.6 micron - 10.2 micron) data with the best noise-equivalent temperature change (NEAT) of 0.25 C after atmospheric corrections and temperature calibration were selected for use in this analysis. This research also examined the relation between land cover irradiance and vegetation amount, using the Normalized Difference Vegetation Index (NDVI), obtained by ratioing the difference and the sum of the red (channel number 3: 0.60-0.63 micron) and reflected infrared (channel number 6: 0.76-0.90 micron) ATLAS data. Based on the mean radiance values, standard deviations, and NDVI extracted from 351 pairs of polygons of day and night channel number 13 images for the city of Huntsville, a spatial model of warming and cooling characteristics of commercial, residential, agricultural, vegetation, and water features was developed using a GIS approach. There is a strong negative correlation between NDVI and irradiance of residential, agricultural, and vacant/transitional land cover types, indicating that the irradiance of a land cover type is greatly influenced by the amount of vegetation present. The predominance of forests, agricultural, and residential uses associated with varying degrees of tree cover showed great contrasts with commercial and services land cover types in the center of the city, and favors the development of urban heat islands. The high-resolution thermal infrared images match the complexity of the urban environment, and are capable of characterizing accurately the urban land cover types for the spatial modeling of the urban heat island effect using a GIS approach.

Lo, C. P.↗

Capture and Decomposition of the Nerve Agent Simulant, DMCP, Using the Zeolitic Imidazolate Framework (ZIF-8)

Understanding mechanisms of decontamination of chemical warfare agents (CWA) is an area of intense research aimed at developing new filtration materials to protect soldiers and civilians in case of state-sponsored or terrorist attack. In this study, we employed complementary structural, chemical, and dynamic probes and in situ data collection, to elucidate the complex chemistry, capture, and decomposition of the CWA simulant, dimethyl chlorophosphonate (DMCP). Our work reveals key details of the reactive adsorption of DMCP and demonstrates the versatility of zeolitic imidazolate framework (ZIF-8) as a plausible material for CWA capture and decomposition. Here, the in situ synchrotron-based powder X-ray diffraction (PXRD) and pair distribution function (PDF) studies, combined with Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), zinc K-edge X-ray absorption near edge structure (XANES), and Raman spectroscopies, showed that the unique structure, chemical state, and topology of ZIF-8 enable accessibility, adsorption, and hydrolysis of DMCP into the pores and revealed the importance of linker chemistry and Zn 2+ sites for nerve agent decomposition. DMCP decontamination and decomposition product(s) formation were observed by thermogravimetric analysis, FT-IR spectroscopy, and phosphorus (P) K-edge XANES studies. Differential PDF analysis indicated that the average structure of ZIF-8 (at the 30 Å scale) remains unchanged after DMCP dosing and provided information on the dynamics of interactions of DMCP with the ZIF-8 framework. Using in situ PXRD and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), we showed that nearly 90% regeneration of the ZIF-8 structure and complete liberation of DMCP and decomposition products occur upon heating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Estimating the Relative Water Content of Leaves in a Cotton Canopy

Remotely sensing plant canopy water status remains a long-term goal of remote sensing research. Established approaches to estimating canopy water status the Crop Water Stress Index, the Water Deficit Index and the Equivalent Water Thickness involve measurements in the thermal or reflective infrared. Here we report plant water status estimates based upon analysis of polarized visible imagery of a cotton canopy measured by ground Multi-Spectral Polarization Imager (MSPI). Such estimators potentially provide access to the plant hydrological photochemistry that manifests scattering and absorption effects in the visible spectral region.Twice during one day, +- 3 hours from solar noon, we collected polarized imagery and relative water content data on a cotton test plot located at the Arid Land Agricultural Research Center, United States Department of Agriculture, Maricopa, AZ. The test plot, a small portion of a large cotton field, contained stressed plants ready for irrigation. The evening prior to data collection we irrigated several rows of plants within the test plot. Thus, ground MSPI imagery from both morning and afternoon included cotton plants with a range of water statuses. Data analysis includes classifying the polarized imagery into sunlit reflecting, sunlit transmitting, shaded foliage and bare soil. We estimate the leaf surface reflection and interior reflection based upon the per pixel polarization and sunview directions. We compare our cotton results with our prior polarization results for corn and soybean leaves measured in the lab and corn leaves measured in the field.

Cotton Canopy↗

Satellite Sensor Requirements for Monitoring Essential Biodiversity Variables of Coastal Ecosystems

The biodiversity and high productivity of coastal terrestrial and aquatic habitats are the foundation for important benefits to human societies around the world. These globally distributed habitats need frequent and broad systematic assessments, but field surveys only cover a small fraction of these areas. Satellite-based sensors can repeatedly record the visible and near-infrared reflectance spectra that contain the absorption, scattering, and fluorescence signatures of functional phytoplankton groups, colored dissolved matter, and particulate matter near the surface ocean, and of biologically structured habitats (floating and emergent vegetation, benthic habitats like coral, seagrass, and algae). These measures can be incorporated into Essential Biodiversity Variables (EBVs), including the distribution, abundance, and traits of groups of species populations, and used to evaluate habitat fragmentation. However, current and planned satellites are not designed to observe the EBVs that change rapidly with extreme tides, salinity, temperatures, storms, pollution, or physical habitat destruction over scales relevant to human activity. Making these observations requires a new generation of satellite sensors able to sample with these combined characteristics: (1) spatial resolution on the order of 30 to 100-m pixels or smaller; (2) spectral resolution on the order of 5 nm in the visible and 10 nm in the short-wave infrared spectrum (or at least two or more bands at 1,030, 1,240, 1,630, 2,125, and/or 2,260 nm) for atmospheric correction and aquatic and vegetation assessments; (3) radiometric quality with signal to noise ratios (SNR) above 800 (relative to signal levels typical of the open ocean), 14-bit digitization, absolute radiometric calibration less than 2%, relative calibration of 0.2%, polarization sensitivity less than 1%, high radiometric stability and linearity, and operations designed to minimize sunglint; and (4) temporal resolution of hours to days. We refer to these combined specifications as H4 imaging. Enabling H4 imaging is vital for the conservation and management of global biodiversity and ecosystem services, including food provisioning and water security. An agile satellite in a 3-d repeat low-Earth orbit could sample 30-km swath images of several hundred coastal habitats daily. Nine H4 satellites would provide weekly coverage of global coastal zones. Such satellite constellations are now feasible and are used in various applications.

aquatic↗

Visualizing Size-Dependent Dynamics of CeO 2-δ {100}-Supported CoO x Nanoparticles Under CO 2 Hydrogenation Conditions

Carbon dioxide is a major greenhouse gas. In order to optimize processes focused on its chemical valorization, one needs detailed information about the effects of CO 2 and/or CO 2 /H 2 mixtures on the structure and morphology of metal/oxide catalysts. Here, in this study, the evolution of a catalyst with cobalt supported on CeO 2 -cube nanostructures under CO 2 hydrogenation conditions was investigated by using a set of in situ characterization techniques (X-ray absorption fine structure, X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, and environmental transmission electron microscopy (TEM)). The {100} facets of the ceria support displayed an unexpectedly high stability due to strong interactions with the aggregates of cobalt oxide. A significant influence of interfacial bonding between CoO x and CeO 2-δ {100} is evident through a clear preference in the orientation of CoO x nanoparticles (NPs) with respect to the substrate. For initially reduced Co/CeO 2 -cube nanostructures, a kinetically controlled oxidation of cobalt upon the introduction of CO 2 was observed during the early stages of CO 2 hydrogenation. Environmental TEM revealed the size-dependent morphological behavior of cobalt oxide NPs due to strong interactions with the CeO 2 {100} surface. When the environment was switched from H 2 to a mixture of H 2 and CO 2 at 250 °C, small CoO x NPs (in the largest dimension < 2.5 nm) rapidly transformed from a pyramidal three-dimensional (3D) form to a planar, monatomic layer attached to the concurrently oxidized CeO 2-δ {100} surface. This maximizes the number of sites available for the binding of CO 2 or reaction intermediates. The shape transformation reflected the oxophilic character of cobalt and strong metal–support interactions. The removal of CO 2 from the gas phase led to a reduction of the cobalt oxide NPs by hydrogen and a reversible two-dimensional → 3D transformation. In contrast, no significant morphological changes, apart from further oxidation, were observed for big CoO x NPs (in the largest dimension > 3 nm). These trends are not seen for nanoparticles of noble metals. The observed morphological and structural changes in the small CoO x NPs affected the stability of reaction intermediates and modified the selectivity of the CoO x /CeO 2 catalyst system for methane production.

36 MATERIALS SCIENCE↗

Mixed Molecular and Dissociative Water Adsorption on Hydroxylated TiO 2 (110): An Infrared Spectroscopy and Ab Initio Molecular Dynamics Study

For this work, we have investigated the structure and dynamics of water (D 2 O) adsorbed on TiO 2 (110) for coverages between 0 and 1 monolayer with infrared reflection absorption spectroscopy (IRAS) and ab initio molecular dynamics (AIMD) simulations. For D 2 O coverages as low as 0.4 monolayers (ML) on a hydroxylated surface, IR spectra typical of hydrogen-bonded chains of water molecules are observed. However, for D 2 O coverages ≥ 0.3 ML, a sharp, high frequency peak is also observed in the p-polarized spectra that is red-shifted relative to the bridging hydroxyl peak. This new peak is not observed for water adsorbed on an oxidized surface. Based on the AIMD simulations and comparisons with previous IR spectra for TiO 2 nanoparticles, the new peak is assigned to terminal hydroxyl groups produced by dissociative adsorption of some of the water on TiO 2 (110). The simulations indicate that water dissociation is related to the presence of defect electrons in the system, but not due to direct interactions between adsorbed water and bridging hydroxyls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multi-site Milling Strategy Reveals Significant Variation in Biomass Composition of Switchgrass ( Panicum virgatum ) Grown at Ten Locations

Cell wall composition influences biomass use as a forage and as a feedstock for biofuel and chemical conversion. To examine the influence of environment on composition of switchgrass (Panicum virgatum L.), we utilized a multi-environment experiment consisting of clones of switchgrass genotypes grown at up to ten locations in the continental US. We tested the influence of different milling treatments on biomass composition trait predictions via near-infrared reflectance spectroscopy (NIRS). We found that most compositional trait predictions (29/34) were significantly different (P < 0.05) when a single lot of biomass was subjected to disparate milling treatments, i.e., knife milling vs. knife milling with an additional cyclone milling. Further, depending on the plant material tested, three to eight compositional trait predictions vary (P < 0.05) when identical biomass was knife milled at different sites followed by cyclone milling at a single site, including for traits such as Klason lignin, nitrogen, and carbon. In some cases, variation due to milling site exceeded environmentally induced compositional variation of a single switchgrass genotype grown at different sites. From these observations, we recommend a protocol with two sequential millings that decouples growth environment from a particular mill. Utilizing this approach, we found that 46/46 biomass composition traits from the warm season herbaceous forage and switchgrass bioethanol NIRS equations vary significantly (P < 0.001) in clones of a switchgrass genotype (WBC) grown at ten sites, with the growth site representing the largest average source of variation (41%). This multi-site milling approach can be used to examine environmental and gene-by-environment influences on composition with the goal of optimizing cell wall composition in different environments for biomass utilization.

09 BIOMASS FUELS↗

Ultrathin Amorphous Silica Membrane Enhances Proton Transfer across Solid-to-Solid Interfaces of Stacked Metal Oxide Nanolayers while Blocking Oxygen

A large jump of proton transfer rates across solid-to-solid interfaces by inserting an ultrathin amorphous silica layer into stacked metal oxide nanolayers is discovered using electrochemical impedance spectroscopy and Fourier-transform infrared reflection absorption spectroscopy (FT-IRRAS). The triple stacked nanolayers of Co 3 O 4 , SiO 2 , and TiO 2 prepared by atomic layer deposition (ALD) enable a proton flux of 2400 ± 60 s -1 nm -2 (pH 4, room temperature), while a single TiO 2 (5 nm) layer exhibits a threefold lower flux of 830 s -1 nm -2 . Based on FT-IRRAS measurements, this remarkable enhancement is proposed to originate from the sandwiched silica layer forming interfacial SiOTi and SiOCo linkages to TiO 2 and Co 3 O 4 nanolayers, respectively, with the O bridges providing fast H + hopping pathways across the solid-to-solid interfaces. Finally, together with the complete O 2 impermeability of a 2 nm ALD-grown SiO 2 layer, the high flux for proton transport across multi-stack metal oxide layers opens up the integration of incompatible catalytic environments to form functional nanoscale assemblies such as artificial photosystems for CO 2 reduction by H 2 O.

36 MATERIALS SCIENCE↗