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At least 127 records · Page 7

Radiometric Calibration of A Non-Imaging Airborne Spectrometer To Measure the Greenland Ice Sheet Surface

Methods to radiometrically calibrate a non-imaging airborne visible-to-shortwave infrared (VSWIR) spectrometer to measure the Greenland ice sheet surface are presented. Airborne VSWIR measurement performance for bright Greenland ice and dark bare rock/soil targets is compared against the MODerate resolution atmospheric TRANsmission (MODTRAN ® ) radiative transfer code (version 6.0), and a coincident Landsat 8 Operational Land Imager (OLI) acquisition on 29 July 2015 during an in-flight radiometric calibration experiment. Airborne remote sensing flights were carried out in northwestern Greenland in preparation for the Ice, Cloud, and land Elevation Satellite 2 (ICESat-2) laser altimeter mission. A total of nine science flights were conducted over the Greenland ice sheet, sea ice, and open-ocean water. The campaign's primary purpose was to correlate green laser pulse penetration into snow and ice with spectroscopic-derived surface properties. An experimental airborne instrument configuration that included a nadir-viewing (looking downward at the surface) non-imaging Analytical Spectral Devices (ASD) Inc. spectrometer that measured upwelling VSWIR (0.35 to 2.5 µm) spectral radiance (Wm −2 sr −1 µm −1 ) in the two-color Slope Imaging Multi-polarization Photon-Counting Lidar's (SIMPL) ground instantaneous field of view, and a zenith-viewing (looking upward at the sky) ASD spectrometer that measured VSWIR spectral irradiance (W m −2 nm −1 ) was flown. National Institute of Standards and Technology (NIST) traceable radiometric calibration procedures for laboratory, in-flight, and field environments are described in detail to achieve a targeted VSWIR measurement requirement of within 5 % to support calibration/validation efforts and remote sensing algorithm development. Our MODTRAN predictions for the 29 July flight line over dark and bright targets indicate that the airborne nadir-viewing spectrometer spectral radiance measurement uncertainty was between 0.6 % and 4.7 % for VSWIR wavelengths (0.4 to 2.0 µm) with atmospheric transmittance greater than 80 %. MODTRAN predictions for Landsat 8 OLI relative spectral response functions suggest that OLI is measuring 6 % to 16 % more top-of-atmosphere (TOA) spectral radiance from the Greenland ice sheet surface than was predicted using apparent reflectance spectra from the nadir-viewing spectrometer. While more investigation is required to convert airborne VSWIR spectral radiance into atmospherically corrected airborne surface reflectance, it is expected that airborne science flight data products will contribute to spectroscopic determination of Greenland ice sheet surface optical properties to improve understanding of their potential influence on ICESat-2 measurements.

Christopher J. Crawford↗

Impact of pellet preparation on reflectance measurements of ammonium sulfate by single-angle reflectance spectroscopy

The optical constants, n and k, are required to model the reflection, refraction and transmission of light at the first surface interface of a material, as well as its propagation through the material; here n corresponds to the real component and k the imaginary component of the refractive index. Several different spectroscopic methods have been used to determine the n and k values for different materials, including single angle reflectance spectroscopy and ellipsometry. The single-angle reflectance method quantitatively records the specular reflectance R(v) from a plane parallel face of the material and uses the Kramers-Kronig transform to extract the n and k values. For most compounds, however, it is difficult to obtain a single crystal or high-quality window of sufficient planarity and of the appropriate dimensions (several mm) to make the measurement. For this reason, we further investigate the use of pressed pellets of neat powdered substances to measure optical constants of these substances using the single-angle reflectance method. We have found that surface roughness can significantly influence the measured quantitative reflectance spectrum R(v) and, consequently, the derived n and k parameters. A collaborative study between Defence Research and Development Canada (DRDC) - Valcartier Research Center and Pacific Northwest National Laboratory (PNNL) has been carried out using different pellets of neat ammonium sulfate [(NH4)2SO4] to show how parameters such as the relative fraction of particle sizes for the component powder along with the grinding process of the pure compound all can affect the reflectance spectrum used to derive the optical constants. All pressed pellets were characterized by single-angle reflectance spectroscopy.

Diaz, Emmanuela↗

Spectroscopic analyses of Fe and water in clays: A Martian surface weathering study

Martian surface morphology suggests the presence of liquid H2O on Mars in the past. Reflectance spectra of the Martian surface include features which correspond to the crystal field transitions of iron, as well as features supporting the presence of ice and minerals containing structural OH and surface water. Researchers initiated further spectroscopic studies of surface iron and water and structural OH in clays in order to determine what remotely obtained spectra can indicate about the presence of clays on Mars based on a clearer understanding of the factors influencing the spectral features. Current technology allows researchers to better correlate the low frequency fundamental stretching and bending vibrations of O-H bonds with the diagnostic near infrared overtone and combination bands used in mineral characterization and identification.

Bishop, J. L.↗

Spectroscopic observation of Mars

A review is given of what is known about the surface of Mars from reflectance spectroscopy, including some new results and providing an overview of the principles involved. While some form of bound water and/or OH has been known on Mars for many years, a new result presented is the identification of structural OH in a dilute or poorly crystalline magnesian clay. The detection of water ice in the residual north polar cap is noted. Also considered is the role that reflectance spectroscopy will play in the future, from earth and as an important part of the NASA Mars Geosciences/Climatology Orbiter mission.

Singer, R. B.↗

Analytical Tools to Assess Polymer Biodegradation: A Critical Review and Recommendations

Many petroleum-derived plastic materials are highly recalcitrant and persistent in the environment, posing significant threats to human and ecological receptors due to their accumulation in ecosystems. In recent years, research efforts have focused on advancing biological methods for polymer degradation. Enzymatic depolymerization has emerged as particularly relevant for biobased plastic recycling, potentially scalable for industrial use. Biodegradation involves adsorption to the plastic solid surface, followed by an interfacial reaction, resulting in cleavage of bonds of polymer chains exposed on the surface. Here, widely varying substrate-specific kinetics are observed, with the polymer’s properties possessing a significant impact on the rate of this interfacial catalysis. Thus, there is a critical need for sensitive and accurate characterization of the material surface during and after interfacial depolymerization to fully understand the reaction mechanisms. Here, we provide a critical review of a range of techniques used in the analysis of material surfaces to characterize the chemical, topological, and morphological features relevant to the study of enzymatic biocatalysis, including microscopy techniques, spectroscopic techniques (e.g., X-ray diffraction analysis, Fourier transform infrared attenuated total reflectance spectroscopy, and mass spectrometry detection of analytes associated with degradation). Techniques for evaluation of surface energy and topology in their relevancy for sensitive detection of biological surface modifications are also discussed. In addition, this paper provides an overview of the strengths of these techniques and compares their performance in both sensitivity and throughput, including emerging techniques, which can be useful, particularly for the rapid analysis of the surface properties of polymeric materials in high-throughput screening of candidate biocatalysts. This research serves as a starting point in selecting and applying appropriate methodologies that provide direct evidence to the ongoing biotic degradation of polymeric materials.

Colachis, Matthew↗

Effective point-charge analysis of crystal fields: Application to rare-earth pyrochlores and tripod kagome magnets 𝑅 ⁢3⁢ Mg⁢ 2 ⁢Sb⁢ 3⁢ O⁢ 14

An indispensable step to understand collective magnetic phenomena in rare-earth compounds is the determination of spatially anisotropic single-ion properties resulting from spin-orbit coupling and crystal field (CF). The CF Hamiltonian has a discrete energy spectrum—accessible to spectroscopic probes such as neutron scattering—controlled by a number of independent parameters reflecting the point symmetry of the magnetic sites. Determining these parameters in low-symmetry systems is often challenging. Here, we describe a general method to analyze CF excitation spectra using adjustable effective point-charges. We benchmark our method to existing neutron-scattering measurements on pyrochlore rare-earth oxides and obtain a universal point-charge model that describes a large family of related materials. We adapt this model to the newly discovered tripod kagome magnets (𝑅 3 ⁢Mg 2 ⁢Sb 3 ⁢O 14 , 𝑅 = Tb, Ho, Er, Yb) for which we report broadband inelastic neutron-scattering spectra. Analysis of these data using adjustable point-charges yields the CF wave functions for each compound. From this, we calculate thermomagnetic properties that accurately reflect our measurements on powder samples and predict the effective gyromagnetic tensor for pseudospin degrees of freedom—a crucial step to understand the exotic collective properties of these kagome magnets at low temperature. We present further applications of our method to other tripod kagome materials and triangular rare-earth compounds 𝑅⁢MgGaO 4 (𝑅 =Yb, Tm). Overall, this study establishes a widely applicable methodology to predict CF and single-ion properties of rare-earth compounds based on interpretable and adjustable models of effective point charges.

Crystal-field theory↗

A comparison of alternative methods for detecting other planetary systems

Independent methods considered for use in the direct or indirect detection of extrasolar planetary systems are compared. Consideration is given to the principles, advantages and disadvantages of indirect astrometric, spectroscopic and photometric methods, and the direct detection of the intrinsic thermal radiation, reflected central star radiation or intrinsic nonthermal radiation of a planet. The importance of a redundance of detection methods as well as instrumentation within a given method is pointed out.

Black, D. C.↗

High temperature kinetic study of the reactions H + O2 = OH + O and O + H2 = OH + H in H2/O2 system by shock tube-laser absorption spectroscopy

The reactions: (1) H + O2 = OH + O; and (2) O + H2 = OH + H are the most important elementary reactions in gas phase combustion. They are the main chain-branching reaction in the oxidation of H2 and hydrocarbon fuels. In this study, rate coefficients of the reactions and have been measured over a wide range of composition, pressure, density and temperature behind the reflected shock waves. The experiments were performed using the shock tube - laser absorption spectroscopic technique to monitor OH radicals formed in the shock-heated H2/O2/Ar mixtures. The OH radicals were detected using the P(1)(5) line of (0,0) band of the A(exp 2) Sigma(+) from X(exp 2) Pi transition of OH at 310.023 nm (air). The data were analyzed with the aid of computer modeling. In the experiments great care was exercised to obtain high time resolution, linearity and signal-to-noise. The results are well represented by the Arrhenius expressions. The rate coefficient expression for reaction (1) obtained in this study is k(1) = (7.13 +/- 0.31) x 10(exp 13) exp(-6957+/- 30 K/T) cu cm/mol/s (1050 K less than or equal to T less than or equal to 2500 K) and a consensus expression for k(1) from a critical review of the most recent evaluations of k(1) (including our own) is k(1) = 7.82 x 10(exp 13) exp(-7105 K/T) cu cm/mol/s (960 K less than or equal to T less than or equal to 5300 K). The rate coefficient expression of k(2) is given by k(2) = (1.88 +/- 0.07) x 10(exp 14) exp(-6897 +/- 53 K/T) cu cm/mol/s (1424 K less than or equal to T less than or equal to 2427 K). For k(1), the temperature dependent A-factor and the correlation between the values of k(1) and the inverse reactant densities were not found. In the temperature range of this study, non-Arrhenius expression of k(2) which shows the upward curvature was not supported.

Ryu, Si-Ok↗

Composition and Origin of Martian Surface Material, Remote Detection of Minerals, and Applications to Astrobiology

Martian surface composition and processes are under study through analysis of spectral, magnetic and chemical data from Mars and analysis of laboratory analog materials. The focus of this study is on potential lander/rover measurements of weathered volcanic tephra and hydrothermal rocks because these samples resulted from processes that may have occurred on Mars. Fine-grained particles from these sources may be responsible for origination of the dust/soil on Mars that is shaping the planet's surface character. Alteration on the surface of Mars likely includes both chemical and physical interactions of soil particles and rock surfaces. Many of the minerals present in hydrothermal samples may be associated with organisms and may be useful as indicators of life or environments supportive of life on Mars. Characterization of the spectroscopic properties in the visible/near-infrared (VIS/NIR) and mid-infrared (IR) regions using reflectance, emittance and Raman, as well as the thermal properties of minerals thought to be present on Mars are being performed in order to identify them remotely. Particular interest is directed toward locating minerals, and hence landing sites, important to Astrobiology.

Bishop, J. L.↗

Rapid Changes in Mercury's Sodium Exosphere

Sodium in the atmosphere of Mercury can be detected by sunlight scattered in the D1 and D2 resonance lines. Images of the sodium emission show that the sodium density changes from day to day and is often concentrated in regions at high or mid latitudes. Drew Potter (NASA/JSC) and Tom Morgan (SWRI) suggested that sputtering by magnetospheric particles was the origin of the sodium. A problem with this is that the magnetic field of Mercury is strong enough that it is believed to shield the surface from solar particles much of the time, although particle precipitation at the magnetospheric cusps could deposit particles to the surface at high latitudes. Ann Sprague (UA/LPL) noted that the "spots" of sodium emission tended to coincide with major geologic features, such as the Caloris Basin. She proposed that the sodium is released from sodiumrich surface rocks that are associated with these features; however, some spots have appeared where there are no obvious geologic features. Some of the difficulty in ascribing a source for the sodium arises from the effect of terrestrial atmospheric blurring of the image. It is hard to tell exactly where the sodium emission originates after the atmosphere has blurred the image. Potter, Killen (SWRI), and Morgan recently developed a technique for correcting sodium images for atmospheric blurring, using images made with a large-area image slicer. They applied this technique to a series of Mercury sodium observations made in November, 1997 at the McMath-Pierce Solar Telescope. Their technique for producing images from the spectroscopic data provides images of both the sodium emission and of the sunlight reflected from the surface.

Potter, Drew↗

The Diverse Surface Compositions of the Galilean Satellites

The galilean satellites represent a diverse collection, ranging from the volcanic moon Io, with a surface that is changing yearly, to Callisto, with a dark, ancient surface overlying ice. The composition of these surfaces are also quite different due to a variety of processes and influences, including tidal heating, radiolysis, gardening, a magnetic field (Ganymede), and meteoritic infall. Io's surface contains large quantities of sulfur dioxide (SO2) and colorful sulfur allotropes, both originating in plumes and flows from the tidally driven volcanoes. A broad, 1-micron band is found at high latitudes and may be due to absorption by long-chain sulfur polymers produced by SO2 radiolysis, although iron and iron sulfide compounds are candidates. An unidentified 3.15 micron absorber is equatorially distributed while a 4.62 micron band, perhaps due to a sulfate compound, exhibits a non-uniform distribution. Hot spots are generally dark, and some exhibit negative reflectance slopes (i.e., blue). The composition of these lavas has not been established spectroscopically, but the high temperatures of some volcanoes suggest ultramafic silicates or perhaps more refractory material such as oxides.

Carlson, R. W.↗

Earth Glint Observations Conducted During the Deep Impact Spacecraft Flyby

We describe observations of Earth conducted using the High Resolution Instrument (HRI) - a 0.3 m f/35 telescope - on the Deep Impact (DI) spacecraft during its recent flybys. Earth was observed on five occasions: 2008-Mar-18 18:18 UT, 2008-May-28 20:05 UT, 2008-Jun-4 16:57 UT, 2009-Mar-27 16:19 and 2009-Oct-4 09:37 UT. Each set of observations was conducted over a full 24-hour rotation of Earth and a total of thirteen NIR spectra were taken on two-hour intervals during each observing period. Photometry in the 450, SSO, 650 and 8S0 nm filters was taken every fifteen minutes and every hour for the 350, 750 and 950 nm filters. The spacecraft was located over the equator for the three sets of observations in 2008, while the 2009- Mar and 2009-Oct were taken over the north and south Polar Regions, respectively. Observations of calibrator stars Canopus and Achernar were conducted on multiple occasions through all filters. The observations detected a strong specular glint not necessarily associated with a body of water. We describe spectroscopic characterization of the glint and evidence for the possibility of detection of reflection from high cirrus clouds. We describe implications for observations of extrasolar planets.

Barry, R. K.↗

Multifunction Imaging and Spectroscopic Instrument

A proposed optoelectronic instrument would perform several different spectroscopic and imaging functions that, heretofore, have been performed by separate instruments. The functions would be reflectance, fluorescence, and Raman spectroscopies; variable-color confocal imaging at two different resolutions; and wide-field color imaging. The instrument was conceived for use in examination of minerals on remote planets. It could also be used on Earth to characterize material specimens. The conceptual design of the instrument emphasizes compactness and economy, to be achieved largely through sharing of components among subsystems that perform different imaging and spectrometric functions. The input optics for the various functions would be mounted in a single optical head. With the exception of a targeting lens, the input optics would all be aimed at the same spot on a specimen, thereby both (1) eliminating the need to reposition the specimen to perform different imaging and/or spectroscopic observations and (2) ensuring that data from such observations can be correlated with respect to known positions on the specimen. The figure schematically depicts the principal components and subsystems of the instrument. The targeting lens would collect light into a multimode optical fiber, which would guide the light through a fiber-selection switch to a reflection/ fluorescence spectrometer. The switch would have four positions, enabling selection of spectrometer input from the targeting lens, from either of one or two multimode optical fibers coming from a reflectance/fluorescence- microspectrometer optical head, or from a dark calibration position (no fiber). The switch would be the only moving part within the instrument.

Mouroulis, Pantazis↗

Nondestructive Evaluation of Thermal Barrier Coatings by Mid-infrared Reflectance

The application of mid-infrared reflectance (MIR) imaging to monitor damage in thermal barrier coatings (TBCs) has been extended from a previously demonstrated area-averaged spectroscopic analysis tool to become a practical imaging tool that provides the spatial resolution needed to quickly identify localized regions of TBC damage by visual inspection, Illumination optics and image collection procedures were developed to produce illumination-normalized flatfield reflectance images after subtraction of the background thermal emission. MIR reflectance images were collected with a bandpass filter centered at a wavelength of 4 microns, which provided the optimum balance between good sensitivity to buried cracks and coating erosion, but with a desirable sensitivity to TBC sintering and absorption from ambient gases. Examples are presented of the application of MIR reflectance imaging to monitor damage progression in plasma-sprayed 8wt% yttria-stabilized zirconia (8YSZ) TBCs subjected to either furnace cycling or alumina particle jet erosion. These results show that MIR reflectance imaging can reliably track the progression of buried delamination cracks produced by thermal cycling and can also be used to determine when any local section of the TBC has eroded beyond an acceptable limit. Modeling of the effects of buried cracks and erosion on reflectance will be presented to show the dependence of damage sensitivity to TBC thickness.

Eldridge, Jeffrey I↗

Supported Electrophilic Organoruthenium Catalyst for the Hydrosilylation of Olefins

A series of supported electrophilic organoruthenium complexes has been synthesized via surface organometallic chemistry (SOMC) techniques and applied to the selective hydrosilylation of olefins. The air-sensitive 16e - complex Cp*RuMes(PCy 3 ) (1) (Cp* = pentamethylcyclopentadienyl, Mes = mesityl) was synthesized by the treatment of Cp*RuCl(PCy 3 ) with mesityl Grignard MesMgBr. This species was chemisorbed onto sulfated zirconia SO 4 /ZrO 2 , but the resulting material was inactive toward cyclohexene hydrosilylation with phenylsilane. Instead, Cp*RuMes(PCy 3 ) was treated with phenylsilane (PhSiH 3 ) to provide a ruthenium disilyl hydride complex Cp*RuH(SiH 2 Ph) 2 (PCy 3 ) (3), which was fully characterized by NMR spectroscopy and single-crystal X-ray diffraction. Grafting this species onto SO 4 /ZrO 2 resulted in the formation of phenylsilane along with the surface electrophilic species [Cp*RuH(R)(X-SiHPh)(PCy 3 )] (R = H, O 3 S-O or O 3 Zr-O; 4a, 4b, X = O 3 S-O, and O 3 Zr-O, respectively) as the major species. Material 4 was characterized via a combination of spectroscopic techniques including dynamic nuclear polarization (DNP)-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray absorption spectroscopy (XAS), and density function theory (DFT) calculations. Further, capping the remaining acid sites on 4 with Me 3 Si-SiMe 3 provides 5, which significantly reduces side reactions, such as olefin isomerization and silane redistribution. Catalyst 5 is a highly robust and selective hydrosilylation catalyst and can be recycled up to 5 times without significant diminishment of activity. Exclusive anti-Markovnikov regiochemistry, cis-addition selectivity, and the inactivity of secondary and tertiary silanes provide support for the proposed Glaser-Tilley mechanism involving cationic ruthenium silylene species analogous to homogeneous systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-Crystal X-Ray Spectropolarimeter

X-ray spectropolarimetry is a diagnostics technique suitable for measuring intense electron beams and strong magnetic fields in hot, dense plasmas. To increase the accuracy achievable, we investigated the possibility of measuring both orthogonal components of linear polarization simultaneously using a single crystal. We demonstrated experimentally for the first time that crystals with cubic symmetry can be used as polarizing beam splitters. We also found that the polarization-splitting planes in cubic crystals can be accessed in two crystal orientations, a property that can be used to decrease the clutter in polarized spectra. In parallel, we developed a ray-tracing code and are working to add the crystal reflectivity to instrument modeling codes, to help us interpret the spectra and to design spectroscopic and spectropolarimetric instruments. This work is motivated by the need to perform measurements of important quantities in difficult experimental conditions, such as the axial magnetic field at stagnation in magnetized liner inertial fusion loads.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Thermal infrared (2.5-13.5-micron) spectroscopic remote sensing of igneous rock types on particulate planetary surfaces

The compositional significance of outstanding spectral features in the reflectance spectra of particulate igneous rocks was investigated by analyzing directional reflectance spectra, obtained with an FTIR spectrophotometer at 2.17-13.5 microns, of a suite of well-characterized igneous rocks ground to fine particle size. It was found that, using spectral features associated with the principal Christiansen frequency and with a region of relative transparency between the Si-O stretching and bending bands, it is possible to identify general rock type using the Walter and Salisbury (1989) SCFM chemical index, SCFM, defined as SCFM = SiO2/(SiO2 + CaO + FeO + MgO). It is emphasized, however, that the appearance and the wavelength of these features may be affected by environmental factors.

Salisbury, John W.↗

Spectroscopic Measurement of Leaf Water Status

A leaf drying experiment was carried out in the laboratory in which simultaneous spectral reflectance in the 350-2450 nm region, and leaf weights, were measured at 10 second intervals over a 40 minute period. As the leaf water weight dropped from approximately 60 to 38%. a nearly-linear rise in reflectance at all wavelengths beyond 1000 nm was observed. A principal components analysis of the time series of spectra in the 2000-2500 nm wavelength region showed that over 99% of the variance in the spectra, that were individually scaled to have a sum equal to that of the mean spectrum and subsequently mean corrected, was in the first component. This result shows that it is feasible to determine leaf water content remotely with an imaging spectrometer independent of the surface irradiance effects caused by topography.

Goetz, Alexander F. H.↗