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At least 775 records · Page 43

Investigating Np(VI) Nitrate Speciation Control through Temperature and Optical Spectroscopy

Numerous areas of nuclear processing, such as radioisotope production, nuclear waste remediation, and separations, depend upon the speciation of f-elements in the solution state. However, fundamental knowledge of the actinides─particularly Np─lags behind most of the elements on the periodic table. Despite the importance of Np(VI) chemistry in separations and nuclear processing, its speciation in HNO 3 remains uncertain. This work addresses some of these gaps by investigating the effect of HNO 3 concentration and temperature on the spectra and speciation of the Np(VI) nitrate system. Six samples of Np in 1 to 10 M HNO 3 were prepared and treated with (NH 4 ) 2 [Ce(NO 3 ) 6 ] to stabilize the hexavalent oxidation state. The absorbance spectrum of the 10 M HNO 3 is drastically different from the spectra of the other samples; the 10 M spectrum indicates coordination of nitrate ligands to the Np(VI)O 2 2+ ion to form a complex with high symmetry. Additionally, absorbance spectra were recorded over the temperature range of 15 to 40 °C, and systematic increases and decreases in certain spectral features of the ultraviolet–visible (UV–vis)–near-infrared (NIR) spectra are present in the spectra. The difference in spectral features suggests that Np(VI) nitrate speciation depends on temperature. Dilution studies of this sample were monitored with UV–vis–NIR and Raman spectroscopies. Spectral data indicate the presence of multiple complexes with different symmetries, including a high-symmetry complex with an inversion center. As samples are diluted and aquo ligands replace nitrate ligands bound to the Np(VI) neptunyl cation, changes in spectroscopic signals indicate a decrease in the high-symmetry nitrate complex and an increase in the lower-symmetry aquo complex. Additionally, the Raman band associated with the Np(VI)O 2 2+ symmetric stretch broadens with dilution and is fitted with two peaks. These peaks are assigned to Np(VI) aquo and nitrato complexes, indicating that this vibrational mode is sensitive to the coordination environment of the Np(VI) neptunyl cation and that contributions from these two Np(VI) complexes can be distinguished. This unique experimental data could be used to advance computational models describing the electronic transitions of complex actinyl ions.

Absorption↗

Microwave-assisted synthesis and characterization of nickel ferrite nanoparticles

Nickel ferrite nanoparticles (NiFe{sub 2}O{sub 4}) were successfully prepared by microwave-assisted combustion method (MWAC) using citric Electron acid as a chelating agent. NiFe{sub 2}O{sub 4} nanoparticles were characterized by X-ray diffraction (XRD) pattern, Scanning Microscopy (SEM), Fourier transform infrared (FTIR) and UV-Visible techniques. XRD analysis revealed that NiFe{sub 2}O{sub 4} nanoparticles have spinel cubic structure with the average crystalline size of 26.38 nm. SEM analysis revealed random and porous structural morphology of particles and FTIR showed absorption bands related to octahedral and tetrahedral sites, in the range 400–600cm{sup −1} which strongly favor the formation of NiFe{sub 2}O{sub 4} nanoparticles. The optical band gap is determined by UV Visible method and found to be 5.4 eV.

36 MATERIALS SCIENCE↗

Validation of Airborne Visible-Infrared Imaging Spectrometer Data at Ray Mine, AZ

We validate 1997 Airborne Visible-Infrared Imaging Spectrometer (AVIRIS) reflectance spectra covering 0.4 meu - 2.4 meu from a stable, flat mineralogically characterized man-made target at Ray Mine, AZ, the site for an EPA/NASA assessment of the utility of remote sensing for monitoring acid drainage from an active open pit mine.

AVIRIS visible-infrared spectrometer imaging↗

Annealing-free synthesis of carbonaceous Nb{sub 2}O{sub 5} microspheres by flame thermal method and enhanced photocatalytic activity for hydrogen evolution

Graphical abstract: Carbonaceous Nb{sub 2}O{sub 5} microspheres were firstly prepared by annealing-free flame thermal approach and its enhanced photocatalytic activity was demonstrated for hydrogen production. - Highlights: • Carbonaceous Nb{sub 2}O{sub 5} microspheres were prepared by annealing-free flame thermal approach in the first time. • Hydrolysis and incomplete combustion gave rise to Nb{sub 2}O{sub 5} incorporated with carbon. • Carbon species act as surface sensitizer to enhance photocatalytic activity. • It is possible to extend the strategy to develop various other metal oxides. - Abstract: An annealing-free synthesis of carbonaceous Nb{sub 2}O{sub 5} photocatalyst via a one-step flame assisted pyrolysis approach was proposed for the first time. Nearly amorphous carbonaceous Nb{sub 2}O{sub 5} microspheres were obtained directly through the facile and waste-free method. The presence of carbonate species was confirmed by means of EDS, XPS, BET and TEM. Both FT-IR and Raman analysis further revealed the existence form of carbon residuals for the resulted sample. UV–vis diffuse reflectance spectra showed the strong absorption of visible light and narrowed band gap for the carbon modified Nb{sub 2}O{sub 5}. On account of the vital role that carbon played in efficient electron-hole separation and light absorption, the hydrogen generation rate was 2.7 times that of the annealed and commercial Nb{sub 2}O{sub 5} samples. Further calcination can foster the crystallinity and expand specific surface area but lower the photocatalytic performance of as-prepared Nb{sub 2}O{sub 5} because of the elimination of carbon species. This work provides a new strategy for the preparation of carbonaceous Nb{sub 2}O{sub 5} candidates with enhanced photocatalytic activity.

36 MATERIALS SCIENCE↗

Space Weathering Maps of (101955) Bennu Using a Radiative Transfer Model

Space weathering is an important process that affects the surfaces of airless bodies, such as (101955) Bennu. The consequences of this process include physical and chemical changes to materials on the surface, which in turn change spectral characteristics, especially in the visible to near infrared wavelengths. These spectral changes are not the same across airless bodies because the changes are dependent on the composition and mineralogy of the surface and even location within the Solar System. The main space weathering products responsible for these spectral changes are submicroscopic particles, which consist of two types, nanophase and microphase particles, and affect visible to near-infrared reflectance spectra differently. Nanophase particles are particles <33 nm in size and occur in agglutinates and within glassy patinas around regolith particles. In contrast, microphase particles are >33 nm in size and are present only within agglutinates. These spectral differences are best illustrated by lunar samples. In lunar soils, the nanophase and microphase particles consist of metallic iron. With increasing abundance of nanophase iron particles in a regolith, its spectrum exhibits a lower overall reflectance in the visible to near infrared, weakened absorption bands, and a reddened continuum slope. In contrast, an increasing abundance of microphase iron only causes decreases in reflectance and not reddening. Because of the spectral differences introduced by these two types of particles, it is possible to model the nanophase and microphase particle abundances of a surface through the radiative transfer technique. Beyond the Moon, the composition of the nanophase and microphase particles can include other phases because the mineralogy of the surfaces of other planetary bodies is different. For example, the nanophase and microphase particles may consist of amorphous carbon (Mercury) and sulfides (Itokawa). The mineralogy of Bennu is consistent with carbonaceous chondrites. From a number of space weathering experiments on CM chondrites, the likely nanophase and microphase mineral phases on Bennu includes iron, magnetite, and sulfides (i.e., pentlandite and troilite). The goal of this work is to input the predicted nanophase and microphase compositions for Bennu into the radiative transfer technique. Next, we use this technique to model the OSIRIS-REx Visible Infrared Spectrometer (OVIRS) so that we can model the nanophase and microphase particle abundances across the surface. This will result in space weathering maps of the surface of Bennu, which are useful for understanding the degree of space weathering across the surface and its relationship to various regions and geological features.

Trang, D.↗

Weak Spectral Features on (101995) Bennu from the OSIRIS-REx Visible and InfraRed Spectrometer

Context. The NASA Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) mission has obtained thousands of spectra of asteroid (101955) Bennu with the OSIRIS-REx Visible and InfraRed Spectrometer (OVIRS). Aims. We present a spectral search for minor absorption bands and determine compositional variations on the surface of Bennu. Methods. Reflectance spectra with low and high spatial resolutions were analyzed for evidence of weak absorption bands. Spectra were also divided by a global average spectrum to isolate unique spectral features, and variations in the strongest band depths were mapped on a surface shape model. The global visible to near-IR spectrum of Bennu shows evidence of several weak absorption bands with depths of a few percent. Results. Several observed bands are consistent with phyllosilicates, and their distribution correlates with the stronger 2.74-μm hydration band. A 0.55-μm band is consistent with iron and is deepest in the spectrally reddest areas on Bennu. The presence of hydrated phyllosilicates and iron oxides indicates substantial aqueous alteration in Bennu’s past. Conclusions. Bennu’s spectra are not identical to a limited set of carbonaceous chondrite spectra, possibly due to compositional properties and spatial scale differences; however, returned samples should contain a mixture of common chondrite materials.

OSIRIS-REx↗

Quantifying Temperature Dependence of Pu(IV) Absorbance Spectra for Advanced Online Monitoring of Nuclear Processes

This article presents a systematic study of Pu(IV) absorbance spectral features as a function of temperature to develop an understanding of this parameter’s effect on chemometric models that can be used as online monitoring tools to support nuclear processing. The descriptive and predictive models that provide real-time feedback of these processes are usually constructed with data collected in conditions typical of a laboratory environment, which can differ drastically from a processing environment. To assess the impact of temperature on Pu(IV) absorbance spectra, 11 samples of Pu(IV) were synthesized with varying HNO 3 concentrations ranging from 0.6 to 9.5 M and heated between 15 and 45 °C. Ultraviolet (UV)–visible (vis)–near-infrared (NIR) absorption spectra collected at different HNO 3 concentrations and temperatures revealed that features associated with Pu(IV) are sensitive to temperature at all HNO 3 concentrations and that changes in features depend on HNO 3 concentration. The contributions of temperature and HNO 3 concentration to variation in Pu(IV) spectral features were evaluated using the principal component analysis of spectra that were baseline-corrected with an asymmetric least-squares method. Furthermore, predictive modeling for HNO 3 concentration with partial least-squares regression of UV–vis–NIR spectra highlighted the importance of accounting for temperature in the calibration set to optimize model performance. This methodology constitutes a new, systematic approach to account for the effect of temperature on the absorption spectra of metal ions and is useful for process monitoring applications in many industries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of isotopic substitution on the visible absorption spectrum of ozone

Gas-phase spectra for (O-16)3 and (O-18)3 are examined to consider the electronic states which cause the Chappuis bands. Specifications of the spectrometer and spectra calibrations are given. The results of both a conventional description of the vibrational structure and an examination of the autocorrelation functions are discussed. Transitions to two electronically excited states are the significant features of the isotope shifts. The transitions are characterized by adiabatic energies about 750/cm apart, and the higher energy approaches 16,400/cm. The vibrational structure of the higher state accompanies a relatively simple progression, and the lower state accompanies one isolated band. The autocorrelation analysis shows that for (O-16)3, major recurrences near 31 and 41 fs are found, and longer equivalent times are found for (O-18)3. At longer times, minor recurrences are also found. The results are considered significant for the understanding of the electronic and vibrational structures of the Chappuis bands. Suggestions for future work based on these results are discussed.

Anderson, Stuart M.↗

Entropic screening preserves non-equilibrium nature of nematic phase while enthalpic screening destroys it

The present manuscript describes the role of entropic and enthalpic forces mediated by organic non-polar (hexane) and polar (methanol) solvents on the bulk and microscopic phase transition of a well known nematic liquid crystalline material MBBA (N-(4-methoxybenzylidene)-4-butylaniline) through Differential Scanning calorimetry (DSC), UV-Visible (UV–Vis), and Fourier Transform Infrared (FTIR) spectroscopy. DSC study indicates continuous linear decreases in both nematic-isotropic (N-I) phase transition temperature and enthalpy of MBBA in presence of hexane while both these parameters show a saturation after an initial decay in methanol. These distinct transitional behaviours were explained in terms of the “depletion force” model for entropic screening in hexane and “screening-self-screening” model for methanol. Heating rate dependent DSC studies find that non-Arrhenius behaviour, characteristic of pristine MBBA and a manifestation of non-equilibrium nature [Dan et al., J. Chem. Phys. 143, 094501 (2015)], is preserved in presence of entropic screening in the hexane solution, while it changes to Arrhenius behaviour (signifying equilibrium behaviour) in presence of enthalpic screening in methanol solution. FTIR spectra show similar dependence on the solvent induced screening in the intensities of the imine (—C = N) stretch and the out-of-plane distortion vibrations of the benzene rings of MBBA with hexane and methanol as in DSC, further establishing our entropic and enthalpic screening models. UV–Vis spectra of the electronic transitions in MBBA as a function of temperature also exhibit different dependences of intensities on the solvent induced screening, and an exponential decrease is observed in presence of hexane while methanol completely changes the nature of interaction to follow a linear dependence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Tagish Lake Meteorite as a Possible Sample from a T or D Type Asteroid

Since the Tagish Lake meteorite fell in January 2000, the one of the kind meteorite has become the hottest issue among meteoriticists as well as astrobiologists. Meanwhile, concerning the physical origin of the meteorite in our solar system, only Hiroi et al. reported that it likely came from a D asteroid based on comparison of their visible-near-infrared (Vis-NIR) reflectance spectra. However, because asteroid classification is usually performed based on a limited range of wavelength, the asteroid classes and surface compositions may not necessarily have one-to-one correspondence. Also, Hiroi et al. precluded the T-type asteroids simply because their average albedo is much higher than the visible reflectance of Tagish Lake although their spectral matches with Tagish Lake were good, and the 3-mm band spectra compiled in were not enough to compare the degree of hydration or kinds of hydrous minerals between primitive asteroids and Tagish Lake. In this paper, we employ more spectral datasets up to the 3-mm range to address the possible connection between two particular asteroids, 773 Irmintraud and 308 Polyxo, and the Tagish Lake meteorite.

Hiroi, T.↗

Vibrational spectra of CO adsorbed on oxide thin films: A tool to probe the surface defects and phase changes of oxide thin films

Thin films of iron oxide were grown on Pt(111) single crystals using cycles of physical vapor deposition of iron followed by oxidative annealing in an ultrahigh vacuum apparatus. Two procedures were utilized for film growth of ∼15–30 ML thick films, where both procedures involved sequential deposition+oxidation cycles. In procedure 1, the iron oxide film was fully grown via sequential deposition+oxidation cycles, and then the fully grown film was exposed to a CO flux equivalent to 8 × 10{sup −7} millibars, and a vibrational spectrum of adsorbed CO was obtained using infrared reflection-absorption spectroscopy. The vibrational spectra of adsorbed CO from multiple preparations using procedure 1 show changes in the film termination structure and/or chemical nature of the surface defects—some of which are correlated with another phase that forms (“phase B”), even before enough of phase B has formed to be easily detected using low energy electron diffraction (LEED). During procedure 2, CO vibrational spectra were obtained between deposition+oxidation cycles, and these spectra show that the film termination structure and/or chemical nature of the surface defects changed as a function of sequential deposition+oxidation cycles. The authors conclude that measurement of vibrational spectra of adsorbed CO on oxide thin films provides a sensitive tool to probe chemical changes of defects on the surface and can thus complement LEED techniques by probing changes not visible by LEED. Increased use of vibrational spectra of adsorbed CO on thin films would enable better comparisons between films grown with different procedures and by different groups.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Improvement of reliability and power consumption for SnSb{sub 4} phase change film composited with Ga{sub 3}Sb{sub 7} by superlattice-like method

Superlattice-like (SLL) SnSb{sub 4}/Ga{sub 3}Sb{sub 7} (SS/GS) thin films were investigated through in-situ film resistance measurement. The optical band gap was derived from the transmittance spectra by using a UV-visible-NIR (ultraviolet-visible-near infrared) spectrophotometer. Transmission electron microscopy was used to observe the micro-structure before and after annealing. Phase change memory cells based on the SLL [SS(3 nm)/GS(4.5 nm)]{sub 7} thin films were fabricated to test and verify the operation consumption and switching endurance. The scanning thermal microscopy was used to probe the nanoscale thermal property.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

In-Flight Performance of the Ozone Monitoring Instrument

The Dutch-Finnish Ozone Monitoring Instrument (OMI) is an imaging spectrograph flying on NASA's EOS Aura satellite since 15 July 2004. OMI is primarily used to map trace-gas concentrations in the Earth's atmosphere, obtaining mid-resolution (0.4-0.6 nm) ultraviolet-visible (UV- VIS; 264-504 nm) spectra at multiple (30-60) simultaneous fields of view. Assessed via various approaches that include monitoring of radiances from selected ocean, land ice and cloud areas, as well as measurements of line profiles in the solar spectra, the instrument shows low optical degradation and high wavelength stability over the mission lifetime. In the regions relatively free from the slowly unraveling "row anomaly" (RA) the OMI irradiances have degraded by 3- 8 %, while radiances have changed by 1-2 %. The long-term wavelength calibration of the instrument remains stable to 0.005-0.020 nm.

ultraviolet↗

Optical modeling and electrical properties of cadmium oxide nanofilms: Developing a meta–heuristic calculation process model

Cadmium oxide thin films were deposited onto glass substrates by sol–gel dip-coating method and annealed in air. The normal incidence transmittance of the films was measured by a spectrophotometer. D.C electrical parameters such as carrier concentration and mobility were analyzed by Hall Effect measurements. A combination of Forouhi–Bloomer and standard Drude model was used to simulate the optical constants and thicknesses of the films from transmittance data. The transmittance spectra of the films in the visible domain of wavelengths were successfully fitted by using the result of a hybrid particle swarm optimization method and genetic algorithm. The simulated transmittance is in good accordance with the measured spectrum in the whole measurement wavelength range. The electrical parameters obtained from the optical simulation are well consistent with those measured electrically by Hall Effect measurements.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Composition of Organics on Asteroid (101955) Bennu

Context: The Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) mission detected an infrared absorption at 3.4μm on near-Earth asteroid(101955) Bennu. This absorption is indicative of carbon species, including organics, on the sur-face. Aims: We aim to describe the composition of the organic matter on Bennu by investigating the spectral features in detail. Methods: We use a curated set of spectra acquired by the OSIRIS-REx Visible and InfraRed Spectrometer (OVIRS) that have features near 3.4μm (3.2 to 3.6μm) attributed to organics. We assess the shapes and strengths of these absorptions in the context of laboratory spectra of extraterrestrial organics and analogs. Results: We find spectral evidence of aromatic and aliphatic CH bonds. The absorptions are broadly consistent in shape and depth with those associated with insoluble organic matter in meteorites. Given the thermal and space weathering environments on Bennu, it is likely that the organics have not been exposed for long enough to substantially decrease the H/C and destroy all aliphatic molecules.

minor planets↗

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↗

Photocatalytic behaviour of CdS/ZnS nanocomposite for dye degradation in presence of visible light

In the present work ZnS-CdS composite was prepared by hydrothermal method. The prepared samples were characterized by X-ray diffraction (XRD) to confirm formation of nano particles, Scanning electron microscopy (SEM) images exhibit nanoscale dimensions of as synthesized individual phases. UV/VIS spectra were recorded for evaluation of photophysical properties. The composite was explored as photocatalysts to study dye degradation using methylene blue in aqueous slurry under irradiation of 663 nm wavelength and congo red under irradiation of 493 nm wavelength. Under the same conditions the photocatalytic activity of the individual phases ZnS and CdS were also examined. The ZnS-CdS composite is found in enhancing the rate of photo degradation of toxic dyes as compare to ZnS and CdS individually in presence of visible light. This ZnS based metal sulphide/oxide semiconductor nanocomposites are high potential material for Photo-degradation of toxic dyes, and act as good photocatalyst in visible light.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Characteristics of In Situ Fine Fraction Aerosol Spectra from 300-700 nm Observed Around the Korean Peninsula During KORUS-OC

In situ aerosol extinction and absorption spectra covering the 300-700 nm range at ≤ 1 nm spectral resolution were measured aboard the R/V Onnuri during the Korea U.S. – Ocean Color (KORUS-OC) cruise around the Korean Peninsula from May 21 through June 3, 2016. Total absorption spectra were obtained from aerosols collected on glass fiber filters and subsequently placed in the center of an integrating sphere (Labsphere DRA-CA-30) attached to a dual beam spectrophotometer (Cary 100 Bio UV-Visible Spectrophotometer, 0.2 nm spectral resolution). Absorption spectra from methanol and deionized water extracts of aerosols collected on Teflon filters were measured in a liquid waveguide capillary cell (World Precision Instruments LWCC- 3100, ~0.4 nm spectral resolution). Extinction spectra were measured with a custom built instrument (SpEx, ~0.8 nm spectral resolution). The measurements were obtained at a height of ~10 m above the sea surface with an inlet that limited the measured aerosols to diameters ≤ 1.3 µm. All four sets of spectra exhibit curvature in log-log space with 2nd order polynomials providing a better fit to the measured spectra than power law fits. The deionized water extracts were also analyzed with an ion chromatograph (Dionex ICS-3000 Ion Chromatography System) and with an aerosol mass spectrometer (Aerodyne Research, Inc. HR-ToF High Resolution Aerosol Mass Spectrometer) to examine chemical composition. These data indicate the optical spectra are sensitive to differing chemical properties of the measured ambient aerosols and suggest differing sources and/or atmospheric processes influence the observed optical signatures. The measured suite of spectra are combined to examine the spectral characteristics of single scattering albedo, as well as to examine the contribution of soluble absorbing chromophores to the total absorption spectra. Additional measurements made during the affiliated Korea U.S. - Air Quality (KORUS-AQ) campaign will be used to provide further insight on the observed spectral characteristics.

Jordan, Carolyn E↗