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At least 289 records · Page 16

Spectroscopy in the study of planetary atmospheres - Abundances from the visible region

Spectrophotometric studies of three molecular constituents - hydrogen, methane, and ammonia - identified in the visible region of the spectra of the outer planets are reviewed. The history of quadrupole line observations for hydrogen molecules and the significance of the HD molecule for the dipole spectrum are considered. Approaches to quantitative estimates of methane concentration in planetary atmospheres are explained, and the detection of ammonia in the atmospheres of Jupiter and Saturn is described.

Lutz, B. L.↗

The equilibrium constant for N2O5 = NO2 + NO3 - Absolute determination by direct measurement from 243 to 397 K

Direct determinations of the equilibrium constant for the reaction N2O5 = NO2 + NO3 were carried out by measuring NO2, NO3, and N2O5 using long-path visible and infrared absorption spectroscopy as a function of temperature from 243 to 397 K. The first-order decay rate constant of N2O5 was experimentally measured as a function of temperature. These results are in turn used to derive a value for the rate coefficient for the NO-forming channel in the reaction of NO3 with NO2. The implications of the results for atmospheric chemistry, the thermodynamics of NO3, and for laboratory kinetics studies are discussed.

Cantrell, C. A.↗

Experimental indication of a naphthalene-base molecular aggregate for the carrier of the 2175 angstroms interstellar extinction feature

Experiments where the simple polycyclic aromatic hydrocarbon (PAH) naphthalene (C10H8) is subjected to the energetic environment of a plasma have resulted in the synthesis of a molecular aggregate that has ultraviolet spectral characteristics that suggest it provides insight into the nature of the carrier of the 2175 angstroms interstellar extinction feature and may be a laboratory analog. Ultraviolet, visible, infrared, and mass spectroscopy, along with gas chromatography, indicate that it is a molecular aggregate in which an aromatic double ring ("naphthalene") structural base serves as the electron "box" chromophore that gives rise to the envelope of the 2175 angstroms feature. This chromophore can also provide the peak of the feature or function as a mantle in concert with another peak provider such as graphite. The molecular base/chromophore manifests itself both as a structural component of an alkyl-aromatic polymer and as a substructure of hydrogenated PAH species. Its spectral and molecular characteristics are consistent with what is generally expected for a complex molecular aggregate that has a role as an interstellar constituent.

NASA Discipline Exobiology↗

Adaptive Optics Imaging and Spectroscopy of Neptune

OBJECTIVES: We proposed to use high spectral resolution imaging and spectroscopy of Neptune in visible and near-IR spectral ranges to advance our understanding of Neptune s cloud structure. We intended to use the adaptive optics (AO) system at Mt. Wilson at visible wavelengths to try to obtain the first groundbased observations of dark spots on Neptune; we intended to use A 0 observations at the IRTF to obtain near-IR R=2000 spatially resolved spectra and near-IR A0 observations at the Keck observatory to obtain the highest spatial resolution studies of cloud feature dynamics and atmospheric motions. Vertical structure of cloud features was to be inferred from the wavelength dependent absorption of methane and hydrogen,

Johnson, Lindley↗

Single mode fiber array for planet detection using a visible nulling interferometer

We report the design, fabrication, and testing of a coherent large mode field diameter fiber array to be used as a spatial filter in a planet finding visible nulling interferometer. The array is a key component of a space instrument for visible-light detection and spectroscopy of Earth like extrasolar planets. In this concept, a nulling interferometer is synthesized from a pupil image of a single aperture which is then spatially filtered by a coherent array of single mode fibers to suppress the residual scattered star light. The use of the fiber array preserves spatial information between the star and planet. The fiber array uses a custom commercial large mode field or low NA step-index single mode fiber to relax alignment tolerances. A matching custom micro lens array is used to couple light into the fibers, and to recollimate the light out of the fiber array. The use of large mode field diameter fiber makes the fabrication of a large spatial filter array with 300 to 1000 elements feasible.

fiber arrays↗

The Visible Nulling Coronagraph--Architecture Definition and Technology Development

This paper describes the advantages of visible direct detection and spectroscopy of Earth-like extrasolar planets using a nulling coronagraph instrument behind a moderately sized single aperture space telescope. Our concept synthesizes a nulling interferometer by shearing the telescope pupil, with the resultant producing a deep null. We describe nulling configurations that also include methods to mitigate stellar leakage, such as spatial filtering by a coherent array of single mode fibers, and post-starlight suppression wavefront sensing and control. With diffraction limited telescope optics and similar quality components in the optical train (lambda/20), suppression of the starlight to 1e-10 is readily achievable. We describe key features of the architecture and analysis, present latest results of laboratory measurements demonstrating achievable null depth and component development, and discuss future key technical milestones.

nulling interferometer↗

The Visible Nulling Coronagraph--Progress Toward Mission and Technology Development

This paper describes a space mission for visible direct detection and spectroscopy of Earth like extrasolar planets using a nulling coronagraph instrument behind a moderately sized (approximately 4m) telescope in space. In our design, a 4 beam nulling interferometer is synthesized from the telescope pupil, producing a deep null proportional to theta (sup 4) which is then filtered by a coherent array of single mode fibers to suppress the residual scattered light. With diffraction limited telescope optics and similar quality components in the optical train (lambda/20), suppression of the starlight to 10 (exp -10) is achievable. We describe key features of the basic analysis, show how this effects a space mission design, present latest results of laboratory measurements demonstrating achievable null depth and component development, and discuss future key technical milestones.

coronagraph↗

Mud Volcanoes - Analogs to Martian Cones and Domes (by the Thousands!)

Mud volcanoes are mounds formed by low temperature slurries of gas, liquid, sediments and rock that erupt to the surface from depths of meters to kilometers. They are common on Earth, with estimates of thousands onshore and tens of thousands offshore. Mud volcanoes occur in basins with rapidly-deposited accumulations of fine-grained sediments. Such settings are ideal for concentration and preservation of organic materials, and mud volcanoes typically occur in sedimentary basins that are rich in organic biosignatures. Domes and cones, cited as possible mud volcanoes by previous authors, are common on the northern plains of Mars. Our analysis of selected regions in southern Acidalia Planitia has revealed over 18,000 such features, and we estimate that more than 40,000 occur across the area. These domes and cones strongly resemble terrestrial mud volcanoes in size, shape, morphology, associated flow structures and geologic setting. Geologic and mineralogic arguments rule out alternative formation mechanisms involving lava, ice and impacts. We are studying terrestrial mud volcanoes from onshore and submarine locations. The largest concentration of onshore features is in Azerbaijan, near the western edge of the Caspian Sea. These features are typically hundreds of meters to several kilometers in diameter, and tens to hundreds of meters in height. Satellite images show spatial densities of 20 to 40 eruptive centers per 1000 square km. Many of the features remain active, and fresh mud flows as long as several kilometers are common. A large field of submarine mud volcanoes is located in the Gulf of Cadiz, off the Atlantic coasts of Morocco and Spain. High-resolution sonar bathymetry reveals numerous km-scale mud volcanoes, hundreds of meters in height. Seismic profiles demonstrate that the mud erupts from depths of several hundred meters. These submarine mud volcanoes are the closest morphologic analogs yet found to the features in Acidalia Planitia. We are also conducting laboratory analyses of surface samples collected from mud volcanoes in Azerbaijan, Taiwan and Japan. X-ray diffraction, visible / near infrared reflectance spectroscopy and Raman spectroscopy show that the samples are dominated by mixed-layer smectite clays, along with quartz, calcite and pyrite. Thin section analysis by optical and scanning electron microscopy confirms the mineral identifications. These samples also contain chemical and morphological biosignatures, including common microfossils, with evidence of partial replacement by pyrite. The bulk samples contain approximately 1 wt% total organic carbon and 0.4 mg / gm volatile hydrocarbons. The thousands of features in Acidalia Planitia cited as analogous to terrestrial mud volcanoes clearly represent an important element in the sedimentary record of Mars. Their location, in the distal depocenter for massive Hesperian-age floods, suggests that they contain fine-grained sediments from a large catchment area in the martian highlands. We have proposed these features as a new class of exploration target that can provide access to minimally-altered material from significant depth. By analogy to terrestrial mud volcanoes, these features may also be excellent sites for the sampling martian organics and subsurface microbial life, if such exist or ever existed.

Allen, Carlton C.↗

Evaluating a New Homogeneous Total Ozone Climate Data Record from GOME/ERS-2, SCIAMACHY/Envisat, and GOME-2/MetOp-A

The European Space Agency's Ozone Climate Change Initiative (O3-CCI) project aims at producing and validating a number of high-quality ozone data products generated from different satellite sensors. For total ozone, the O3-CCI approach consists of minimizing sources of bias and systematic uncertainties by applying a common retrieval algorithm to all level 1 data sets, in order to enhance the consistency between the level 2 data sets from individual sensors. Here we present the evaluation of the total ozone products from the European sensors Global Ozone Monitoring Experiment (GOME)/ERS-2, SCIAMACHY/Envisat, and GOME-2/MetOp-A produced with the GOME-type Direct FITting (GODFIT) algorithm v3. Measurements from the three sensors span more than 16 years, from 1996 to 2012. In this work, we present the latest O3-CCI total ozone validation results using as reference ground-based measurements from Brewer and Dobson spectrophotometers archived at the World Ozone and UV Data Centre of the World Meteorological Organization as well as from UV-visible differential optical absorption spectroscopy (DOAS)/Système D′Analyse par Observations Zénithales (SAOZ) instruments from the Network for the Detection of Atmospheric Composition Change. In particular, we investigate possible dependencies in these new GODFIT v3 total ozone data sets with respect to latitude, season, solar zenith angle, and different cloud parameters, using the most adequate type of ground-based instrument. We show that these three O3-CCI total ozone data products behave very similarly and are less sensitive to instrumental degradation, mainly as a result of the new reflectance soft-calibration scheme. The mean bias to the ground-based observations is found to be within the 1 plus or minus 1 percent level for all three sensors while the near-zero decadal stability of the total ozone columns (TOCs) provided by the three European instruments falls well within the 1-3 percent requirement of the European Space Agency's Ozone Climate Change Initiative project.

Satellite sensors↗

On the Importance of Laboratory Astrophysics and Astrochemistry and Interdisciplinary Research: Two Success Stories

Here we present two examples that demonstrate how cross-disciplinary research projects, where experimentalists, modelers and observers work together to answer science questions, allow expertise to be shared and misconceptions or missing key elements to be tackled by looking at the problem from different perspectives. They also show how, by working in unison, the group can accomplish more than the sum of its parts by combining results into a higher-level understanding of the chemical processes taking place. The first project is a collaborative study between experimentalists, modelers and observers to1) produce laboratory analogs of cosmic grains and planetary aerosols (Titan, Pluto...) from different gas mixtures in cold astrophysically relevant conditions (<200 K); and 2) characterize them with scanning electron microscopy and visible-to-far-infrared spectroscopy in order to assess the impact of the precursors on their growth structure and optical properties. We can then produce and study analogs that are representative of different formation stages or environments, and provide their complex refractive indices to the scientific community. We will show how, by using these experimental optical constants of more representative analogs in radiative transfer and reflectance spectra models, better interpretations of (exo)planetary atmosphere- and surface observations are possible. The second project is an interdisciplinary study of the formation of benzene clouds in the atmosphere of Saturn’s largest moon, Titan. We will show how combining Earth and Planetary Science laboratory expertise, modeling and observations has led to providing to the scientific community, for the first time, experimental vapor pressures for benzene at cold temperatures(<200K) relevant to Titan’s atmospheric conditions. These have been used in microphysical models instead of the higher temperature extrapolations used previously, allowing a better match to observations.

Ella Sciamma-o'Brien↗

Habitability Potential of Martian Hydrothermal Systems Constrained from Exploration of a Magma-Sediment Hydrothermal System in the Colorado Plateau

Mars has a crust predominately composed of basalt, which displays wide-spread processes including volcanic hydrothermal systems and reference within. There is an abundance of evidence of previous low temperature hydrous alteration; however, finding evidence of high-temperature hydrothermal activity has been challenging. Therefore, we are investigating a mafic dike and the surrounding metamorphic contact zone to constrain how to find such systems on Mars and their habitability potential on Earth and by extension Mars. DC Dike (DCD) is in the Colorado Plateau, in south-central Utah, and intruded the Entrada formation Sandstone between 3.8 and 4.6 Ma. We chose Mars analog instrumentation to make our results directly applicable to those on Mars: Visible-Near Infrared reflectance spectroscopy (VNIR), X-Ray Diffraction (XRD), and Scanning Electron Microscope (SEM). 21 samples were analyzed with an Ore Express VNIR with wavelengths from 350-2500 nm. Bulk mineralogy is determined by using a Panalytical XRD including for clay fraction and soil separation analysis. Finally, samples are prepped as thin sections and will be analyzed using a SEM. All these techniques will be used to constrain: the mineralogy of the system, how the hydrothermal system cooled, the habitability of the cooling system, and how DCD relates to similar dikes in the area and on Mars. All of these results will then be compared to similar systems Mars, and if they too could have been habitable environments.

R. A. Slank↗

Oxidation of Glycolate in the Defense Waste Processing Facility (DWPF) Recycle Collection Tank - 20305

The Savannah River Site's Defense Waste Processing Facility (DWPF) operations are being upgraded with the introduction of the Nitric-Glycolic Flowsheet. Glycolic acid has been shown superior to formic acid as the reducing acid used during chemical processing. The new flowsheet improves or maintains necessary parameters such as 1) reduction of mercury, 2) adjustment of feed rheology and 3) adjustment of melter oxidation/reduction potential. Further, the potential for catalytic hydrogen generation in DWPF processing is virtually eliminated. DWPF process condensates are collected and returned to the SRS Concentration, Storage and Transfer Facilities (CSTF). The Recycle Collection Tank (RCT) collects off-gas condensate during chemical processing, vitrification, and other unit operations performed in DWPF and is the singular return vessel delivering recycle effluent back to CSTF. Each batch of recycle may contain a small amount of glycolate from chemical processing and melter off-gas condensates. To avoid potential flammability issues due to thermolysis of glycolate in the CSTF, chemical oxidation within the RCT has been investigated as an option for mitigating the transfer of glycolate. Sodium permanganate has been down-selected as the best option for oxidation of glycolate. Testing was performed using both 2-L and 22-L reactors (16,800:1 and 1,530:1 scale by volume) with non-radioactive waste simulants to approximate the expected RCT compositions. RCT simulants were evaluated at various process pH and temperature conditions. Also, RCT operations, namely the sequence of addition of corrosion inhibitors (NaOH and NaNO{sub 2}) versus a permanganate strike, were evaluated. Glycolate was introduced via a sludge simulant to mimic both expected entrainment and abnormal process foam-over conditions - the range being between 68 and 5100 mg/kg glycolate. Glycolate destruction was monitored by ion chromatography (IC). The corresponding manganese behavior was monitored in real-time using in situ ultraviolet-visible (UV-Vis) spectroscopy. RCT glycolate content can be reduced to below the IC detection limit within 90 minutes for all concentrations investigated. Ion Chromatography analysis revealed that under alkaline conditions, glycolate is primarily oxidized to oxalate with no significant formation of CO{sub 2} or carbonate, and nitrite is not oxidized to nitrate. Initially, complete oxidation of organics species and nitrite was assumed. Determination of the mechanistic chemical reaction has allowed the required amount of permanganate to be more accurately predicted and the total addition to be significantly reduced. UV-Vis measurements reveal that permanganate (Mn{sup 7+}) is reduced to manganate (Mn{sup 6+}) in the RCT. The oxidant stoichiometry is defined by using the initial permanganate to glycolate (P/G) molar ratio. At low initial glycolate concentration (68 and 140 mg/kg), the minimum required initial permanganate to glycolate (P/G) molar ratio was found to be 5-6. With high initial glycolate concentrations (5100 mg/kg) a lower (P/G) molar ratio of ∼2.5 was needed. The final portion of this effort supporting the nitric/glycolic flowsheet will be to test actual (fully radioactive) RCT samples as per the above simulant tests. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Insight into the Chemistry of PETN Under Shock Compression Through Ultrafast Broadband Mid-Infrared Absorption Spectroscopy

In this study, thin films of pentaerythritol tetranitrate (PETN) were shock compressed using the laser driven shock apparatus at Los Alamos National Laboratory (LANL). Two spectroscopic probes were available to this apparatus: visible white light transient absorption spectroscopy (VIS) from 400 to 700 nm and mid-infrared transient absorption spectroscopy (MIR) from 1150 to 3800 cm –1 . Important PETN vibrational modes are the symmetric and antisymmetric NO 2 stretches at 1280 and 1650 cm –1 , respectively, as well as CH stretches at ~2900 cm –1 . Shock strength was varied from approximately 3 to 55 GPa to span from the chemically unreactive regime to the regime in which fast chemical reaction took place on the 250 ps time scale of the measurements. VIS and MIR results suggest irreversible chemistry was induced in PETN at pressures above 30 GPa. At lower shock pressures, the spectroscopy showed minimal changes attributable to pressure induced effects. Under the higher-pressure reactive conditions, the frequency region at the antisymmetric NO 2 stretch mode had a significantly increased absorption while the region around the symmetric NO 2 stretch did not. No observable increased absorption occurred in the higher frequency regions where CH-, NH-, and OH- bond absorptions would be observed. A broad absorption appeared on the shoulder at the red-edge of the CO 2 vibrational band around 2200 cm –1 . In addition to the experiments, reactive molecular dynamics were carried out under equivalent shock conditions to correlate the evolution of the infrared spectrum to molecular processes. The simulations show results consistent to experiments up to 30 GPa but suggest that NO and NO 2 related features provided the strongest contributions to the shocked infrared changes. Proposed mechanisms for shocked PETN chemistry are analyzed as consistent or inconsistent with the data presented here. Our experimental data suggests C≡O or N 2 O bond formation, nitrite formation, and absence of significant hydroxyl or amine concentrations in the initial chemistry steps in PETN shocked above 30 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA’s Pandora SmallSat Mission: Simulating the Impact of Stellar Photospheric Heterogeneity and Its Correction

Stellar photospheric heterogeneity is a dominant astrophysical systematic impacting exoplanet transmission spectroscopy. NASA’s Pandora SmallSat Mission is designed to address this challenge through contemporaneous visible-band photometry and near-infrared spectroscopy of exoplanet host stars. Here, we present an end-to-end simulation study quantifying Pandora’s ability to infer stellar photospheric properties and correct stellar contamination using out-of-transit observations. We construct eight representative stellar activity scenarios and generate 160 simulated Pandora datasets, incorporating time-dependent stellar spectra, instrument response, and noise. Given accurate models, Bayesian retrievals of joint visible photometry (0.4–0.7 μm) and near-infrared spectroscopy (0.9–1.6 μm, R ≈ 120) recover photospheric temperatures with typical uncertainties of ≈30 K, with no significant bias. Models with two spectral components (i.e., a quiescent photosphere and spots) are strongly favored in 95% of cases; one-component models are preferred when true spot filling factors fall below a detection threshold of ≈0.3%. We propagate the true and inferred stellar parameters to compute true, inferred, and residual contamination signals under physically motivated spot geometries. For simple spot distributions, contamination signals of 10 2 –10 3 ppm are reduced to ≲10 ppm—well below Pandora’s expected transmission spectroscopy precision (30–100 ppm). For more complex spot distributions, geometric degeneracies limit deterministic corrections, leaving residual contamination at the 10 3 ppm level that must be mitigated using additional constraints, such as spot-crossing events and joint stellar–planetary retrievals of transmission spectra. These results define regimes in which stellar contamination can be corrected from stellar observations alone and show how Pandora stellar observations can identify cases where additional information is required.

Astronomy and AstroPhysics↗

Spectroscopy of Degenerate One-Dimensional Electrons in Carbon Nanotubes (Final Report)

The goal of this research program was to understand the fundamental properties of degenerate one-dimensional (1-D) electrons in single-wall carbon nanotubes (SWCNTs). SWCNTs provide an ideal 1-D environment in which to study many-body physics. Semiconducting SWCNTs exhibit rich optical spectra dominated by extremely stable 1-D excitons, whereas metallic SWCNTs contain massless 1-D carriers with ultralong mean-free paths. Despite the large number of electrical, optical, and magnetic studies of SWCNTs during the last two decades, most of the predicted exotic properties of interacting 1-D electrons have yet to be observed, and some reported experimental results remain highly controversial. Here, we report on our research projects for the last 16 years summarizing spectroscopy on SWCNTs using an arsenal of spectroscopic methods from the terahertz to the visible spectral range, including ultrafast optical spectroscopy and ultrahigh magnetic fields. These studies provided a wealth of new insights into the nature of strongly correlated carriers in the ultimate 1-D limit that will lead to novel nanodevice concepts and implementations. Particular emphasis was placed on dynamical 1-D phenomena in the terahertz, infrared, and optical frequency ranges. Because SWCNTs are direct-band-gap materials, they are one of the leading candidates to unify electronic and optical functions in nanoscale circuits and elucidate how electron correlations can affect and control finite-frequency phenomena in 1-D systems. As a result, we have published 78 research articles (Web of Science), including ten reviews and book volumes/chapters. Below, we highlight and summarize several accomplishments that provided new insights into the fundamental properties of1-D carriers, excitons, and phonons of SWCNTs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Raman spectroscopy of zirconium hydride

The characterization of zirconium hydride is important in the nuclear industry because of the hydrogen-induced embrittlement of Zircaloy cladding and its use as a neutron moderator. This paper introduces the use of Raman spectroscopy for the characterization of zirconium hydride. First-principles density functional theory (DFT) calculations were used to predict the Raman spectra of ζ-ZrH 0.5 , γ-ZrH, δ-ZrH 1.5 , δ-ZrH 1.66 , and ε-ZrH 2 with all their predicted symmetries; ζ-ZrH 0.5 (P3m1, R$\overline{3}$m, C2/m, Cm, Cmmm, and Pn$\overline{3}$m); γ-ZrH (P222, Ccce, and P4 2 /mmc); δ-ZrH 1.5 (P$\overline{4}$m2, P4 2 /mcm, Fmmm, Pn$\overline{3}$m, Ibam, P2/c, PI, and P4 2 /nnm); δ-ZrH 1.66 (Fm$\overline{3}$m); and ε-ZrH 2 (Fm$\overline{3}$m, R$\overline{3}$m, and I 4 /mmm). Two samples of Zircaloy-4 containing 133 wt ppm and 360 wt ppm hydrogen were characterized by Raman spectroscopy, showing two signal lines at 215 cm -1 and 1,187 cm -1 , which were assigned to the presence of δ-ZrH 1.66 . These signals had a good spatial correlation with visible hydride precipitates in Raman spectroscopy images. In conclusion, this work provides the basis for the characterization of all possible zirconium hydride compositions and structures using Raman spectroscopy.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗