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At least 433 records · Page 24

BASS. XXIX. The Near-infrared View of the Broad-line Region (BLR): The Effects of Obscuration in BLR Characterization

Virial black hole (BH) mass (M BH ) determination directly involves knowing the broad-line region (BLR) clouds' velocity distribution, their distance from the central supermassive BH (R BLR ), and the virial factor (f). Understanding whether biases arise in M BH estimation with increasing obscuration is possible only by studying a large (N > 100) statistical sample of obscuration-unbiased (hard) X-ray-selected active galactic nuclei (AGNs) in the rest-frame near-infrared (0.8–2.5 μm) since it penetrates deeper into the BLR than the optical. We present a detailed analysis of 65 local Burst Alert Telescope (BAT) selected Seyfert galaxies observed with Magellan/FIRE. Adding these to the near-infrared BAT AGN spectroscopic survey database, we study a total of 314 unique near-infrared spectra. While the FWHMs of Hα and near-infrared broad lines (He i, Paβ, Paα) remain unbiased to either BLR extinction or X-ray obscuration, the Hα broad-line luminosity is suppressed when N H ≳ 10 21 cm –2 , systematically underestimating M BH by 0.23–0.46 dex. Near-infrared line luminosities should be preferred to Hα until N H < 10 22 cm –2 , while at higher obscuration a less-biased R BLR proxy should be adopted. We estimate f for Seyfert 1 and 2 using two obscuration-unbiased M BH measurements, i.e., the stellar velocity dispersion and a BH mass prescription based on near-infrared and X-ray, and find that the virial factors do not depend on the redshift or obscuration, but some broad lines show a mild anticorrelation with M BH . Furthermore, our results show the critical impact obscuration can have on BLR characterization and the importance of the near-infrared and X-rays for a less-biased view of the BLR.

79 ASTRONOMY AND ASTROPHYSICS↗

Climate Change Observation Accuracy: Requirements and Economic Value

This presentation will summarize a new quantitative approach to determining the required accuracy for climate change observations. Using this metric, most current global satellite observations struggle to meet this accuracy level. CLARREO (Climate Absolute Radiance and Refractivity Observatory) is a new satellite mission designed to resolve this challenge is by achieving advances of a factor of 10 for reflected solar spectra and a factor of 3 to 5 for thermal infrared spectra. The CLARREO spectrometers can serve as SI traceable benchmarks for the Global Satellite Intercalibration System (GSICS) and greatly improve the utility of a wide range of LEO and GEO infrared and reflected solar satellite sensors for climate change observations (e.g. CERES, MODIS, VIIIRS, CrIS, IASI, Landsat, etc). A CLARREO Pathfinder mission for flight on the International Space Station is included in the U.S. Presidentâ€"TM"s fiscal year 2016 budget, with launch in 2019 or 2020. Providing more accurate decadal change trends can in turn lead to more rapid narrowing of key climate science uncertainties such as cloud feedback and climate sensitivity. A new study has been carried out to quantify the economic benefits of such an advance and concludes that the economic value is ~ $9 Trillion U.S. dollars. The new value includes the cost of carbon emissions reductions.

Wielicki, Bruce↗

Radioactive Transfer Models for Saturn and Titan

The infrared spectra of the earth's atmosphere and planetary atmospheres contains information about atmospheric physical and chemical processes. Atmospheric molecular constituents absorb and emit infrared radiation by rotational and vibrational transition. Observed spectra exhibit characteristic features in the electromagnetic spectrum region. Observation of the absorption or thermal emission spectra may be obtained with space-borne high resolution infrared spectrometers in the 10-5000 cm(exp -1) (2-1000 micro-m) spectral region. Information about the atmospheric thermal structure, composition, and the chemical and physical processes of the observed spectral was accomplished. A preliminary version of a P-T retrieval algorithm for Saturn using all three modes for temperature inversion, e.g., CH4-limb, and H2-nadir spectra was completed and tested for accuracy. Radiative transfer and inversion programs were studied and analyzed for applications to infrared limb thermal emission observations of Saturn and Titan from the Cassini Orbiter, as well as Earth's atmosphere. Analysis and modification of the existing radiative transfer and inversion programs for Earth and planetary atmospheres are being made. Data analysis and retrieval of information form the observations by digital calculations were carried out at UAH and MSFC computer. The working program for generating and reading g-k arrays for using the c-k arrays via the c-k method for radiative transfer calculations for desired atmospheric and instrumental parameters was completed, tested for accuracy and resides at the MSFC computer.

Wu, S. T.↗

TPSAS-NF1676L-20735-DND

Higher than normal accuracy is required to rigorously observe decadal climate change. But what level is needed? How can this be quantified? This presentation will summarize a new more rigorous and quantitative approach to determining the required accuracy for climate change observations (Wielicki et al., 2013, BAMS). Most current global satellite observations cannot meet this accuracy level. A proposed new satellite mission to resolve this challenge is CLARREO (Climate Absolute Radiance and Refractivity Observatory). CLARREO is designed to achieve advances of a factor of 10 for reflected solar spectra and a factor of 3 to 5 for thermal infrared spectra (Wielicki et al., Oct. 2013 BAMS). The CLARREO spectrometers are designed to serve as SI traceable benchmarks for the Global Satellite Intercalibration System (GSICS) and to greatly improve the utility of a wide range of LEO and GEO infrared and reflected solar passive satellite sensors for climate change observations (e.g. CERES, MODIS, VIIIRS, CrIS, IASI, Landsat, SPOT, etc). Providing more accurate decadal change trends can in turn lead to more rapid narrowing of key climate science uncertainties such as cloud feedback and climate sensitivity. A study has been carried out to quantify the economic benefits of such an advance as part of a rigorous and complete climate observing system. The study concludes that the economic value is ~ $12 Trillion U.S. dollars in Net Present Value for a nominal discount rate of 3% (Cooke et al. 2013, J. Env. Sys. Dec.). A brief summary of these two studies and their implications for the future of climate science will be presented.

Bruce Wielicki↗

High resolution infrared absorptivities for gaseous chlorine nitrate

High resolution infrared absorptivities of chlorine nitrate (ClONO2) are required in order to quantitatively evaluate, by examination of infrared spectra obtained recently from balloon-borne spectrometers, the possible occurrence of this compound in the stratosphere. In the present study, infrared absorptivities for four absorption bands of gaseous ClONO2 have been measured at 0.0625 per cm spectral resolution with a Fourier transform infrared (FT-IR) system. Spectra were obtained at two pressures (0.05 and 1.05 torr) of pure ClONO2 and with 125 torr of N2 added to a 0.50 torr sample. Absorptivities for a range of spectral resolutions (0.0625, 0.125, 0.25 and 0.50 per cm) have been calculated from the data.

Graham, R. A.↗

Infrared diffuse reflectance spectra of carbonaceous chondrites: Amount of hydrous minerals

Infrared diffuse reflectance spectra (2.53-25 microns) of some carbonaceous (C) chondrites were measured. The integrated intensity of the absorption bands near 3 microns caused by hydrous minerals were compared with the modal content of hydrous minerals for the meteorites. The CM and CI chondrites show larger values of the intergated intensity than those of the unique C chondrites Y82162, Y86720 and B7904, suggesting that the amount of hydrous minerals in the CM and CI chondrites is larger, which supports the contention that hydrous minerals were dehydrated by thermal metamorphism in the unique chondrites. Orgueil (CI) has the largest value of the integrated intensity among the C chondrites we measured and shows a sharp absorption band at 3685/cm (2.71 microns) that is not seen in the spectra of the CM chondrites. There is an excellent correlation between the observed hydrogen content in C chondrites and the integrated intensity. The CM chondrites show a wide variation in the strength of absorption bands at 1470/cm (6.8 microns), despite the similarity in absorption features near 3 micron for all CM chondites. The 1470/cm band could be due to the presence of some hydrocarbons but may also be a result of terrestrial alteration processes.

Miyamoto, M.↗

Computational and Experimental Mechanistic Insights into the Ethanol-to-Butanol Upgrading Reaction over MgO

The mechanism of ethanol upgrading to higher products is still under debate, especially regarding intermediate species and hydrogenation and dehydrogenation steps. In this work, we conducted a combined theoretical and experimental approach to contribute to this discussion. For such, detailed electronic structure density functional theory calculations (aiming at probing density of states, infrared spectra, geometric parameters, charge densities, and reaction energetics) and diffuse reflectance infrared Fourier transform spectroscopy experiments were carried out revealing the relevance of an appropriate combination of reactive surface sites to support the formation of several intermediates that are formed in the C-C coupling over MgO. The roles of Mg and O sites were also studied under an electronic perspective and different geometrical arrangements. We found that a kink configuration was the most adequate for ethanol to 1-butanol upgrading. Our calculations also gave us arguments to propose distinct reaction routes, whose mutual predominance would depend upon reaction temperature. At temperatures up to 573 K, the so-called β-route, which goes through scission of a Cβ-H bond and formation of an oxametallacycle-like intermediate, would dominate the coupling, whereas at higher temperatures, up to 673 K, a more usual Guerbet mechanism, via an aldol coupling step and then consecutive hydrogenations, would be expected. Here, the theoretical conclusions were followed by a careful experimental strategy using sequential experimental planning techniques in order to estimate accurate parameters with the lowest possible experimental load. Information from these different sources were coupled to develop a mathematical model for the rate of the ethanol upgrading reaction, using a Langmuir-Hinshelwood-Hougen-Watson approach. The developed and statistically validated model adequately described the experimental data at 673 K and 1.1 bar total pressure for ethanol partial pressures in the range from 0 to 20 kPa.

09 BIOMASS FUELS↗

The 4 micron spectra of compact infrared sources

High resolution 5 arcsec spectra in the 4 micron region are presented of the central 5 arcsec of the compact near infrared sources K3-50, W51-IRS2 East, and G333.6-0.2. From measured Br-alpha/Pf-beta line ratios and previously published infrared and radio maps, it is concluded that standard recombination theory fails to explain our observations in at least two cases. It is demonstrated that the data are consistent with thermal excitation of the hydrogen lines in strong stellar winds. The Pf-beta Hu-epsilon line ratio, which is completely insensitive to differential extinction, confirms the need for the stellar wind model for the core of G333.6-0.2. From the (K III) line it is estimated that the potassium abundance in G333.6-0.2 is at least equal to the solar value, and possibly enhanced by a factor up to 10.

Hofmann, R.↗

Toward Mapping the Detailed Density Structure of Classical Be Circumstellar Disks

We present the preliminary results of near contemporaneous optical and infrared spectroscopic observations of select classical Be stars. We find strong evidence of oppositely oriented V/R hydrogen line profiles in the optical versus infrared spectra of zeta Tau, and briefly discuss how sustained contemporaneous optical and infrared spectroscopic observations might enable us to trace the detailed density structure of classical Be circumstellar disks.

Wisniewski, J. P.↗

Detection and Signal Processing for Near-Field Nanoscale Fourier Transform Infrared Spectroscopy

Researchers from a broad spectrum of scientific and engineering disciplines are increasingly using scattering-type near-field infrared spectroscopic techniques to characterize materials non-destructively with nanoscale spatial resolution. However, a sub-optimal understanding of a technique's implementation can complicate data interpretation and act as a barrier to entering the field. Here the key detection and processing steps involved in producing scattering-type near-field nanoscale Fourier transform infrared spectra (nano-FTIR) are outlined. The self-contained mathematical and experimental work derives and explains: i) how normalized complex-valued nano-FTIR spectra are generated, ii) why the real and imaginary components of spectra qualitatively relate to dispersion and absorption respectively, iii) a new and generally valid equation for spectra which can be used as a springboard for additional modeling of the scattering processes, and iv) an algebraic expression that can be used to extract an approximation to the sample's local extinction coefficient from nano-FTIR. The algebraic model for weak oscillators is validated with nano-FTIR and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra on samples of polystyrene and Kapton and further provides a pedagogical pathway to cementing some of the technique's key qualitative attributes.

36 MATERIALS SCIENCE↗

The spectral properties of interplanetary dust particles

The observed spectral and mineralogical properties of interplanetary dust particles (IDP) allows the conclusion that: (1) the majority of IDP infrared spectra are dominated by olivine, pyroxene, or layer lattice silicate minerals, (2) to the first order the emission spectra of comets Halley and Kohoutek can be matched by mixtures of these IDP infrared types, implying that comets contain mixtures of these different crystalline silicates and may vary from comet to comet and perhaps even within a single comet, (3) do not expect to observe a single 20 micron feature in cometary spectra, (4) carbonaceous materials dominate the visible spectra properties of the IDPs even though the mass in these particles consists primarily of silicates, and (5) the particle characteristics summarized need to be properly accounted for in future cometary emission models.

Sandford, Scott A.↗

The spectral properties of collected interplanetary dust particles

The observed spectral and mineralogical properties of interplanetary dust particles (IDP) allows the conclusion that: (1) the majority of IDP infrared spectra are dominated by olivine, pyroxene, or layer lattice silicate minerals, (2) to the first order the emission spectra of comets Halley and Kohoutek can be matched by mixtures of these IDP infrared types, implying that comets contain mixtures of these different crystalline silicates and may vary from comet to comet and perhaps even within a single comet, (3) do not expect to observe a single 20 micron feature in cometary spectra, (4) carbonaceous materials dominate the visible spectra properties of the IDPs even though the mass in these particles consists primarily of silicates, and (5) the particle characteristics summarized need to be properly accounted for in future cometary emission models.

Sandford, S. A.↗

H 2 O-assisted O 2 reduction by H 2 on Pt and PtAu bimetallic nanoparticles: Influences of composition and reactant coverages on kinetic regimes, rates, and selectivities

Hydrogen peroxide (H 2 O 2 ) can replace hazardous oxidants in industrial processes but is currently too expensive for many such applications. While direct synthesis of H 2 O 2 (H 2 + O 2 → H 2 O 2 ) may reduce costs in comparison to incumbent technology, current catalysts lack the requisite stability and selectivity. Here, we examine the direct synthesis of H 2 O 2 on bimetallic Pt 1 Au x (0 ≤ x ≤ 230) and Pt catalysts at steady-state in pure water and relate kinetic parameters for H 2 O 2 and H 2 O formation to possible active site structures informed by complementary characterization methods. X-ray photoelectron spectra show significant Pt surface enrichment compared to the bulk composition. Analysis of infrared spectra of mixed monolayers of 12 CO* and 13 CO* indicate that Pt and Au form substitutional surface alloys. The Pt 1 Au x nanoparticles with the greatest mole fractions of Au predominantly expose Pt monomers (i.e., isolated Pt atoms), yet Pt atoms exposed upon all these nanoparticles possess electronic structures distinct from bulk Pt. Despite these differences, rate measurements are consistent with product formation through proton-electron transfer pathways for all Pt 1 Au x catalysts. In situ XAS indicate that Pt remains metallic during H 2 O 2 synthesis. Under the most oxidizing conditions, selectivities toward H 2 O 2 increase strongly with the Au to Pt ratio from 2% for monometallic Pt to 85% for Pt 1 Au 170 . However, selectivities are similar among all catalysts within reducing conditions. Comparisons of apparent activation enthalpies for the formation of H 2 O 2 and H 2 O across these catalysts and the range of conditions suggest that Pt monomers within Au provide the greatest selectivities for H 2 O 2 formation, because these active sites present high barriers for O-O bond rupture. Further, selectivities decrease with increasing ratios of H 2 to O 2 pressures, because Pt atoms aggregate and form oligomers that readily dissociate dioxygen intermediates. The combined use of spectroscopy, kinetics, and concepts employed in reaching these conclusions take inspiration from the legacy of Prof. Michel Boudart, and specifically his elegant methods for interrogating bimetallic catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The thermal structure and dynamics of the atmosphere of Venus between 70 and 90 km from the Galileo-NIMS spectra

An analysis of thermal profiles and dynamics over a wide range of latitudes for the venusian atmosphere between 70 and 90 km is presented based on high spatial resolution infrared spectra of the night side obtained by the near infrared mapping spectrometer (NIMS) experiment during the Galileo-Venus encounter in February 1990. Using the 4.3-micrometer CO2 absorption band, the temperature profile is retrieved in the 75- to 91-km altitude region over a latitudinal range of -59 deg to +64 deg. Compared to earlier observations from the Pioneer Venus mission, the temperature at 91 km is about 10 K higher and between 74 and 83 km about 3.6 K colder. An equator to pole warming at constant pressure levels is found and implications for the zonal wind profiles are drawn under the assumption that the atmosphere is in cyclostrophic balance in the region of 70 to 90 km. The results are in correspondence with direct wind measurements from ground-based observations at 95 km and 105 km altitude.

Roos-Serote, M.↗

The mid-infrared spectrum of the carbon star HD 38218 and its possible relation to polycyclic aromatic hydrocarbons

The mid-infrared spectra of carbon giant stars with hot companions are investigated in order to search for infrared emission bands from polycyclic aromatic hydrocarbons (PAH) in the envelopes of the C giants. A strong 8-micron emission band found in TU Tau = HD 38218 is attributed to the binary A star companion. It is argued that if the 8-micron feature in HD 38218 arises from PAHs, they seem to be important constituents of the C-giant shell, and they might be large compared with some interstellar PAHs. It is suggested that because no other IR spectra of C giants show clear PAH features, the greater flux of hard radiation in the binary HD 38218 seems likely to be responsible for the 8-micron feature and for its absence in many other C giants. Thus, PAHs could be present in the same amounts relative to SiC grains in the shells of similar single C giants, and the formation of carbonaceous grains could proceed through the formation of PAHs in C giant shells.

Buss, Richard H., Jr.↗