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At least 775 records · Page 43

Infrared spectra of the Orgueil /C-1/ chondrite and serpentine minerals

Infrared spectroscopy of the Orgueil C-1 chondrite and polymorphs of serpentine was performed in order to further define the mineralogy of Orgueil. Spectra of the meteorite and a synthetic serpentine (Mg3(Si2O5)(OH)4) were obtained in the regions from 1400 to 200 and from 4000 to 2500 kayers using a double beam infrared spectrometer. The spectra of Orgueil are found to be incompatible with those of the chrysotile, antigorite and lizardite polymorphs of serpentine, indicating a very low abundance of these minerals in the meteorite. It is suggested that chamosite or minerals related to chamosites may prove to be compatible with the compositional, structural and infrared properties of Orgueil.

Zaikowski, A.↗

The Hyperluminous Infrared Quasar 3C 318 and Its Implications for Interpreting Sub-MM Detections of High-Redshift Radio Galaxies

We present near-infrared spectroscopy and imaging of the compact steep-spectrum radio source 3C 318 which shows it to be a quasar at redshift z = 1.574 (the z = 0.752 value previously reported is incorrect). 3C 318 is an IRAS, ISO and SCUBA source so its new redshift makes it the most intrinsically luminous far-infrared (FIR) source in the 3C catalogue (there is no evidence of strong gravitational lensing effects). Its bolometric luminosity greatly exceeds the 10(exp 13) solar luminosity level above which an object is said to be hyperluminous. Its spectral energy distribution (SED) requires that the quasar heats the dust responsible for the FIR flux, as is believed to be the case in other hyperluminous galaxies, and contributes (at the greater than 10% level) to the heating of the CIA dust responsible for the sub-mm emission. We cannot determine whether a starburst makes an important contribution to the heating of the coolest dust, so evidence for a high star-formation rate is circumstantial being based on the high dust, and hence gas, C-1 mass required by its sub-mm detection. We show that the current sub-mm and FIR data available for the highest-redshift radio galaxies are consistent with SEDs similar to that of 3C 318. This indicates that at least some of this population may be detected in the sub-mm because of dust heated by the quasar nucleus, and that interpreting sub-mm detection as evidence for very high (approx. less than 1000 solar mass/yr) star-formation rates may not always be valid. We show that the 3C318 quasar is slightly reddened (A(sub v) approx. = 0.5), the most likely cause of which is SMC-type dust in the host galaxy. If very distant radio galaxies are reddened in a similar way then we show that only slightly greater amounts of dust could obscure the quasars in these sources. We speculate that the low fraction of quasars amongst the very high redshift (z approx. greater than 3) objects in low-frequency radio-selected samples is the result of such obscuration. The highest-z objects might be preferentially obscured because like 3C318 they are inevitably observed very shortly after the jet-triggering event, or because their host galaxies are richer in dust and gas at earlier cosmic epochs, or because of some combination of these two effects.

Willott, Chris J.↗

Modification of Jupiter's Stratosphere Three Weeks After the 2009 Impact

Infrared spectroscopy sensitive to thermal emission from Jupiter's stratosphere reveals effects persisting 23 days after the impact of a body in late July 2009. Measurements obtained on 2009 August II UT at the impact latitude of 56 S (planetocentric), using the Goddard Heterodyne Instrument for Planetary Wind and Composition mounted on the NASA Infrared Telescope Facility, reveal increased ethane abundance and the effects of aerosol opacity. An interval of reduced thermal continuum emission at 11. 744 ~lm is measured ~60o-80 towards planetary east of the impact site, estimated to be at 3050 longitude (System Ill). Retrieved stratospheric ethane mole fraction in the near vicinity of the impact site is enhanced by up to -60% relative to quiescent regions at this latitude. Thermal continuum emission at the impact site, and somewhat west of it, is significantly enhanced in the same spectra that retrieve enhanced ethane mole fraction. Assuming that the enhanced continuum brightness near the impact site results from thermalized aerosol debris blocking contribution from the continuum formed in the upper troposphere and indicating the local temperature, then continuum emission by a haze layer can be approximated by an opaque surface inserted at the 45-60 mbar pressure level in the stratosphere in an unperturbed thermal profile, setting an upper limit on the pressure and therefore a lower limit on the altitude of the top of the impact debris at this time. The reduced continuum brightness east of the impact site can be modeled by an opaque surface near the cold tropopause, which is consistent with a lower altitude of ejecta/impactor-formed opacity or significantly lesser column density of opaque haze material. The physical extent of the observed region of reduced continuum implies a minimum average velocity of 21 m/s transporting material prograde (planetary east) from the impact.

Fast, Kelly E.↗

In-Situ Measurements of the Radiation Stability of Amino Acids at 15-140 K

We present new kinetics data on the radiolytic destruction of amino acids measured in situ with infrared spectroscopy. Samples were irradiated at 15, 100, and 140 K with D.8-MeV protons, and amino-acid decay was followed at each temperature with and without H2O present. Observed radiation products included CO2 and amines, consistent with amino-acid decarboxylation. The half-lives of glycine, alanine, and phenylalanine were estimated for various extraterrestrial environments. Infrared spectral changes demonstrated the conversion from the non-zwitterion structure NH2-CH2(R)-COOH at 15 K to the zwitterion structure +NH3-CH2(R)-COO- at 140 K for each amino acid studied.

Gerakines, Perry A.↗

Modification of Jupiter's Stratosphere Three Weeks After the 2009 Impact

Infrared spectroscopy sensitive to thermal emission from Jupiter's stratosphere reveals effects persisting 3 1/2 weeks after the impact of a body in late July 2009. Measurements obtained at 11.7 microns on 2009 August 11 UT at the impact latitude of 56degS (planetocentric), using the Goddard Heterodyne Instrument for Planetary Winds and Composition (HIPWAC) mounted on the NASA Infrared Telescope facility, reveal an interval of reduced thermal continuum emission that extends approx.60deg-80deg towards planetary East of the impact site, estimated to be at 305deg longitude (System III). Retrieved stratospheric ethane mole fraction in the near vicinity of the impact site is enhanced by up to approx.60% relative to quiescent regions at this latitude. Thermal continuum emission at the impact site, and somewhat west of it, is significantly enhanced in the same spectra that retrieve enhanced ethane mole fraction. Assuming that the enhanced continuum brightness near the impact site results from thermalized aerosol debris, then continuum emission by a haze layer can be approximated by an opaque surface inserted at the 45-60 mbar pressure level in the stratosphere in an unperturbed thermal profile, setting a lower limit on the altitude of the top of the ejecta cloud at this time. The reduced continuum brightness east of the impact site can be modeled by an opaque surface near the cold tropopause, consistent with a lower altitude of ejecta/impactor-formed opacity or significantly lesser column density of opaque haze material. The physical extent of the observed region of reduced continuum implies a minimum average velocity of 21 m/s transporting material prograde (East) from the impact. Spectra acquired further East, with quiescent characteristics, imply an average zonal velocity of less than 63 m/s.

Fast, Kelly Elizabeth↗

Infrared observations of the Jovian system from Voyager 2

As on Voyager 1, the infrared spectroscopy and radiometry instrument on Voyager 2 returned a large number of spectral and radiometric data on Jupiter and its satellites for varying conditions of latitude, longitude, local time, and phase and emission angles. The Voyager 2 average spectrum is slightly noisier than that from Voyager 1. The paper presents selected examples of results from the Voyager 2 infrared investigation, with particular reference to latitudinal variation of the abundance ratio of ethane to acetylene, atmospheric thermal structure, Jupiter's ring, and satellites.

Hanel, R.↗

Spontaneous crack healing in calcite reveals the influence of dynamic strain evolution and surface chemistry

The mechanics of fracture healing in calcite remain poorly constrained yet are fundamental to managing fluid transport in geothermal reservoirs and hydrocarbon systems. Here, we apply microfocused synchrotron Laue X-ray diffraction and infrared spectroscopy to investigate subcritical crack healing in a 1 mm-thick calcite crystal subjected to controlled loading in a double-torsion device. Over a 44-hour period following load removal, we map the evolution of residual strain fields surrounding the crack tip and observe a progressive increase in compressive strain perpendicular to the crack plane accompanied by infrared spectroscopic signatures that reveal enhanced accumulation of water at the healed interface. The correlation between strain evolution and surface chemistry suggests that spontaneous crack healing in calcite is driven by dynamic anelastic relaxation coupled with irreversible fluid-mineral interactions. These findings offer insight into time-dependent crack closure processes in carbonates and highlight the role of chemically-mediated plasticity in subsurface fracture evolution.

materials science↗

Fiber Optic Sensors for Health Monitoring of Morphing Airframes: Chemical Sensing Using Optical Fibers with Bragg Gratings - Part 2

Part 1 of this two part series described the fabrication and calibration of Bragg gratings written into a single mode optical fiber for use in strain and temperature monitoring. Part 2 of the series describes the use of identical fibers and additional multimode fibers, both with and without Bragg gratings, to perform near infrared spectroscopy. The demodulation system being developed at NASA Langley Research Center currently requires the use of a single mode optical fiber. Attempts to use this single mode fiber for spectroscopic analysis are problematic given its small core diameter, resulting in low signal intensity. Nonetheless, we have conducted a preliminary investigation using a single mode fiber in conjunction with an infrared spectrometer to obtain spectra of a high-performance epoxy resin system. Spectra were obtained using single mode fibers that contained Bragg gratings; however, the peaks of interest were barely discernible above the noise. The goal of this research is to provide a multipurpose sensor in a single optical fiber capable of measuring a variety of chemical and physical properties.

Wood, Karen↗

Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction

Abstract Chloroaluminate ionic liquids selectively transform (waste) polyolefins into gasoline-range alkanes through tandem cracking-alkylation at temperatures below 100 °C. Further improvement of this process necessitates a deep understanding of the nature of the catalytically active species and the correlated performance in the catalyzing critical reactions for the tandem polyolefin deconstruction with isoalkanes at low temperatures. Here, we address this requirement by determining the nuclearity of the chloroaluminate ions and their interactions with reaction intermediates, combining in situ 27 Al magic-angle spinning nuclear magnetic resonance spectroscopy, in situ Raman spectroscopy, Al K-edge X-ray absorption near edge structure spectroscopy, and catalytic activity measurement. Cracking and alkylation are facilitated by carbenium ions initiated by AlCl 3 - tert -butyl chloride (TBC) adducts, which are formed by the dissociation of Al 2 Cl 7 − in the presence of TBC. The carbenium ions activate the alkane polymer strands and advance the alkylation cycle through multiple hydride transfer reactions. In situ 1 H NMR and operando infrared spectroscopy demonstrate that the cracking and alkylation processes occur synchronously; alkenes formed during cracking are rapidly incorporated into the carbenium ion-mediated alkylation cycle. The conclusions are further supported by ab initio molecular dynamics simulations coupled with an enhanced sampling method, and model experiments using n-hexadecane as a feed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

FTIR quantification of industrial hydraulic fluids in perchloroethylene

The purpose of this summer research project was to investigate whether perchloroethylene can be used as a solvent for the quantitative analysis of industrial hydraulic fluids by infrared spectroscopy employing Beer's law. Standard calibration curves using carbon-hydrogen stretching (generic) and ester absorption peaks were prepared for a series of standard dilutions at low ppm levels of concentration of seven hydraulic fluids in perchloroethylene. The absorbance spectras were recorded with 1.5-10 mm fixed and variable path length sample cells made of potassium bromide. The results indicate that using ester infrared spectral peak, it is possible to detect about 20 ppm of the hydraulic fluid in perchloroethylene.

Mehta, Narinder K.↗

Charge Transfer and Spin Dynamics in a Zinc Porphyrin Donor Covalently Linked to One or Two Naphthalenediimide Acceptors

We report quantum coherence effects on charge transfer and spin dynamics in a system having two degenerate electron acceptors are studied using a zinc 5,10,15-tri(n-pentyI)-20-phenylporphyrin (ZnP) electron donor covalently linked to either one or two naphthalene-1,8:4,5-bis(dicarboximide) (NDI) electron acceptors using an anthracene (An) spacer, ZnP-An-NDI (1) and ZnP-An-NDI 2 (2), respectively. Following photoexcitation of 1 and 2 in toluene at 295 K, femtosecond transient absorption spectroscopy shows that the electron transfer (ET) rate constant for 2 is about three times larger than that of 1, which can be accounted for by the statistical nature of incoherent ET as well as the electron couplings for the charge separation reactions. In contrast, the rate constant for charge recombination (CR) of 1 is about 25% faster than that of 2. Using femtosecond transient infrared spectroscopy and theoretical analysis, we find that the electron on NDI 2 ∙- in 2 localizes onto one of the two NDIs prior to CR, thus precluding electronically coherent CR from NDI 2 ∙- . Conversely, CR in both 1 and 2 is spin coherent as indicated by the observation of a resonance in the 3* ZnP yield following CR as a function of applied magnetic field, giving spin-spin exchange interaction energies of 2J = 210 and 236 mT, respectively, where the line width of the resonance for 2 is greater than 1. These data show that while CR is a spin-coherent process, incoherent hopping of the electron between the two NDIs in 2, consistent with the lack of delocalization noted above, results in greater spin decoherence in 2 relative to 1.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The reddening and variability of XX Ophiuchi

We present polarization data on the XX Oph system which suggest that the interstellar extinction to this object has been overestimated in the past: our data imply A(V) = 1.6 mag. Our photometry and infrared spectroscopy suggest a spectral class of M7III for the late component, and a BOV companion that ionizes the wind of the cool component. XX Oph seems more like a Zeta Aur/VV Cep system than a 'symbiotic object'. The photometric variability of XX Oph seems to have a number of causes, ranging from shell-type variability in the U band to variations in the M component in the infrared.

Evans, A.↗

New Candidate Extreme T Subdwarfs from the Backyard Worlds: Planet 9 Citizen Science Project

Schneider et al. presented the discovery of WISEA J041451.67−585456.7 and WISEA J181006.18−101000.5, which appear to be the first examples of extreme T-type subdwarfs (esdTs; metallicity ≤−1 dex, T(eff) ≲ 1400 K). Here, we present new discoveries and follow-up of three T-type subdwarf candidates, with an eye toward expanding the sample of such objects with very low metallicity and extraordinarily high kinematics, properties that suggest membership in the Galactic halo. Keck/NIRES near-infrared spectroscopy of WISEA J155349.96+693355.2, a fast-moving object discovered by the Backyard Worlds: Planet 9 citizen science project, confirms that it is a mid-T subdwarf. With H(W2) = 22.3 mag, WISEA J155349.96+693355.2 has the largest W2 reduced proper motion among all spectroscopically confirmed L and T subdwarfs, suggesting that it may be kinematically extreme. Nevertheless, our modeling of the WISEA J155349.96+693355.2 near-infrared spectrum indicates that its metallicity is only mildly subsolar. In analyzing the J155349.96+693355.2 spectrum, we present a new grid of low-temperature, low-metallicity model atmosphere spectra. We also present the discoveries of two new esdT candidates, CWISE J073844.52−664334.6 and CWISE J221706.28−145437.6, based on their large motions and colors similar to those of the two known esdT objects. Finding more esdT examples is a critical step toward mapping out the spectral sequence and observational properties of this newly identified population.

Aaron M. Meisner↗

Infrared fine-structure line diagnostics of shrouded active galactic nuclei

Far-infrared spectroscopy of celestial objects will improve dramatically in the coming decade, allowing astronomers to use fine-structure line emission to probe photoionized regions obscured in the optical band by thick clouds of dust. The ultraluminous far-IR galaxies revealed by IRAS, quasar-like in luminosity but smothered in molecular gas, probably conceal either immense starbursts or luminous active nuclei. In both scenarios, these objects ought to produce copious infrared fine-structure emission with several lines comparable to H(beta) in luminosity. This paper shows how these lines, if detected, can be used to determine the electron densities and far-IR obscurations of shrouded photoionized regions and to constrain the shape and ionization parameter of the ionizing spectra. The presence of (Ne V) emission in particular will distinguish shrouded AGN's from shrouded starbursts. Since all active galaxies photoionize at least some surrounding material, these diagnostics can also be applied to active galaxies in general and will aid in studying how an active nucleus interacts with the interstellar medium of its host galaxy.

Voit, G. M.↗

Microfibril orientation and compositional heterogeneity in fiber and vessel cell walls of poplar xylem studied by AFM-IR and SFG spectroscopy

Understanding the structural organization of cellulose microfibrils (CMFs) within individual plant cell walls is essential for connecting cell wall architecture to its mechanical and physiological functions. However, due to the complex hierarchical structure and nanoscale heterogeneity of cell walls, it remains technically challenging to resolve detailed compositional and orientational information at subcellular levels of individual cell walls. This study investigates the internal 3D structure, chemical composition, and sublayer organization of fiber and vessel cell walls in the xylem tissue of a two-year-old field-grown hybrid poplar tree (Populus alba × P. glandulosa) using photothermal atomic force microscopy coupled with infrared spectroscopy (AFM-IR) and sum frequency generation (SFG) hyperspectral microscopy. AFM-IR provided nanoscale chemical imaging, revealing localized compositional heterogeneity, including variations between adjacent cell walls and transitional layers beyond the traditional S1, S2, and S3 sublayers. SFG microscopy revealed that CMFs in fiber walls are highly aligned along the stem axis, consistent with their role in mechanical support, while vessel cell walls exhibited slightly tilted CMFs, reflecting their function in hydraulic transport. Together, these results offer new insights into cell-type-specific CMF organization and compositional gradients in hybrid poplar xylem. These findings highlight the structural and chemical complexity of secondary cell walls in woody plants and demonstrate the value of AFM-IR and SFG spectroscopy in elucidating plant cell wall architecture.

60 APPLIED LIFE SCIENCES↗

Kinetics of the ClO + NO2 + M reaction

The ClO + NO2 + M reaction has been studied with two techniques: Fourier transform infrared spectroscopy of the products, and flash photolysis-ultraviolet absorption to monitor the decay of ClO in excess NO2. The measured third-order rate constant is 1.5 x 10 to the -31st cm to the 6th/molecule-squared per sec at 298 K with M = N2, in good agreement with previous literature values, but the rate constant appears to decrease by up to a factor of three in the presence of increasing amounts of OClO. For the infrared studies a stoichiometric mixture of ClO and NO2 was prepared in a flow system by mixing NO with OClO; at least as much NO2 as ClONO2 was produced under a variety of experimental conditions. These two sets of results are incompatible with the assumption made in previous kinetic studies that ClONO2 is the only recombination product; other isomers such as OClONO or ClOONO are likely to be formed three to four times faster. These results imply that potential stratospheric ozone depletion due to chlorofluoromethanes may be even larger than previously thought.

Molina, M. J.↗

Detection Opportunity for Aromatic Signature in Titan's Aerosols in the 4.1-5.3 μm Range

The Cassini/Huygens mission provided new insights on the chemistry of the upper atmosphere of Titan. The presence of large molecules and ions (>100's of amu) detected by Cassini at high altitude was not expected, and questions the original assumptions regarding the aerosol formation pathways. From recent laboratory studies, it has been shown that the inclusion of trace amounts of aromatic species drastically impacts the chemistry of aerosol formation and induces observable changes in the properties of the aerosols. In this Letter we focus on the effect of one of the simplest nitrogenous aromatics, pyridine (C5H5N), on the infrared signature of Titan's aerosol analogs. We introduce initial gas mixtures of (i) N2–C5H5N (100%/250 ppm), (ii) N2–CH4–C5H5N (99%/1%/250 ppm), and (iii) N2–CH4 (99%/1%) in a cold plasma discharge. The material produced, herein called tholins, is then analyzed by mid-infrared spectroscopy. When adding pyridine in the discharge, the tholins produced present an aromatic signature in the 4.1–5.3 μm (1850–2450 cm−1) spectral region, attributed to overtones of aromatic C–H out-of-plane bending vibrations. We also observe a spectral shift of the nitrile and iso-nitrile absorption band with the inclusion of pyridine in the gas mixture. These results could help to investigate the data obtained at Titan by the Cassini/Visual and Infrared Mapping Spectrometer (VIMS) instrument in the 1–5 μm infrared window.

Mathé, Christophe↗