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At least 199 records · Page 11

Characterization of the Effects of Precursor Mineralogy on Hematite Spectra: Application to Martian Hematite Mineralization

The Thermal Emission Spectrometer (TES) instrument aboard Mars Global Surveyor discovered several isolated deposits of gray, crystalline hematite in Sinus Meridiani, Aram Chaos, and Valles Marineris. A variety of formation mechanisms has been proposed for the martian hematite deposits, including aqueous and nonaqueous processes. Comparison of the average Sinus Meridiani hematite spectrum measured by TES to laboratory emissivity spectra for a variety of naturally occurring hematites shows small but potentially important differences. In particular, the emissivity minimum at 300 and 445/cm in the Sinus Meridiani (SM) spectrum is displaced 10-25/cm to lower frequencies compared to some natural hematite samples. In addition, these bands in the TES data are narrower than the broad bands seen in many natural hematite spectra. These differences may imply that the natural variability of hematite spectra has not been fully characterized, especially with respect to the reaction pathway (precursor mineralogy and temperature of hematite formation) and crystal morphology. Here, we describe the thermal infrared spectral characteristics of several series of synthetic hematite samples derived by direct precipitation, dehydroxylation of fine-grained goethite and the oxidation of magnetite. Several natural hematite sample spectra are also presented for comparison. Transmission electron microscopy (TEM) and Mossbauer spectral analyses of selected samples were performed in order to help determine the causes of the changes seen in the infrared spectra.

Glotch, Timothy D.↗

Tumor‐pH‐value responsive non‐peripheral substituted phthalocyanines: Synthesis, investigation of photophysical and photochemical properties

Cancer is one of the diseases with the highest mortality rate worldwide. Although PDT has recently produced encouraging outcomes, there are still many areas that need to be improved. The first of these is the negative consequences faced by patients treated with the PDT method when exposed to sunlight. For this reason, a new PDT method has been developed in recent years, and it is aimed at using photosensitizer molecules that can be active in acidic conditions. Since the pH values of tumor tissues are more acidic than normal tissues, preparing molecules that act effectively in acidic conditions will allow for more effective results in treating cancer with PDT. In this context, within the scope of this study, 3‐(4‐propionylphenoxy)phthalonitrile ( 1 ) and its non‐peripheral tetra‐substituted phthalocyanine derivatives [( 2 ), ( 3 ), and ( 4 )] were prepared. With these phthalocyanine derivatives, the novel compounds ( 5 ), ( 6 ), and ( 7 ) were synthesized for the first time. The aggregation tendencies of newly synthesized phthalocyanines ( 5–7 ) were investigated in solvent media. The effects of pH changes upon UV–Vis and fluorescence spectra were performed. The electronic and emission spectra of synthesized phthalocyanine derivatives are highly sensitive to pH changes. Formation constant (Log K) values of mono‐ and di‐protonated phthalocyanine forms were calculated by the Henderson–Hasselback equation. The mono‐ and di‐protonated species' equilibrium constants (logK 1 and logK 2 ) were calculated as ~5.0. This value may be promising for pH‐sensitizing photosensitizers. Also, the photophysical and photochemical properties of synthesized metallophthalocyanine derivatives ( 2 ) and ( 5 ) were studied at different pH values. The singlet oxygen quantum yield of ( 2 ) and ( 5 ) was calculated to be 0.78 and 0.81 in DMSO, respectively. When pH = 6.4, that is, tumor‐pH‐values, this value for ( 5 ) has increased to 0.92. The newly synthesized phthalocyanines are suitable photosensitizers for PDT applications, especially with high singlet oxygen quantum yield at pH 6.4.

Genc Bilgicli, Hayriye↗

High-Resolution Studies of Extreme-Ultraviolet Emission from CO by Electron Impact

We report a high-resolution study [0.0036 nm full width at half maximum (FWHM) of electron-impact-induced emission spectra of CO 1t 30, 75 and 100 eV electron-impact energies. The spectral features were acquired in optically thin conditions, and represent the highest resolution single-scattering emission spectrum of CO induced by electron impact yet available.

high-resolution↗

Development of a laser fluorosensor for airborne surveying of the aquatic environment

A field based laser fluorosensor, employing a pulsed nitrogen laser and telescope photomultiplier detector system, has been successfully tested at night from a cliff top site overlooking Lake Ontario providing target ranges greater than 274 meters. Remotely sensed spectra and amplitude changes in the fluorescence emission of natural waters have shown potential as a water quality indicator. In this connection, a convenient internal reference standard with which to gauge the amplitude of the fluorescence signal is realized in the form of the concurrent water Raman emission. Remote measurements of oil fluorescence emission spectra suggest that airborne laser fluorosensors are capable of detecting and characterizing the oil in a given slick and that environmental aging of these slicks does not significantly alter their fluorescence emission signature.

Bristow, M. P. F.↗

Lasing efficiency of krypton ions in the (8 – 14)-nm band upon pulsed laser excitation

The emission spectra of krypton plasma in the range of 8 – 14 nm upon excitation of a pulsed gas jet by 1.06-mm Nd : YAG laser radiation with a pulse energy of 0.85 J, pulse duration of 5.2 ns, and repetition rate of 10 Hz are investigated. The krypton emission spectrum is a wide (8 – 14 nm) band, peaking at 10.3 nm, which is formed by a series of much narrower lines. The observed lines are identified, and the fraction of laser pulse energy converted into the (8 – 14)-nm emission band and emitted into half-space (2π sr) is determined. The maximum conversion efficiency is found to be 21 %. The expected throughputs of lithographic systems with sources based on Sn, Xe, and Kr ions for different wavelengths, corresponding to the emission peaks of ions of these materials, are compared. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

The hemispheric reflectance of a plane water surface for atmospheric radiation

The hemispheric reflectance of a plane water surface is computed for clear sky and low overcast sky emission spectra. The gross features of clear sky emission are described by a model that has a deficiency of emission in the 8- to 13-micron band. The deficiency is most pronounced in the zenith but disappears as the zenith angle approaches the horizon. The radiation from a low overcast sky is assumed to be blackbody. The computation is made using Fresnel formulas for a conducting medium. The hemispheric reflectance for clear sky radiation is found to be approximately 0.018 higher than the overcast (blackbody) value, which ranged from 0.113 to 0.107 for atmospheric temperatures ranging from 273 to 313 K, respectively.

Boudreau, R. D.↗

High-resolution Spectra of Earth-like Planets Orbiting Red Giant Host Stars

In the near future we will have ground- and space-based telescopes that are designed to observe and characterize Earth-like planets. While attention is focused on exoplanets orbiting main-sequence stars, more than 150 exoplanets have already been detected orbiting red giants, opening the intriguing question of what rocky worlds orbiting in the habitable zone (HZ) of red giants would be like and how to characterize them. We present a high-resolution spectral database of reflection and emission spectra for nominal Earth-like planets orbiting in the red giant HZ from the visible to infrared (0.4–20 μm) for planets orbiting at the Earth-equivalent distance. We also show the change of such planetary spectra through the evolution of their red giant hosts. While the luminosity of the host increases the contrast ratio between star and planet, the increased orbital distance of the HZ for red giant hosts relaxes the light suppression requirements close to the star, which could make such planets interesting targets to characterize and search for signs of life, if new coronagraph designs with higher suppression at larger orbital separations could be developed. We assess the feasibility of characterizing atmospheric features including biosignatures for such planets with the proposed mission concept Large UV/Optical/IR Surveyor (LUVOIR).

79 ASTRONOMY AND ASTROPHYSICS↗

A Quantum Band Model of the nu3 Fundamental of Methanol (CH3OH) and Its Application to Fluorcescence Spectra of Comets

Methanol (CH3OH) radiates efficiently at infrared wavelengths, dominating the C-H stretching region in comets, yet inadequate quantum-mechanical models have imposed limits on the practical use of its emission spectra. Accordingly, we constructed a new line-by-line model for the 3 fundamental band of methanol at 2844 / cm (3.52 micron) and applied it to interpret cometary fluorescence spectra. The new model permits accurate synthesis of line-by-line spectra for a wide range of rotational temperatures, ranging from 10 K to more than 400 K.We validated the model by comparing simulations of CH3OH fluorescent emission with measured spectra of three comets (C/2001 A2 LINEAR, C/2004 Q2 Machholz and 8P/Tuttle) acquired with high-resolution infrared spectrometers at high-altitude sites. The new model accurately describes the complex emission spectrum of the nu3 band, providing distinct rotational temperatures and production rates at greatly improved confidence levels compared with results derived from earlier fluorescence models. The new model reconciles production rates measured at infrared and radio wavelengths in C/2001 A2 (LINEAR). Methanol can now be quantified with unprecedented precision and accuracy in astrophysical sources through high-dispersion spectroscopy at infrared wavelengths

Villanueva, Geronimo L.↗

Theoretical study of the X-ray emission from astrophysical shock waves

Theoretical X-ray emission spectra are needed to interpret the X-ray emission observed by many low and moderate resolution X-ray instruments, and to provide diagnosis of physical conditions for high resolution spectra. Over the past decade, a set of model codes which compute the X-ray and XUV emission for a wide set of physical conditions, including high or low densities, photoionized gas, and time-dependent ionization balance was developed. In the past year, the atomic rate coefficients in the code was improved. Further capabilities were added, and applied to several astrophysical problems.

Raymond, J.↗

Study of polyphenyl ether fluid /5P4E/ in operating elastohydrodynamic contacts by infrared emission spectroscopy

Infrared emission spectra of 5P4E polyphenyl ether were obtained from an operating elastohydrodynamic sliding contact at different speeds and loads by Fourier emission microspectrophotometry. The spectra were found to be polarized with respect to the direction of the conjunction line, especially at high shear rates. Film and metal surface temperatures were calculated from the spectra, and film thicknesses were determined under various operating conditions. Changes of polarized band structure above a critical shear rate, at which the slope of the film temperature versus shear curve changes abruptly and at which the film thickness assumes a minimum value, are consistent with a transition of the lubricant from a viscous liquid to a viscoelastic liquid or to an elastic solid.

Lauer, J. L.↗

3D Printable Polymers for Radiological Applications

Additive manufacturing of polymers is a widely used and growing technology throughout the DOE complex. Composite filaments for Fused Deposition Modeling (FDM) printers are commonly used to enhance material properties such as mechanical strength, operating temperature and chemical resistance. Radio luminescent properties were added to 3D filaments by impregnating clear poly(ethylene terephthalate)-glycol (PETG) with X-ray scintillator powder. X-ray scintillators have unique, narrow emission spectra which can be imaged with low light DSLR cameras, photomultiplier tubes, or spectrometers. Filament Production: 1. Pellets are loaded into the hopper. 2. Temperature and extrusion speed are set on extruder. 3. Extruder turned on and filament is pulled from nozzle along air path to cool. 4. Spooler drive speeds set. 5. Filament is inserted through Filameasure then guided along drive wheels and into traverse. 6. Parameters adjusted to obtain 1.75 mm diameter 7. Filament is inserted into spooler wheel. Traverse speed set and slip nut adjusted to make tight and even roll. From Raw Materials to Printed Part: Clear PETG pellets were dipped in ZnS:Cu scintillator powder to coat pellets. Coated and uncoated pellets were mixed together before inserting into hopper. Filament showed trace amounts of powder and luminesced under UV light. Powder distribution is random and not reproducible thus providing a unique identification marker potentially useful for national security applications. Multiple X-ray scintillators can be arranged in a panel to discriminate incident X-ray photon energies. Variable panel arrangement: pixelated, layered, solid from homogenous filament. Ratio of emission intensities. Response varies with incident photon energy. Spectrally separate scintillators. Scintillators: Yttrium Oxide Europium Doped - Red, Gadolinium Oxysulfide Terbium Doped - Green, Barium Magnesium Aluminate Europium Doped - Blue, Zinc Sulfide Copper Doped - Green. Powder concentrations will need to be increased in the filament for use in the energy discriminating panel. Homogeneity in the filament will be a challenge that can be solved by turning the pellets into a powder and mixing it with scintillator powder prior to extrusion. The panels will be tested using x-ray booths and button sources such as Am-241, Cs-137, and Co-60.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Detecting Atmospheric Molecules of Nontransiting Temperate Terrestrial Exoplanets Using High-resolution Spectroscopy in the Mid-infrared Domain

Motivated by the development of high-dispersion spectrographs in the mid-infrared (MIR) range, we study their application to the atmospheric characterization of nearby nontransiting temperate terrestrial planets around M-type stars. We examine the detectability of CO{sub 2}, H{sub 2}O, N{sub 2}O, and O{sub 3 }features in high-resolution planetary thermal emission spectra at 12–18 μm assuming an Earth-like profile and a simplified thermal structure. The molecular line width of such planets can be comparable to or broader than the Doppler shift due to the planetary orbital motion. Given the likely difficulty in knowing the high-resolution MIR spectrum of the host star with sufficient accuracy, we propose observing the target system at two quadrature phases and extracting the differential spectra as the planetary signal. In this case, the signals can be substantially suppressed compared with the case where the host star spectrum is perfectly known, as some parts of the spectral features do not remain in the differential spectra. Despite this self-subtraction, the CO{sub 2} and H{sub 2}O features of nearby (≲5 pc) systems with mid-/late-M host stars would be feasible with a 6.5 m class cryogenic space telescope, and orbital inclination could also be constrained for some of them. For CO{sub 2} and N{sub 2}O in a 1 bar Earth-like atmosphere, this method would be sensitive when the mixing ratio is 1–10{sup 3} ppm. The detectability of molecules except O{sub 3} is not significantly improved when the spectral resolution is higher than R≳10,000, although the constraint on the orbital inclination is improved. This study provides some benchmark cases useful for assessing the value of MIR high-resolution spectroscopy in terms of characterization of potentially habitable planets.

47 OTHER INSTRUMENTATION↗

Fine-grained Goethite as a Precursor for Martian Gray Hematite

Several isolated deposits of gray, crystalline hematite on Mars were discovered using data returned from the Thermal Emission Spectrometer (TES) instrument aboard the Mars Global Surveyor spacecraft. Christensen et al. provided five testable hypotheses regarding the formation of crystalline hematite on Mars: 1) low-temperature precipitation of Fe oxides/hydroxides from standing, oxygenated, Fe-rich water, followed by subsequent alteration to gray hematite, 2) low-temperature leaching of iron-bearing silicates and other materials leaving a Fe-rich residue laterite-style weathering) which is subsequently altered to gray hematite, 3) direct precipitation of gray hematite from Fe-rich circulating fluids of hydrothermal or other origin, 4) formation of gray hematitic surface coatings during weathering, and 5) thermal oxidation of magnetite-rich lavas. Since this initial work, several authors have examined the hematite deposits to determine their formation mechanism. Lane et al. cited the absence of a 390/ cm absorption in the martian hematite spectrum as evidence for platy hematite grains. Their model for the formation of the deposits includes deposition of any of a variety of iron oxides or oxyhydroxides by aqueous or hydrothermal fluids, burial and metamorphosis to gray platy hematite grains, and exhumation in recent times. Based on a detailed geomorphic examination of the Sinus Meridiani region, Hynek et al. conclude that the most likely method of hematite formation was either emplacement by a hydrothermal fluid or oxidation of a magnetite-rich pyroclastic deposit. Similarly, Arvidson et al., favor a model involving the alteration of pyroclastic deposits by aqueous or hydrothermal fluids. Finally, based on geochemical modeling and an examination of Aram Chaos, Catling and Moore favor emplacement by hydrothermal fluids with a minimum temperature of 100 C. Comparison of the average martian hematite spectrum measured by TES to hematite emissivity spectra for a variety of naturally occurring hematites shows small but potentially important differences. In particular, band shapes, positions and relative band emissivities of hematite spectra vary over the range of samples. These differences imply that the natural variability of thermal infrared hematite spectra has not been fully characterized, especially with respect to the reaction pathway and crystal structure.

T D Glotch↗

JWST Noise Floor. I. Random Error Sources in JWST NIRCam Time Series

James Webb Space Telescope (JWST) transmission and emission spectra will provide invaluable glimpses of transiting exoplanet atmospheres, including possible biosignatures. This promising science from JWST, however, will require exquisite precision and understanding of systematic errors that can impact the time series of planets crossing in front of and behind their host stars. Here, we provide estimates of the random noise sources affecting JWST Near-Infrared Camera (NIRCam) time-series data on the integration-to-integration level. We find that 1/f noise can limit the precision of grism time series for two groups (230–1000 ppm depending on the extraction method and extraction parameters), but will average down like the square root of N frames/reads. The current NIRCam grism time-series mode is especially affected by 1/f noise because its GRISMR dispersion direction is parallel to the detector fast-read direction, but could be alleviated in the GRISMC direction. Care should be taken to include as many frames as possible per visit to reduce this 1/f noise source: thus, we recommend the smallest detector subarray sizes one can tolerate, four output channels, and readout modes that minimize the number of skipped frames (RAPID or BRIGHT2). We also describe a covariance-weighting scheme that can significantly lower the contributions from 1/f noise as compared to sum extraction. We evaluate the noise introduced by pre-amplifier offsets, random telegraph noise, and high dark current resistor capacitor (RC) pixels and find that these are correctable below 10 ppm once background subtraction and pixel masking are performed. We explore systematic error sources in a companion paper.

79 ASTRONOMY AND ASTROPHYSICS↗

The ground-based measurement of ozone in the 9.6 micron band

Stratospheric ozone has been measured using infrared emission spectroscopy of the 9.6 micron band. Thermal emission spectra of the zenith sky were measured from the ground. The spectra show the presence of the 1020 cm(exp -1) spectral feature of ozone on clear days. The spectra were measured with a BOMEM model 100 emission interferometer with a resolution of 4 cm(exp -1). The feature corresponds to a mixing ratio of 5 ppmv if the ozone is assumed to be uniformly distributed in the stratosphere from 25 to 35 km. The development of an inversion algorithm to derive the altitude distribution of the ozone in 3 layers is described. These measurements have been conducted from Peterborough, Ontario since June 1991; further investigations are planned to study the comparisons with Dobson and LIDAR ozone measurements.

Evans, W. F. J.↗

Emission Lines of Fe xiv, Fe xv, and Fe xvi in the Extreme Ultraviolet Region 40–100 Å

We report on emission spectra of iron in the extreme ultraviolet recorded at an electron density of ~10 11 cm -3 on the Lawrence Livermore electron beam ion trap facility. We present a summary of the observed emission lines, including wavelengths and emission intensities, and present spectra of pure Fe xiv through Fe xvi emission derived from our measurements in the 40–100 Å wavelength range. We show that spectral models, especially the current version of CHIANTI v10.0, describe the M-shell emission from these three charge states of iron reasonably well, and we are able to verify several transitions in CHIANTI for the first time.

74 ATOMIC AND MOLECULAR PHYSICS↗