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At least 271 records · Page 15

Measurement of atmospheric OH by titration of near-IR fluorescent dyes

Recent research has shown that certain polymethine dyes can be detected at ultratrace levels (greater than or equal to 6x10(exp -14) M) in solution by fluorimetry. These detection limits are possible because of the inherent sensitivity of fluorescence techniques, because the dyes fluoresce in the near infrared region where background interference is negligible, and because powerful infrared diode lasers are now available to improve the signal to noise ratio. Other work has shown that the hydroxyl radical destroys the ability of polymethine dyes to fluoresce. These observations form the basis for a new hydroxyl radical detector that is essentially a fluorometric titrator. Theoretically, the detector should show an acceptable sensitivity and response time. Assuming that the atmospheric HO concentration is about 10(exp -11) moles m(exp -3) (i.e. 10(exp 6) molecules cm(exp -3)), then 10 L of air 'titrated' with 20 mL of 10(exp -11) M dye solution (an easily detected concentration) should result in a drop in the fluorescent signal of 50 percent - a readily detectable change. At a flow rate of 3 L min(exp -1) the sampling time would be 3 minutes. The biggest potential problem is selectivity: other oxidants may also cause the fluorescence signal to be lost. The chemistry of polymethine dyes has not been studied in detail and so no quantitative data are available. However, a survey of the literature suggests that in general HO should react up to six orders of magnitude faster than HO2 and other radicals such as RO2 and RO. It should also react much more rapidly than H2O2 and O3. Thus it may be possible to discriminate kinetically against potential interfering substances. It was shown in the laboratory that 10(exp -4) M H2O2 has little effect on the absorption spectrum of the dye IR125 over a period of hours but that the band at 780 nm is slowly lost in water over a period of days even under argon in the dark. By contrast, DMSO solutions of IR125 are stable.

Betterton, Eric A.↗

Development of nonintrusive, scatter-independent techniques for measurement of liquid density inside dense sprays

A nonintrusive optical technique for measuring the liquid density in sprays used to simulate LOX injector flows is under development. This manuscript is a report on work toward that development which is currently in progress. The technique is a scatter-independent, absorption-based approach which depends on the numerical inversion of a collection of absorption profiles. For the case in which visible radiation passes through liquid-gas interfaces so numerous in sprays, substantial reductions and alterations in the signal result from scattering even in the absence of absorption. To avoid these problems, X-Rays will be used as the absorbed radiation. The experimental process is simulated by integrating the absorption spectrum for a known distribution, adding instrument noise to this 'measurement', creating a projection from the 'measurement', filtering the projection, inverting the projection, and comparing the results with the original prescribed distribution.

Hartfield, Roy↗

Ozone absorption spectroscopy in search of low-lying electronic states

A spectrometer capable of detecting ozone absorption features 9 orders of magnitude weaker than the Hartley band has been employed to investigate the molecule's near-infrared absorption spectrum. At this sensitivity a wealth of information on the low-lying electronically excited states often believed to play a role in atmospheric chemistry is available in the form of vibrational and rotational structure. We have analyzed these spectra using a combination of digital filtering and isotope substitution and find evidence for three electronically excited states below 1.5 eV. The lowest of these states is metastable, bound by approximately 0.1 eV and probably the (3)A2 rather than the (3)B2 state. Its adiabatic electronic energy is 1.24 +/- 0.01 eV, slightly above the dissociation energy of the ground state. Two higher states, at 1.29 +/- 0.03 and 1.48 +/- 0.03 eV are identified as the (3)B2 and the (3)B1, respectively. Combined with other recent theoretical and experimental data on the low-lying electronic states of ozone, these results imply that these are, in fact, the lowest three excited states; that is, there are no electronically excited states of ozone lying below the energy of O(3P) + O2((3)Sigma(-), v = 0). Some of the implications for atmospheric chemistry are considered.

Anderson, S. M.↗

Analysis of cloud top height and cloud coverage from satellites using the O2 A and B bands

Cloud height and cloud coverage detection are important for total ozone retrieval using ultraviolet and visible scattered light. Use of the O2 A and B bands, around 761 and 687 nm, by a satellite-borne instrument of moderately high spectral resolution viewing in the nadir makes it possible to detect cloud top height and related parameters, including fractional coverage. The measured values of a satellite-borne spectrometer are convolutions of the instrument slit function and the atmospheric transmittance between cloud top and satellite. Studies here determine the optical depth between a satellite orbit and the Earth or cloud top height to high accuracy using FASCODE 3. Cloud top height and a cloud coverage parameter are determined by least squares fitting to calculated radiance ratios in the oxygen bands. A grid search method is used to search the parameter space of cloud top height and the coverage parameter to minimize an appropriate sum of squares of deviations. For this search, nonlinearity of the atmospheric transmittance (i.e., leverage based on varying amounts of saturation in the absorption spectrum) is important for distinguishing between cloud top height and fractional coverage. Using the above-mentioned method, an operational cloud detection algorithm which uses minimal computation time can be implemented.

Kuze, Akihiko↗

Determination of the major groups of phytoplankton pigments from the absorption spectra of total particulate matter

The contributions of detrital particles and phytoplankton to total light absorption are retrieved by nonlinear regression on the absorption spectra of total particles from various oceanic regions. The model used explains more than 96% of the variance in the observed particle absorption spectra. The resulting absorption spectra of phytoplankton are then decomposed into several Gaussian bands reflecting absorption by phytoplankton pigments. Such a decomposition, combined with high-performance liquid chromatography data on phytoplankton pigment concentrations, allows the computation of specific absorption coefficients for chlorophylls a, b, and c and carotenoids. The spectral values of these in vivo absorption coefficients are then discussed, considering the effects of secondary pigments which were not measured quantitatively. We show that these coefficients can be used to reconstruct the absorption spectra of phytoplankton at various locations and depths. Discrepancies that do occur at some stations are explained in terms of particle size effect. These coefficients can be used to determine the concentrations of phytoplankton pigments in the water, given the absorption spectrum of total particles.

Hoepffner, Nicolas↗

Infrared, Submillimeter, and RadioAstronomy Program Astophysics Division

The object of my research for the NASA grant NAGW-4769 was to observe infrared spectra of molecular ions with special astrophysical interest in plasmas both in the laboratory and in space. Progress made during the period from September 1995 to September 1996 is summarized in the following: 1. Detection of Interstellar H3(+) The discovery of interstellar H3(+) through its mid-infrared absorption spectrum was by far the most inspiring development during this fiscal year. H3(+), the simplest stable polyatomic system, has been postulated to play the central role in the ion-neutral reaction scheme of interstellar chemistry, but its presence had not been directly observed in spite of intensive searches by several groups. 2. Observation of High Revibrational States of H3(+). The initial discovery of H3(+) in the Jovian aurora region was made through the identification of the 2(nu)(sub 2)(sup 2) approaches O overtone band indicating the population of H3(+) in high revibration state. 3. Observation of Ortho-Para H3(+) selection rules in plasma chemistry. Celection rules that relate quantum states before and ufter various processes are fascinating subject based on the symmetry argument. 4. Spectroscopy of other ions. Spectroscopy of carbocations ch3(+), CH2(+), C2H3(+) and C2H2(+) has been continued.

Oka, Takeshi↗

The Origin, Composition and History of Comets from Spectroscopic Studies

A wealth of information essential to understanding the composition and physical structure of cometary ice and hence gain deep insight into the comet's origin and history, can be gleaned by carrying out a full range of spectroscopic studies on the returned sample. These studies ought to be among the first performed as they are generally non-destructive and will provide a broad data bank which will be crucial in planning subsequent analysis. Examples of the spectroscopic techniques along with relative sensitivities and transitions probed, are discussed. Different kind of "spectroscopy" is summarized, with emphasis placed on the kind of information each provides. Infrared spectroscopy should be the premier method of analysis as the mid-IR absorption spectrum of a substance contains more global information about the identity and structure of that material than any other property. In fact, the greatest strides in our understanding of the composition of interstellar ices (thought by many to be the primordial material from which comets have formed) have been taken during the past ten years or so because this was when high quality infrared spectra of the interstellar medium (ISM) first became available. The interpretation of the infrared spectra of mixtures, such as expected in comets, is often (not always) ambiguous. Consequently, a full range of other non-destructive, complementary spectroscopic measurements are required to fully characterize the material, to probe for substances for which the IR is not well suited and to lay the groundwork for future analysis. Given the likelihood that the icy component (including some of the organic and mineral phases) of the returned sample will be exceedingly complex, these techniques must be intensely developed over the next decade and then made ready to apply flawlessly to what will certainly be one of the most precious, and most challenging, samples ever analyzed.

Allamandola, L. J.↗

Chemical Sensors Based on IR Spectroscopy and Surface-Modified Waveguides

Sol-gel processing techniques have been used to apply thin porous films to the surfaces of planar infrared (IR) waveguides to produce widely useful chemical sensors. The thin- film coating serves to diminish the concentration of water and increase the concentration of the analyte in the region probed by the evanescent IR wave. These porous films are composed of silica, and therefore, conventional silica surface modification techniques can be used to give the surface a specific functional character. The sol-gel film was surface-modified to make the film highly hydrophobic. These sensors were shown to be capable of detecting non-polar organic analytes, such as benzonitrile, in aqueous solution with detection limits in the ppb range. Further, these porous sol-gel structures allow the analytes to diffuse into and out of the films rapidly, thus reaching equilibrium in less than ten seconds. These sensors are unique because of the fact that their operation is based on the measurement of an IR absorption spectrum. Thus, these sensors are able to identify the analytes as well as measure concentration with high sensitivity. These developments have been documented in previous reports and publications. Recently, we have also targeted detection of the polar organic molecules acetone and isopropanol in aqueous solution. Polar organics are widely used in industrial and chemical processes, hence it is of interest to monitor their presence in effluents or decontamination process flows. Although large improvements in detection limits were expected with non-polar organic molecules in aqueous solutions using very hydrophobic porous sol-gel films on silicon attenuated total reflectance (Si ATR) waveguides, it was not as clear what the detection enhancements might be for polar organic molecules. This report describes the use of modified sol-gel-coated Si ATR sensors for trace detection and quantitation of small polar organic molecules in aqueous solutions. The detection of both acetone and isopropanol molecules in aqueous solution has been previously reported for chalcogenide fiber optic sensors. The sol-gel film was produced using a mixture of ethyltriethoxysilane and tetraethoxysilane and the surface modification was carried out using trimethylchlorosilane. We have demonstrated that this film concentrates the target polar analytes from aqueous solution in the region probed by the evanescent wave to improve detection limits by as much as a factor of 450.

Lopez, Gabriel P.↗

A Fluorescent Source NDIR Carbon Monoxide Analyzer

This paper describes a new technique for measuring trace quantities of carbon monoxide by the nondispersive infrared (NDIR) methods. The technique uses the property of infrared fluorescence in a gas to generate a specific source of radiation which is an exact match of the absorption spectrum of the fundamental band of carbon monoxide. This results in an instrument with high sensitivity and specificity for CO. A novel method of referencing using an isotopic species of CO confers great stability on the instrument.

Link, W. T.↗

Ab Initio Calculations of Singlet and Triplet Excited States of Chlorine Nitrate and Nitric Acid

Ab initio calculations of vertical excitations to singlet and triplet excited states of chlorine nitrate and nitric acid are reported. The nature of the electronic transitions are examined by decomposing the difference density into the sum of detachment and attachment densities. Counterparts for the three lowest singlet excited states of nitric acid survive relatively unperturbed in chlorine nitrate, while other low-lying singlet states of chlorine nitrate appear to be directly dissociative in the ClO chromophore. These results suggest an assignment of the two main peaks in the experimental chlorine nitrate absorption spectrum. In addition, triplet vertical excitations and the lowest optimized triplet geometries of both molecules are studied.

Grana, Ana M.↗

Beer Law Constants and Vapor Pressures of HgI2 over HgI2(s,l)

The optical absorption spectra of the vapor phase over HgI2(s,l) were measured for wavelengths between 200 and 600 nm. The spectra show that the sample sublimed congruently into HgI2 with no Hg or I2 absorption spectrum observed. The Beer's Law constants for 15 wavelengths between 200 and 440 nm were determined. From these constants the vapor pressure of H912, P, was established as a function of temperatures for the liquid and the solid Beta-phases. The expressions correspond to the enthalpies of vaporization and sublimation of 15.30 and 20.17 Kcal/mole, respectively, for the liquid and the Beta-phase HgI2. The difference in the enthalpies gives an enthalpy of fusion of 4.87 Kcal/mole and the intersection of the two expressions gives a melting point of 537 K.

Su, Ching-Hua↗

Measuring the Spectral Expression of Carbon Dioxide in the Solar Reflected Spectrum with AVIRIS

Carbon dioxide is a low-concentration, but important, component of the Earth's atmosphere. This gas absorbs electromagnetic radiation (EMR) in several regions of the spectrum. Absorption of energy by carbon dioxide adds heat to the atmosphere. In the world today, the burning of fossil fuels and other anthropogenic processes adds carbon dioxide to the atmosphere. Other natural processes in the Earth's system both add and remove carbon dioxide. Overall, measurements of atmospheric carbon dioxide at selected sites around the globe show an increased carbon dioxide concentration in the atmosphere. A figure shows the measured carbon dioxide from Mauna Loa, Hawaii, from 1958 to 2000. Overall, the concentration has increased from 315 to 365 ppm at this site over this period. (There is also a yearly cycle to the concentration that is timed with and hypothesized to be related to the vegetation growing season in the Northern Hemisphere.) The overall expected effect of this increase of atmospheric carbon dioxide is trapping of heat in the atmosphere and global warming. While this overall relationship between carbon dioxide and global warming seems straightforward, many of the specific details relating to regional and local sources and sinks and gradients of carbon dioxide are not well understood. A remote sensing capability to measure carbon dioxide could provide important inputs for scientific research to better understand the distribution and change in atmospheric carbon dioxide at detailed spatial and temporal levels. In pursuit of this remote sensing of carbon dioxide objective, this paper analyzes the expression of carbon dioxide in the spectral range measured by the Airborne Visible/Infrared Imagery Spectrometer (AVIRIS). Based on these analyses, a spectral-fitting algorithm that uses AVIRIS measured spectra and MODTRAN radiative-transfer code modeled spectra to derive total column carbon dioxide abundance has been developed. This algorithm has been applied to an AVIRIS data set acquired over Pasadena, California, in 1999 and a data set acquired over the Pacific Ocean near Hawaii in 2000 with promising results. This is ongoing research; the current initial analyses, measurements, and results are reported in this paper.

Green, Robert O.↗

Clues to Coral Reef Health: Integrating Radiative Transfer Modeling and Hyperspectral Data

An important contribution to coral reef research is to improve spectral distinction between various health states of coral species in areas subject to harmful anthropogenic activity and climate change. New insights into radiative transfer properties of corals under healthy and stressed conditions can advance understandings of ecological processes on reefs and allow better assessments of the impacts of large-scale bleaching and disease events, Our objective was to examine the spectral and spatial properties of hyperspectral sensors that may be used to remotely sense changes in reef community health. We compare in situ reef environment spectra (healthy coral, stressed coral, dead coral, algae, and sand) with airborne hyperspectral data to identify important spectral characteristics and indices. Additionally, spectral measurements over a range of water depths, relief, and bottom types are compared to help quantify bottom-water column influences. In situ spectra were collected in July and August 2002 at the Long Rock site in the Andros Island, Bahamas coastal zone coral reef. Our primary emphasis was on Acropora palmata (or elkhorn coral), a major reef building coral, which is prevalent in the study area, but is suffering from white band disease. A. palmata is currently being, proposed as an endangered species because its populations have severely declined in many areas of the Caribbean. In addition to the A. palmata biotope, we have collected spectra of at least seven other coral biotopes that exist within the study area, each with different coral community composition, density of corals, relief, and size of corals. Coral spectral reflectance was then input into a radiative transfer model, CORALMOD (CM1), which is based on a leaf radiative transfer model. In CM1, input coral reflectance measurements produce modeled reflectance through an inversion at each visible wavelength to provide the absorption spectrum. Initially, we imposed a scattering baseline that is the same regardless of the coral condition and that coral is optically thick and no light is transmitted through coral. Here we will focus on methodology, experimental design, and initial findings of the in situ spectral measurements and preliminary output from the radiative transfer model.

Guild, Liane↗

A Program to Detect and Characterize Extra-Solar Giant Planets

We initiated a significant hardware upgrade to the AFOE, to increase its efficiency for precise radial velocity studies to the level where we can continue to contribute usefully to extrasolar planet research on relatively bright stars. The AFOE, at a 1.5-m telescope, will of course not have the sensitivity of radial velocity instruments at larger telescopes, such as the HIRES on Keck or the Hectochelle on the MMT telescope (about to come on line). However, it has been possible to increase its efficiency for precise radial velocity studies by a factor of 4 to 5, which-combined with the large amount of telescope time available at the 1.5-m telescope-will permit us to do intensive follow-up observations of stars brighter than about 8 magnitude. The AFOE was originally designed primarily for asteroseismology using a ThAr reference. This provided useful wavelength stability over tens of minutes as required for asteroseismology, but we were unable to get a long-term (month-to-month) velocity precision better than about 15 m/s with that setup. Hence, we implemented an iodine cell as a wavelength reference for extrasolar planet studies. However, the optical design of the original AFOE did not completely span the wavelength range covered by the iodine absorption spectrum, and furthermore the optics suffered significant light loss through optical obscuration in the camera secondary. To remedy this, we replaced the AFOE grating with a new one that covered the entire iodine spectral range at somewhat lower spectral resolution, and replaced the camera with a transmitting lens. (The use of a lens was made possible by restricting the spectral range covered by the upgraded AFOE to only the iodine region.) These upgrades were successfully completed, and the instrument was tested for three nights in fall of 2002. The expected improvement in sensitivity by a factor of 4 to 5 was observed: that is, the same velocity precision as previously attained (of order 5 to 7 m/s) was now obtained on a stars that are about 4 to 5 times fainter. Unfortunately, just after installing the new AFOE optics, there was a catastrophic failure of the old Tektronix CCD. A careful investigation was made, and it was determined that the failure was probably due to too many thermal cyclings over the previous 8 years. The only solution was to purchase a new CCD. Internal funds of $16,000 were found for this purpose, and the new CCD (a thinned, back-illuminated Marconi 2K x 2K device with 13.5 micron pixels, and employing dual readout channels to keep the readout time as short as 20 seconds) was ordered, has now arrived, and is currently under test before 1 being installed in the AFOE liquid nitrogen dewar. At the same time, we expect to implement new CCD control electronics. This system should be better in many ways than the previous detector (including eliminating the need for UV flashing to maximize the quantum efficiency). We plan to install the detector on the telescope and begin operations again in April of this year.

Lindstrom, David↗

Optical Spectra of Extrasolar Giant Planets

The flux distribution of a planet relative to its host star is a critical quantity for planning space observatories to detect and characterize extrasolar giant planets (EGP's). In this paper, we present optical planet-star contrasts of Jupiter-mass planets as a function of stellar type, orbital distance, and planetary cloud characteristics. As originally shown by Sudarsky et al. (2000, 2003), the phaseaveraged brightness of an EGP does not necessarily decrease monotonically with greater orbital distance because of changes in its albedo and absorption spectrum at lower temperatures. We apply our results to Eclipse, a 1.8-m optical telescope + coronograph to be proposed as a NASA Discovery mission later this year.

Heap, Sara R.↗

Performance characteristics of narrow linewidth fiber laser pumped mid-IR difference frequency mixing light source for methane detection

A high-power, narrow-linewidth Yb fiber laser with a fiber Bragg grating (FBG) pumped difference frequency generation (DFG) in a periodically poled lithium niobate (PPLN) crystal was investigated in detail. A mid-IR power of approximately 2.3 microW at 3.3 micrometers with a slope efficiency of 0.85 mW/W2 was achieved. A Doppler-broadened absorption spectrum of CH4 at 3038.497 cm-1 (3.2911 micrometers) was obtained with a 0.1-m long-gas cell at a pressure of 133 Pa. The linewidth of the DFG source was evaluated to be less than 96 MHz from the observed spectral linewidth. Real-time monitoring of CH4 (approximately 1.78 ppm) in ambient air in a multipass cell which has an optical path length of 10 m was also demonstrated.

Non-NASA Center↗

Development of an automated diode-laser-based multicomponent gas sensor

The implementation and application of a portable fiber-coupled trace-gas sensor for the detection of several trace gases, including CO2, CH4, and H2CO, are reported. This particular sensor is based on a cw fiber-amplified near-infrared (distributed Bragg reflector) diode laser and an external cavity diode laser that are frequency converted in a periodically poled lithium niobate crystal to the mid-IR spectroscopic fingerprint region (3.3-4.4 micrometers). A continuous absorption spectrum of CH4 and H2CO from 3.37 to 3.10 micrometers with a spectral resolution of 40 MHz (approximately 0.0013 cm-1) demonstrated the spectral performance that can be achieved by means of automated wavelength tuning and phase matching with stepper motor control. Autonomous long-term detection of ambient CO2 and CH4 over a 3- and 7-day period was also demonstrated.

NASA Discipline Environmental Health↗

Plasma processing of interstellar PAHs into solar system kerogen

Processes resulting in the formation of hydrocarbons of carbonaceous chondrites and the identity of the interstellar molecular precursors involved are an objective of investigations into the origin of the solar system and perhaps even life on earth. We have combined the resources and experience of an astronomer and physicists doing laboratory simulations with those of a chemical expert in the analysis of meteoritic hydrocarbons, in a project that investigated the conversion of polycyclic aromatic hydrocarbons (PAHs) formed in stellar atmospheres into alkanes found in meteorites. Plasma hydrogenation has been found in the University of Alabama at Birmingham Astrophysics Laboratory to produce from the precursor PAH naphthalene, a new material having an IR absorption spectrum (Lee, W. and Wdowiak, T.J., Astrophys. J. 417, L49-L51, 1993) remarkably similar to that obtained at Arizona State University of the benzene-methanol extract of the Murchison meteorite (Cronin, J.R. and Pizzarello, S., Geochim. Cosmochim. Acta 54, 2859-2868, 1990). There are astrophysical and meteoritic arguments for PAH species from extra-solar sources being incorporated into the solar nebula, where plasma hydrogenation is highly plausible. Conversion of PAHs into alkanes could also have occurred in the interstellar medium. The synthesis of laboratory analogs of meteoritic hydrocarbons through plasma hydrogenation of PAH species is underway, as is chemical analysis of those analogs. The objective is to clarify this heretofore uninvestigated process and to understand its role during the origin of the solar system as a mechanism of production of hydrocarbon species now found in meteorites. Results have been obtained in the form of time-of-flight spectroscopy and chemical analysis of the lab analog prepared from naphthalene.

NASA Discipline Exobiology↗