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Murcray, D. G.

Publications and source records attributed to Murcray, D. G..

At least 19 records

Thermal infrared spectra of the Moon

Contrary to recent assertions in the literature, lunar emission spectra obtained at an altitude of 32 km with a balloon-borne telescope are virtually undistorted by atmospheric absorption, except in the ozone region. These spectra have been found to correlate closely with laboratory emission spectra of returned lunar samples measured in a simulated lunar environment. Thus, lunar spectra obtained with the balloon-borne telescope system are the standards against which groundbased spectral measurements of the Moon should be compared. Comparison of balloon-borne measurements with recent groundbased spectral measurements suggests that the latter suffer from some source of systematic error. When high-quality lunar spectra are available, they will be best interpreted by comparison with returned lunar samples, rather than terrestrial minerals or rocks, because of subtle spectral differences between lunar and terrestrial minerals perhaps associated with incipient alteration of the latter.

Salisbury, John W.↗

Infrared spectroscopic measurements of the ethane (C2H6) total column abundance above Mauna Loa, Hawaii -- seasonal variations

About 200 i.r. solar spectra recorded at 0.01/cm resolution on 71 days between November 1991 and July 1993 at the Network for the Detection of Stratospheric Change (NDSC) station at Mauna Loa, Hawaii (latitude 19.53 deg N, longitude 155.58 deg W, elevation 3.459 km) have been analyzed with a nonlinear least-squares spectral fitting technique to study temporal variations in the total column of atmospheric ethane (C2H6) above the site. The results were derived from the analysis of the unresolved nu(sub 7) band (P)Q(sub 3) subbranch at 2976.8/cm. A distinct seasonal cycle is observed with a factor of 2 variation, a maximum total column of 1.16 x 10(exp 16) mol/sq cm at the end of winter, and a minimum total column of 0.53 x 10(exp 16) mol/sq cm at the end of summer. Our measurements are compared with previous observations and model predictions.

Rinsland, C. P.↗

High resolution studies of heacy NO(y) molecules in atmospheric spectra

New line parameters for two heavy odd nitrogen molecules HNO3 in the nu(sub 5)/2nu(sub 9) region, and ClONO2 in the nu(sub 4) region are incorporated in the analysis of high resolution i.r. atmospheric spectra. The line parameters are tested and renormalized vs laboratory spectra, and then applied to retrievals from balloon-borne and ground-based solar absorption spectra.

Goldman, A.↗

The determination of HNO3 column amounts from tunable diode laser heterodyne spectrometer spectra taken at Jungfruajoch, Switzerland

In May of 1991 a tunable diode laser heterodyne spectrometer built by the National Physical Laboratory was operated at the International Scientific Station of the Jungfraujoch (46.5 deg N, 8.0 deg E, altitude 3.56 km). Nitric acid spectra in the region of 868 wavenumbers were recorded at sunset and sunrise on two separate days at a resolution of 0.0013 wavenumbers with a signal-to-noise ratio of approximately 130:1. A vertical column amount of HNO3 of 1.61 x 10(exp 16) molecules/sq cm was determined using an atmospheric transmission model developed at the University of Denver. The mean of a number of mid-latitude, northern hemisphere profiles was used as the initial profile for the inversion. A comparison of different initial profiles provides information on the sensitivity of the retrieved column amount of 1.61 x 10(exp 16) molecules/sq cm lies within the range of values published in the World Meteorological Organization Report no. 16 (1986), but is considerably larger than the value of (0.99 - 1.29) x 10(exp 16) reported by Rinsland et al. (1991) for June during the period 1986 to 1990.

Fogal, P. F.↗

Infrared Spectroscopic Measurements of the Ethane (C2H6) Total Column Abundance Above Mauna Loa, Hawaii: Seasonal Variations

About 200 i.r. solar spectra recorded at 0.01/ cm resolution on 71 days between November 1991 and July 1993 at the Network for the Detection of Stratospheric Change (NDSC) station at Mauna Loa, Hawaii (latitude 19.53 deg N, longitude 155.58 deg W, elevation 3.459 km) have been analyzed with a nonlinear least-squares spectral fitting technique to study temporal variations in the total column of atmospheric ethane (C2H6) above the site. The results were derived from the analysis of the unresolved nu(sub 7) band (sup P)Q(sub 3) subbranch at 2976.8/cm. A distinct seasonal cycle is observed with a factor of 2 variation, a maximum total column of 1.1 6 x 10(exp 16) mol /sq cm at the end of winter, and a minimum total column of 0.53 x 10(exp 16) mol/sq cm at the end of summer. Our measurements are compared with previous observations and model predictions.

Rinsland, C. P.↗

High Resolution Studies of Heavy NO(y) Molecules in Atmospheric Spectra

New line parameters for two heavy odd nitrogen molecules HNO3 in the upsilon(sub 5)/2upsilon(sub 9) region, and ClONO2 in the upsilon(sub 4) region are incorporated in the analysis of high resolution i.r. atmospheric spectra. The line parameters arc tested and renormalized vs laboratory spectra, and then applied to retrievals from balloon-borne and ground-based solar absorption spectra.

Goldman, A.↗

Stratospheric HNO3 measurements from 0.002/cm resolution solar occultation spectra and improved spectroscopic line parameters in the 5.8-micron region

Very-high-resolution FWHM solar-occultation spectra are investigated with a balloon-borne interferometer using revised spectroscopic line parameters for HNO3, O3, and H2O. The O3 and H2O data are evaluated to determine their capacity for interference in the HNO3 line which is studied in the nu sub 2 band at 5.8 microns. The line parameters developed with the stratospheric data are compared to data based on a HITRAN compilation as well as laboratory spectra with a 0.002/cm resolution. The line list is calculated and shown to include J and Ka transitions which improve the line parameters for HNO3 by accounting for the weaker absorption features in the stratospheric spectra. The stratospheric HNO3 profile developed analytically is compared to those based on reported measurements, and the one developed with the stratospheric solar spectra is found to be consistent with the measurements and confirm inherent measurement biases.

Goldman, A.↗

Mt. Pinatubo SO2 column measurements from Mauna Loa

Absorption features of the nu sub 1 band of SO2 are identified in high-resolution IR solar-absorption spectra recorded from Mauna Loa, Hawaii, on July 9 and 12, 1991, shortly after the arrival of the first eruption plume from the Mt. Pinatubo volcano. A total SO2 vertical column amount of (5.1 +/- 0.5) x 10 exp 16 molecules/sq cm on July 9 is retrieved based on nonlinear least-squares spectral fittings of 9 selected SO2 absorption features with an updated set of SO2 spectral parameters. A SO2 total-column upper limit of 0.9 x 10 exp 16 molecules/sq cm deduced from measurements on September 20-24, 1991, is consistent with the dispersion of the SO2 cloud and the rapid conversion of the SO2 vapor into volcanic aerosol particles.

Goldman, A.↗

Mt. Pinatubo SO2 Column Measurements From Mauna Loa

Absorption features of the nu(sub 1) band of SO2 have been identified in high resolution infrared solar absorption spectra recorded from Mauna Loa, Hawaii, on July 9 and 12, 1991, shortly after the arrival of the first eruption plume from the Mt. Pinatubo volcano in the Phillipines. A total SO2 vertical column amount of (5.1 +/- 0.5) x 10(exp 16) molecules/sq cm on July 9 has been retrieved based on nonlinear least- squares spectral fittings of 9 selected SO2 absorption features with an updated set of SO2 spectral parameters. A SO2 total column upper limit of 0.9 x 10(esp 16) molecules/sq cm deduced from measurements on September 20-24, 1991, is consistent with the dispersion of the SO2 cloud and the rapid conversion of the SO2 vapor into volcanic aerosol particles.

Goldman, A.↗

The fundamental quadrupole band of (N-14)2 - Line positions from high-resolution stratospheric solar absorption spectra

Accurate measurements of the positions of O- and S-branch lines of the (1-0) vibration-rotation quadrupole band of molecular nitrogen (N-14)2 are reported. Improved Dunham coefficients were derived from a simultaneous least squares analysis of these measurements and selected infrared and far infrared data. The new measurements were performed using stratospheric solar occultation spectra recorded with Fourier transform spectrometer instruments, operated at unapodized spectral resolutions of 0.002 and 0.01/cm.

Rinsland, C. P.↗

Analysis of atmospheric trace constituents from high resolution infrared balloon-borne and ground-based solar absorption spectra

Results of ongoing studies of high-resolution solar absorption spectra aimed at the identification and quantification of trace constituents of importance in the chemistry of the stratosphere and upper troposphere are presented. An analysis of balloon-borne and ground-based spectra obtained at 0.0025/cm covering the 700-2200/cm interval is presented. The 0.0025/cm spectra, along with corresponding laboratory spectra, improves the spectral line parameters, and thus the accuracy of quantifying trace constituents. Results for COF2, F22, SF6, and other species are presented. The retrieval methods used for total column density and altitude distribution for both ground-based and balloon-borne spectra are also discussed.

Goldman, A.↗

Determination of the altitude of the nitric acid layer from very high resolution ground-based IR solar spectra

A ground-based solar spectrum at a spectral resolution of about 0.002/cm is used to determine the altitude of the HNO3 layer. The 870/cm spectral region, which is essentially free from absorptions from other species, is employed. The data were obtained with the University of Denver 2.5-m maximum path difference Fourier Transform interferometer spectrometer system. A set of 13 HNO3 vertical profiles were used in the analysis. The best fit obtained for the 'starting' profile (which is centered at 24 km), and the best fit for the profile centered at 26 km are shown. For displacements of greater than 2 km, the discrepancy between the synthetic and observed spectra becomes readily discernible by inspection of the spectra. It is shown that the 'best fit' rms residuals are quite sensitive to the assumed altitude of the HNO3 layer.

Blatherwick, R. D.↗

High-resolution studies of atmospheric IR emission spectra

Atmospheric emission spectra obtained with two different spectrometer systems are presented. The first system (the BOMEM Michelson interferometer) is designed for emission work. Spectra were obtained under adverse conditions in the Antarctic, and are still of good absolute accuracy. The second system (a modified Bruker Instruments IFS120 very high spectral resolution interferometer) demonstrates the sensitivity that can be achieved even at higher spectral resolution. This system shows that mid-IR atmospheric emission spectra can be obtained with a good SNR in a reasonable length of time at a relatively high resolution. A properly designed high resolution system should achieve high accuracy, sensitivity, and resolution, thereby permitting measurements of many atmospheric constituents when solar spectra cannot be obtained.

Murcray, F. J.↗

Analysis of Atmospheric Trace Constituents from High Resolution Infrared Balloon-Borne and Ground-Based Solar Absorption Spectra

Recent results and ongoing studies of high resolution solar absorption spectra will be presented. The analysis of these spectra is aimed at the identification and quantification of trace constituents important in atmospheric chemistry of the stratosphere and upper troposphere. Analysis of balloon-borne and ground-based spectra obtained at 0.0025/ cm covering the 700-2200/ cm interval will be presented. Results from ground-based 0.02/ cm solar spectra, from several locations such as Denver, South Pole, M. Loa, and New Zealand will also be shown. The 0.0025/ cm spectra show many new spectroscopic features. The analysis of these spectra, along with corresponding laboratory spectra, improves the spectral line parameters, and thus the accuracy of trace constituents quantification. The combination of the recent balloon flights, with earlier flights data since 1978 at 0.02/ cm resolution, provides trends analysis of several stratospheric trace species. Results for COF2, F22, SF6, and other species will be presented. Analysis of several ground-based solar spectra provides trends for HCl, HF and other species. The retrieval methods used for total column density and altitude distribution for both ground-based and balloon-borne spectra will be presented. These are extended for the analysis of the ground-based spectra to be obtained by the high resolution interferometers of the Network for Detection of Stratospheric Change (NDSC). Progress or the University of Denver studies for the NDSC will be presented. This will include intercomparison of solar spectra and trace gases retrievals obtained from simultaneous scans by the high resolution (0.0025/ cm) interferometers of BRUKER and BOMEM.

Goldman, A.↗

The Fundamental Quadrupole Band of (14)N2: Line Positions from High-Resolution Stratospheric Solar Absorption Spectra

The purpose of this note is to report accurate measurements of the positions of O- and S-branch lines of the (1-0) vibration-rotation quadrupole band of molecular nitrogen ((14)N2) and improved Dunham coefficients derived from a simultaneous least-squares analysis of these measurements and selected infrared and far infrared data taken from the literature. The new measurements have been derived from stratospheric solar occultation spectra recorded with Fourier transform spectrometer (FTS) instruments operated at unapodized spectral resolutions of 0.002 and 0.01 /cm. The motivation for the present investigation is the need for improved N2 line parameters for use in IR atmospheric remote sensing investigations. The S branch of the N2 (1-0) quadrupole band is ideal for calibrating the line-of-sight airmasses of atmospheric spectra since the strongest lines are well placed in an atmospheric window, their absorption is relatively insensitive to temperature and is moderately strong (typical line center depths of 10 to 50% in high-resolution ground-based solar spectra and in lower stratospheric solar occultation spectra), and the volume mixing ratio of nitrogen is constant in the atmosphere and well known. However, a recent investigation has'shown the need to improve the accuracies of the N2 fine positions, intensities, air-broadened half-widths, and their temperature dependences to fully exploit this calibration capability (1). The present investigation addresses the problem of improving the accuracy of the N2 line positions.

Rinsland, C. P.↗

Long-Term Trends in the Concentrations of SF6, CHClF2, and COF2 in the Lower Stratosphere from Analysis of High-Resolution Infrared Solar Occultation Spectra

Long-term trends in the concentrations of SF6, CHClF2 (CFC-22), and COF2 in the lower stratosphere have been derived from analysis of ca. 1980 and more recent infrared solar occultation spectra recorded near 32 deg N latitude at approx. 0.02/ cm resolution. Consistent sets of line parameters and spectral calibration methods have been used in the retrievals to minimize systematic error effects. Quoted error limits are 1 sigma estimated precisions. The SF6 and CHClF2 results are based on spectra recorded by balloon-borne interferometers in March 1981 and June 1988 and a comparison of these results with the Atmospheric Trace Molecule Spectroscopy (ATMOS) Experiment/Spacelab 3 measurements obtained in May 1985 near 30 deg N latitude. In the 13-18 km altitude range the mean measured SF6 mixing ratio in parts per trillion by volume (pptv) increased from 1.17 +/- 0.21 in March 1981 to 2.02 +/- 0.20 pptv in June 1988, and the CHClF2 mixing ratio below 15 km altitude increased from 51 +/- 8 pptv in March 1981 to 102 +/- 10 pptv in June 1988. The CHClF2 retrievals used new empirical CHClF2 line parameters derived from 0.03/cm resolution laboratory spectra recorded at six temperatures between 203 and 293 K; the derived mixing ratios are approx. 30% higher than obtained with earlier sets of line parameters, thereby removing a large discrepancy noted previously between IR and in situ measurements of CHClF2. Assuming an exponential growth model for fitting the trends, SF6 and CHClF2 mean increase rates of 7.4% +/- 1.9% and 9.4% +/- 1.3% /year, are obtained, respectively, which correspond to cumulative increases by factors of approx. 1.7 and -2.0 in the concentrations of these gases over the 7.2-year measurement period. Analysis of spectra recorded in October 1979 and April 1989 yields COF2 volume mixing ratios that are respectively 0.44 +/- 0.17 and 1.21 +/- 0.24 times the ATMOS/Spacelab 3 values, from which an average COF2 increase rate of 10.3 +/- 1.8%/ year over this time period has been estimated. The present results are compared with previously reported observations and trends and with one-dimensional model calculations. The model calculated trends are in reasonably good agreement with the observations.

Rinsland, C. P.↗

Heterodyne spectrophotometry of ozone in the 9.6-micron band using a tunable diode laser

Tunable diode laser heterodyne spectrophotometry (TDLHS) has been used to make extremely high resolution (0.0003/cm) solar spectra in the 9.6-micron ozone band. Observations have shown that a signal-to-noise ratio of 120:1 (about 30 percent of theoretical) for an integration time of 1/8 s can be achieved at a resolution of 0.0013 wave numbers. The spectral data have been inverted to yield a total column amount of ozone, in good agreement with that measured at the nearby NOAA ozone monitoring facility in Boulder, Colorado. Line positions for several ozone lines in the spectral region 996-997/cm are reported. Recent improvements have produced a signal-to-noise ratio of 95:1 (about 40 percent of theoretical) at 0.0003/cm and extended the range of wavelengths which can be observed.

Mcelroy, C. T.↗

New spectral features of stratospheric trace gases

A new Michelson-type interferometer system operating in the infrared at very high resolution (0.002 to 0.003 wavenumber FWHM) was used to record numerous balloon-borne solar absorption spectra of the stratosphere, ground-based solar absorption spectra, and laboratory spectra of molecules of atmospheric interest. Results obtained are reported for several important stratospheric trace gases, HNO3, ClONO2, HO2NO2, NO2, and COF2, in the 8 to 12 micron spectral region. Many features of these gases were identified in the stratospheric spectra. Comparison of the spectra with line-by-line simulations shows previous spectral parameters are often inadequate. New analysis of high resolution laboratory and atmospheric spectra and improved theoretical calculations will be required for all bands. Preliminary versions of several sets of improved line parameters are presented.

Goldman, A.↗