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Murcray, F. J.

Publications and source records attributed to Murcray, F. J..

At least 37 records · Page 2

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 in the lower stratosphere are derived using results from analyses of the 1980 and of several more recently obtained IR solar occultation spectra. Results show that the increase rates of SF6 and CHClF2 were about 7.4/yr and 9.4/yr, respectively, which correspond to cumulative increases by factors of about 1.7 and 2.0 in the concentrations of these gases over the 7.2 yr measurement period. The average increase rate for COF2 was 10.3/yr over the same time period. The present results are compared with previously reported observations and trends and with one-dimensional model calculations.

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.↗

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.↗

Infrared emission measurements of morning stratospheric N2O5

Infrared emission spectra obtained during a balloon flight of the Air Force Geophysics Laboratory Stratospheric Cryogenic Interferometer Balloon Experiment system by the University of Denver are used to measure stratospheric N2O5 after sunrise over New Mexico (latitude 33 deg N). This is the first daytime measurement of N2O5. Comparisons with photochemical modeling show consistency between the observed and predicted decline of N2O5 during the morning hours.

Blatherwick, R. D.↗

New spectral features of stratospheric trace gases identified from high-resolution infrared balloon-borne and laboratory spectra

A new Michelson-type interferometer system operating in the infrared at very high resolution has been 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. In the present work results obtained for several important stratospheric trace gases, HNO3, CIONO2, HO2NO2, NO2, and COF2, in the 8- to 12-micron spectral region are reported. Many new features of these gases have been identified in the stratospheric spectra. Comparison of the new spectra with line-by-line simulations shows that previous spectral line parameters are often inadequate and that new analysis of high-resolution laboratory and atmospheric spectra and improved theoretical calculations will be required for many bands. Preliminary versions of several sets of improved line parameters under development are discussed.

Goldman, A.↗

Isotopic abundances of stratospheric ozone from balloon-borne high-resolution infrared solar spectra

IR solar absorption spectra at 0.002-0.0003/cm resolution in the 10-micron region obtained during two balloon flights near 32 deg N latitude are examined to determine the isotopic ratios of (O-16)(O-16)(O-18) and (O-16)(O-18)(O-16) relative to normal ozone in the stratosphere. For November 18, 1987, the results show column-averaged isotopic enhancement ratios of 1.20 + or - 0.14 and 1.40 + or - 0.18 for (O-16)(O-18)(O-16)/(O-16)(O-16)(O-16) and (O-16)(O-16)(O-18)/(O-16)(O-16)(O-16), respectively. The corresponding values for June 6, 1988, show ratios of 1.16 + or - 0.08 and 1.25 + or - 0.12. The results are compared with heavy-to-normal O3 ratios obtained using other techniques.

Goldman, A.↗

Intercomparison of NO column measurements during MAP/GLOBUS 1985

Simultaneous NO column measurements made in France in September, 1985, using several techniques, are compared with one another. The observed NO distributions vary significantly from day to day. It is shown that NO measurements using IR or UV absorption are self-consistent and show good agreement with predictions from a one-dimensional photochemical model. In situ chemiluminescent measurements produced NO columns which were systematically higher than those predicted.

Mckenzie, R. L.↗

Infrared measurements of atmospheric gases above Mauna Loa, Hawaii, in February 1987

The IR absorptions spectra of 13 minor and trace atmospheric gases, recorded by the NOAA's Geophysical Monitoring for Climate Change (GMCC) program station at Mauna Loa, Hawaii, for four days in February 1987, were analyzed to determine simultaneous total vertical column amounts for these gases. Comparisons with other data indicate that the NOAA GMCC surface volume mixing ratios are good measures of the mean volume mixing ratios of these gases in the troposphere and that Mauna Loa is a favorable site for IR monitoring of atmospheric gases. The ozone total columns deduced from the IR spectra agreed with the correlative Umkehr observations.

Rinsland, C. P.↗

Infrared Measurements of Atmospheric Gases Above Mauna Loa, Hawaii, in February 1987

Infrared solar absorption spectra recorded at 0.02/ cm resolution from the National Oceanic and Atmospheric Administration (NOAA) Geophysical Monitoring for Climate Change (GMCC) program station at Mauna Loa, Hawaii (latitude 19.5 deg N, longitude 155.6 deg W, elevation 3.40 km), in February 1997 have been analyzed to determine simultaneous total vertical column amounts for 13 atmospheric gases. Average tropospheric concentrations of CO2, N2O, CH4, and CHCIF2 and the daytime diurnal variations or the total columns of NO and NO2 have also been inferred. The retrieved total columns (in molecules /sq cm) of the nondiurnally varying gases are 1.6 +/- 0.2 x 10(exp 15) for HCl, 5.9 +/- 1.2 x 10(exp 15) for HNO3, 2.0 +/- 0.2 x 10(exp 21) for H2O16, 4.4 +/- 0.7 x 10(exp 18) for H2O18, 2.7 +/- 0.1 x 10(exp 17) for HDO, 2.3 +/- 0.2 x 10(exp 19) for CH4, 5.0 +/- 0.5 x 10(exp 21) for CO2, 6.7 +/- 0.8 x 10(exp 18) for O3, 4.3 +/- 0.4 x 10(exp 18) for N2O, 1.0 +/- 0.2 x 10(exp 16) for C2H6, and 9.7 +/- 2.5 x 10(exp 14) for CHClF2. We compare the total column measurements of HCl and HNO3 with previously reported ground-based, aircraft, and satellite measurements. The results for HCl are or particular interest because of the expected temporal increase in the concentration of this gas in the stratosphere. However, systematic differences among stratospheric HCl total column measurements from 1978 to 1980 and the absence of observations of free tropospheric HCl above Mauna Loa make it impossible to obtain a reliable estimate of the trend in the total burden of HCl. The measured HNO3 total column is consistent with aircraft measurements from approx. 12 km altitude. The O3 total column deduced from the IR spectra agrees with correlative Mauna Loa Umkehr measurements within the estimated error limits. The column-averaged D/H ratio of water vapor is (68 +/- 9) x- 10(exp -6), which is 0.44 +/- 0.06 times the reference value of 155.76 x 10(exp -6) for standard mean ocean water (SMOW). This large depletion in the D content of water vapor is similar to published measurements of the upper troposphere and lower stratosphere. Average tropospheric concentrations deduced for CO2, N2O, and CH4 are in good agreement with correlative NOAA GMCC surface data, indicating consistency between the measurement techniques for determining tropospheric volume mixing ratios. Results of the present study indicate that Mauna Loa is a favorable site for infrared monitoring of atmospheric gases. The site is particularly favorable for monitoring the tropospheric volume mixing ratios of long-lived gases, since the high altitude of the tropopause reduces corrections required to account for the decrease in volume mixing ratio in the stratosphere.

Rinsland, C. P.↗

Infrared measurements in the spring 1987 ozone hole

Solar spectra were recorded from Arrival Heights (McMurdo), Antartica, with a FTIR system during the austral spring of 1987. Spectra were recorded on 22 days from September 13 through October 28. The instrument was setup with 2 detectors for simultaneous operation in 2 wavelength regions. Several stratospheric gases have measurable absorptions in these regions including HCl, HNO3, O3, ClONO2, and NO2. The system is equipped with an automatic solar tracking system and records data on tape cartridges. A portable personal computer allows Fourier transforming and initial processing of some of the data. The HNO3 gas column amount shows large variations, but no apparent correlation with stratospheric temperature. The HCl column shows a steady increase from 0.9 x 10 to the 15th power molecules/sq.cm. on September 13 to 1.5 x 10 to the 15th power on October 6. McMurdo moved out of the polar vortex for a few days, and the HCl column jumped to 2.9 x 10 to the 15th power by October 11. Although McMurdo moved back under the vortex, the HCl continued to increase, reaching 3.4 x 10 to the 15th power at the end of the period.

Murcray, F. J.↗

Infrared measurements of column abundances of several trace gases in the Antarctic atmosphere

Atmospheric emission measurements were made in 1978 from an LC 130 aircraft from Point Mugu, CA, to McMurdo Station, Antarctica, and from McMurdo over the Antarctic continent on several different flights. These included a number of flights over the South Pole. In December 1980, infrared solar spectra were obtained from the ground at South Pole Station. Infrared solar spectra were also obtained from South Pole during late November and early December of 1986. These latter measurements were extended to cover additional spectral regions to obtain column densities of a number of additional constituents. The results obtained from these measurement series are reviewed and, where measurements were made during both periods, compared. Spectral absorption or emission features due to HNO3, NO, NO2, HCl, (H-16)2O, (H-18)2O, HDO, CH4, and N2O were used to obtain data on the total column abundances for these compounds.

Murcray, F. J.↗

Infrared measurements of several nitrogen species above the South Pole in December 1980 and November-December 1986

This paper reports the results of the determinations of total column amounts of HNO3 for December 1980 and November 1986, and NO and NO2 for November-December 1986, deduced from ground-based high-resolution IR solar absorption spectra recorded from the Amundsen-Scott South Pole Station. The measurements were obtained shortly after the austral spring ozone minimum and define, for the first time, the ambient levels of these nitrogen species immediately following the break up of the polar vortex.

Murcray, F. J.↗

Infrared Measurements of Several Nitrogen Species Above the South Pole in December 1980 and November - December 1986

In December 1980 and November-December 1986, the University of Denver atmospheric spectroscopy group recorded numerous high-resolution infrared solar absorption spectra from the Amundsen-Scott south pole station. These spectra were obtained by Frank J. Murcray and Frank H. Murcray with a Michelson-type Fourier transform spectrometer and show absorption features of a number of minor and trace atmospheric gases with a minimum of atmospheric water vapor absorption. Quantifications of the total column amounts of O3, CH4, N2O, and H2O from the 1980 observations and RCI from the 1986 observations have been reported along with an atlas of the 750-960/ cm spectral region. In the present study, we report measurements of HNO3 total column amounts deduced from both data sets and NO, and NO2 total column amounts from the 1986 data set. Nitric acid may be important in the chemistry which creates the spring Antarctic ozone minimum, since it may condense in the cold winter polar stratosphere and become the dominant component of polar stratospheric clouds. The present measurements were obtained shortly after the austral spring ozone minimum and define for the first time the ambient levels of these nitrogen species immediately following the breakup of the polar vortex.

Murcray, F. J.↗

Quantification of HCl from High Resolution Infrared Solar Spectra Obtained at the South Pole in December 1986

Ground-based infrared solar spectra at 0.02/ cm resolution obtained at the Amundsen-Scott South Pole station in December 1986 have been analysed for the atmospheric content of HCl. Nonlinear least-squares spectral fitting applied to the spectra yields a total HCl column amount of (6.4 +/- 0.8) x 10(exp 15) molec/sq cm, most being stratospheric. This amount is larger than that extrapolated from earlier results on the latitudinal distribution of atmospheric HCl.

Goldman, A.↗

Quantification of HCl from high-resolution, ground-based, infrared solar spectra in the 3000 per cm region

Recent ground-based infrared solar spectra at 0.02 per cm resolution in the 3000 per cm region have been analyzed for the atmospheric content of HCl. Nonlinear spectral least-squares fitting applied to spectra obtained at several zenith angles shows little sensitivity of the results to tropospheric HCl but provides an accurate measurement of the total column amount.

Goldman, A.↗