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Rinsland, C. P.

Publications and source records attributed to Rinsland, C. P..

At least 73 records · Page 4

Identification of the HNO3 3 nu(sub 9) - nu(sub 9) band Q branch in stratospheric solar occultation spectra

The spectroscopic identification for the HNO3 3 nu(sub 9) - nu(sub 9) band Q branch at 830.4/cm is reported based on 0.01/cm resolution solar occultation spectra of the lower stratosphere recorded by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer and a recent analysis of this band. Least-squares fits to 0.0025/cm resolution laboratory spectra in the Q branch region indicate an integrated intensity of 0.529 x 10(exp -18)/cm/mol/sq cm at 296 K for this weak band. Stratospheric HNO3 retrievals derived from the ATMOS data are consistent with this value within its estimated uncertainty of about +/- 30%. A set of spectroscopic line parameters suitable for atmospheric studies has been generated.

Perrin, A.↗

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.↗

Increase in Levels of Stratospheric Chlorine and Fluorine Loading between 1985 and 1992

Mixing ratios of 3.44 ppbv (parts per billion by volume) and 1.23 ppbv for HCl and HF above 50 km, surrogates for total chlorine and fluorine, have been measured by the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment on a March 1992 flight of the Space Shuttle. Compared to the measured values obtained on a 1985 flight, these correspond to a 37% and 62% increase for HCl and HF, respectively. The derived trend in HCl (approx. 0.13 ppbv per year) is in good agreement with the model-predicted increase in chlorine loading of 0.13 ppbv per year, and with the measured trends in HCl total column abundance from reported ground-based observations. The main source of this change can be attributed to the release of man-made chlorofluorocarbons (CFC's) and hydro-chloro-fluoro-carbons (HCFC's). This new value for HCl represents an upper limit to the inorganic chlorine concentration in the stratosphere available for participation in photochemical processes which destroy ozone.

Gunson, M. R.↗

Profiles of stratospheric chlorine nitrate (ClONO2) from atmospheric trace molecule spectroscopy/ATLAS 1 infrared solar occultation spectra

Stratospheric volume mixing ratio profiles of chlorine nitrate (ClONO2) have been retrieved from 0.01/cm resolution infrared solar occultation spectra recorded at latitudes between 14 deg N and 54 deg S by the atmospheric trace molecule spectroscopy Fourier transform spectrometer during the Atmospheric Laboratory for Applications and Science (ATLAS) 1 shuttle mission (March 24 to April 2, 1992). The results were obtained from nonlinear least squares fittings of the ClONO2 nu(sub 4) band Q branch at 780.21/cm with improved spectroscopic parameters generated on the basis of recent laboratory work. The individual profiles, which have an accuracy of about +/- 20%, are compared with previous observations and model calculations.

Rinsland, C. P.↗

Increase of carbonyl fluoride (COF2) in the stratosphere and its contribution to the 1992 budget of inorganic fluorine in the upper stratosphere

Volume mixing ratio profiles of COF2 have been derived through most of the stratosphere between 30 deg N and 54 deg S from series of 0.01-/cm resolution infrared solar spectra recorded in the occultation mode by the atmospheric trace molecule spectroscopy (ATMOS) instrument during the ATLAS 1 space shuttle mission of March-April 1992. When compared with similar results obtained from the ATMOS/Spacelab 3 mission of April-May 1985, the cumulative increase in the burden of COF2 in the middle and upper stratosphere was found to be 67% for that 7-year time interval. By combining a subset of these COF2 results with upper stratospheric concentrations of HF also derived from the ATMOS observations, it was further found that the budget of inorganic fluorine above 35 km altitude increased by (60 +/- 10)% over the 1985-1992 time interval, which corresponds to an average exponential rate of increase of (6.7 +/- 1/1)%/yr, or a linear rate of increase reference to 1985 of (8.5 +/- 1.3)%/yr at the 1 sigma confidence level. The total inorganic F atom volume mixing ratio found in the upper stratosphere for 1985 and 1992 and the increase during this perid mirror the rise in man-made fluorine-bearing compounds at the ground during the early to mid 1980s. This demonstrates the negligible impact of natural sources of fluorine, in particular volcanic activity, on the observed change in F in the upper stratosphere. Implications of the present findings and comparison with model results are discussed.

Zander, R.↗

Secular trend and seasonal variability of the column abundance of N2O above the Jungfraujoch station determined from IR solar spectra

Infrared solar spectra recorded at the International Scientific Station of the Jungfraujoch (3580 m altitude), Switzerland, in 1950-1951 and from 1984 to 1992 have been analyzed to determine vertical column abundances of nitrous oxide (N2O) above the station. The best fit to the relatively dense set of measurements made between 1984 and 1992 indicates a mean exponential rate of increase equal to 0.36 +/- 0.06%/yr (1 sigma) and a seasonal modulation of 7.2% peak to peak, the minimum occurring at the end of the winter and the maximum in early September. The column abundances for April of the years 1951, 1984, and 1992 were found equal to 3.49 x 10(exp 18), 3.76 x 10(exp 18), and 3.87 x 10(exp 18) molecules/sq cm, respectively; they translate into N2O concentrations at the altitude of the Jungfraujoch equal to 275, 296, and 305 parts per billion by volume. These results indicate that the exponential rate of increase for 1951-1984 was equal to 0.23 +/- 0.04%/yr (1 sigma), thus substantially lower than for the 1984-1992 time interval and that the so-called preindustrial levels of N2O pertained until 1951 with most of the increase in atmospheric N2O occurring thereafter.

Zander, R.↗

Increase of carbonyl fluoride (COF2) in the stratosphere and its contribution to the 1992 budget of inorganic fluorine in the upper stratosphere

Volume mixing ratio profiles of COF2 have been derived through most of the stratosphere between 30 deg N and 54 deg S from series of 0.01-cm(exp -1) resolution infrared solar spectra recorded in the occultation mode by the atmospheric trace molecule spectroscopy (ATMOS) instrument during the ATLAS 1 space shuttle mission of March-April 1992. When compared with similar results obtained from the ATMOS/Spacelab 3 mission of April-May 1985, the cumulative increase in the burden of COF2 in the middle and upper stratosphere was found to be 67% for that 7-year time interval. By combining a subset of these COF2 results with upper stratospheric concentrations of HF also derived from the ATMOS observations, it was further found that the budget of inorganic fluorine above 35 km altitude increased by (60 +/- 10) % over the 1985-1992 time interval, which corresponds to an average exponential rate of increase of(6.7 +/- 1.1) % /yr , or a linear rate of increase referenced to 1985 of (8.5 +/- 1.3) % /yr at the 1(sigma) confidence level. The total inorganic F atom volume mixing ratio found in the upper stratosphere for 1985 and 1992 and the increase during this period mirror the rise in man-made fluorine-bearing compounds at the ground during the early to mid 1980s. This demonstrates the negligible impact of natural sources of fluorine, in particular volcanic activity, on the observed change of F in the upper stratosphere. Implications of the present findings and comparison with model results are discussed.

Zander, R.↗

Heterogeneous conversion of N2O5 to HNO3 in the post-Mount Pinatubo eruption stratosphere

Simultaneous stratospheric volume mixing ration (VMR) profiles of dinitrogen pentoxide (N2O5) and nitric acid (HNO3) at sunrise between 25 deg N and 15 deg S latitude and profiles of HNO3 at sunset between 42 deg S and 53 deg S latitude have been derived from 0.01/cm resolution infrared solar occultation spectra recorded 9.5 months after the massive eruption of the Mount Pinatubo volcano in the Philippine Islands. The measurements were obtained by the atmospheric trace molecule spectroscopy (ATMOS) Fourier transform spectrometer during the ATLAS 1 shuttle mission (March 24 to April 2, 1992). The measured HNO3 VMRs are higher at all altitudes and latitudes than corresponding values measured by the limb infrared monitor of the stratosphere (LIMS) instrument during the same season in 1979, when the aerosol loading was near background levels. The largest relative increase in the HNO3 VMR occurred near the equator at 30-km altitude, where the ATMOS/ATLAS 1 values are about a factor of 2 higher than the LIMS measurements. Two-dimensional model calculations show that the increase in HNO3 and the ATMOS/ATLAS 1 measurement of a steep decrease in the N2O5 VMR below 30 km can be explained by the enhanced conversion of N2O5 to HNO3 on the surfaces of the Mount Pinatubo sulfate aerosols. Our profile results demonstrate the global impact of the N2O5 + H2O yields 2HNO3 heterogeneous reaction in altering the partitioning of stratospheric odd nitrogen after a major volcanic eruption.

Rinsland, C. P.↗

Temperature dependence of Lorentz air-broadening and pressure-shift coefficients of (12)CH4 lines in the 2.3-micron spectral region

High-resolution (0.01/cm) absorption spectra of lean mixtures of CH4 in dry air were recorded with the McMath-Pierce Fourier transform spectrometer (FTS) of the National Solar Observatory on Kitt Peak at various temperatures between 24 and -61 C. The spectra have been analyzed to determine the values at room temperature of pressure-broadened widths and pressure-induced shifts of more than 740 transitions. The temperature dependence of air-broadened widths and pressure-induced shifts was deduced for approx. 370 transitions in the nu(sub 1) + nu(sub 4), nu(sub 3) + nu(sub 4), and nu(sub 2) + nu(sub 3) bands of (12)CH4 located between 4118 and 4615/cm. These results were obtained by analyzing a total of 29 spectra simultaneously using a multi-spectral non-linear least-squares fitting technique. This new technique allowed the determination of correlated spectral line parameters (e.g. intensity and broadening coefficient) better than the procedure of averaging values obtained by fitting the spectra individually. This method also provided a direct determination of the uncertainties in the retrieved parameters due to random errors. For each band analysed in this study the dependence of the various spectral line parameters upon the tetrahedral symmetry species and the rotational quantum numbers of the transitions is also presented.

Devi, V. Malathy↗

Secular evolution of the vertical column abundances of CHClF2 (HCFC-22) in the Earth's atmosphere inferred from ground-based IR solar observations at the Jungfraujoch and at Kitt Peak, and comparison with model calculations

Series of high-resolution infrared solar spectra recorded at the International Scientific Station of the Jungfraujoch, Switzerland, between 06/1986 and 11/1992, and at Kitt Peak National Observatory, Tucson, Arizona (U.S.A.), from 12/1980 to 04/1992, have been analyzed to provide a comprehensive ensemble of vertical column abundances of CHClF2 (HCFC-22; Freon-22) above the European and the North American continents. The columns were derived from nonlinear least-squares curve fittings between synthetic spectra and the observations containing the unresolved 2 nu(sub 6) Q-branch absorption of CHClF2 at 829.05/cm. The changes versus time observed in these columns were modeled assuming both an exponential and a linear increase with time. The exponential rates of increase at one-sigma uncertainties were found equal to (7.0 +/- 0.35)%/yr for the Junfraujoch data and (7.0 +/- 0.23)%/yr for the Kitt Peak data. The exponential trend of 7.0%/yr found at both stations widely separated in location can be considered as representative of the global increase of the CHClF2 burden in the Earth's atmosphere during the period 1980 to 1992. When assuming two realistic vertical volume mixing ratio profiles for CHClF2 in the troposphere, one quasi constant and the other decreasing by about 13% from the ground to the tropopause, the concentrations for mid-1990 were found to lie between 97 and 111 pptv (parts per trillion by volume) at the 3.58 km altitude of the Jungfraujoch and between 97 and 103 pptv at Kitt Peak, 2.09 km above sea level. Corresponding values derived from calculations using a high vertical resolution-2D model and recently compiled HCFC-22 releases to the atmosphere, were equal to 107 and 105 pptv, respectively, in excellent agreement with the measurements. The model calculated lifetime of CHClF2 was found equal to 15.6 years. The present results are compared critically with similar data found in the literature. On average, the concentrations found here are lower by 15-20% than those derived from in situ investigations; this difference cannot be explained by the absolute uncertainty of +/- 11% assigned presently to the infrared remote measurements.

Zander, R.↗

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.↗

Profiles of Stratospheric Chlorine Nitrate from ATMOS/ATLAS 1 Infrared Solar Occultation Spectra

Stratospheric volume mixing ration profiles of chlorine nitrate have been retrieved from 0.01-cm(sub -1) resolution infrared solar occutation spectra recorded at latitudes between 14 degrees N and 54 degrees S by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer during the ATLAS 1 shuttle mission (March 24 to April 2, 1992).

chlorine nitrate ATMOS/ATLAS spectroscopic paramet↗

ATMOS/ATLAS 1 measurements of sulfur hexafluoride (SF6) in the lower stratosphere and upper troposphere

Vertical profiles of sulfur hexafluoride (SF6) in the lower stratosphere and upper troposphere have been retrieved from 0.01/cm resolution infrared solar occultation spectra recorded by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer during the ATLAS (Atmospheric Laboratory for Applications and Science) 1 shuttle mission of March 24 to April 2, 1992. Based on measurements of the unresolved absorption by the SF6 mu(sub 3) band Q branch at 947.9/cm, average SF6 volume mixing ratios and 1-sigma uncertainties of 3.20 +/- 0.54 parts per trillion by volume (pptv; 10(exp -12) ppv) at 200 mbar (approximately 11.8 km) declining to 2.86 +/- 0.29 pptv at 100 mbar (approximately 16.2 km) and 1.95 +/- 0.50 pptv at 30 mbar (approximately 23.9 km) have been retrieved. The profiles show no obvious dependence with latitude over the range of the measurements (eight occultations spanning 28 deg S to 54 deg S). Assuming an exponential growth model and applying a correction for the interhemispheric concentration difference, an average SF6 rate of increase of 8.7 +/- 2.2% per year, 2 sigma, between 12 and 18 km has been derived by fitting the present measurements, ATMOS measurements from the April-May 1985 Spacelab 3 mission, and balloon-borne IR measurements obtained in March 1981 and June 1988.

Rinsland, C. P.↗

Stratospheric N2O5, CH4, and N2O profiles from IR solar occultation spectra

Stratospheric volume mixing ratio profiles of N2O5, CH4, and N2O have been retrieved from a set of 0.052/cm resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur l'Adour, France (44 N latitude) on 12 October 1990. The N2O5 results have been derived from measurements of the integrated absorption by the 1246/cm band. Assuming a total intensity of 4.32 x 10 exp -17 cm/molecule/sq cm independent of temperature, the retrieved N2O5 volume mixing ratios in ppbv, interpolated to 2 km height spacings, are 1.64 +/- 0.49 at 37.5 km, 1.92 +/- 0.56 at 35.5 km, 2.06 +/- 0.47 at 33.5 km, 1.95 +/- 0.42 at 31.5 km, 1.60 +/- 0.33 at 29.5 km, 1.26 +/- 0.28 at 27.5 km, and 0.85 +/- 0.20 at 25.5 km. Error bars indicate the estimated 1-sigma uncertainty including the error in the total band intensity. The retrieved profiles are compared with previous measurements and photochemical model results.

Camy-Peyret, C.↗