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Rinsland, Curtis P.

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

At least 37 records · Page 2

Air- and N2-Broadening Coefficients and Pressure-Shift Coefficients in the C-12(O2-16) Laser Bands

In this paper we report the pressure broadening and the pressure-induced line shift coefficients for 46 individual rovibrational lines in both the (12)C(16)O2, 00(sup 0)1-(10(sup 0)0-02(sup 0)0)I, and 00(sup 0)1-(10(sup 0)0-02(sup 0)0)II, laser bands (laser band I centered at 960.959/cm and laser band II centered at 1063.735/cm) determined from spectra recorded with the McMath-Pierce Fourier transform spectrometer. The results were obtained from analysis of 10 long-path laboratory absorption spectra recorded at room temperature using a multispectrum nonlinear least-squares technique. Pressure effects caused by both air and nitrogen have been investigated. The air-broadening coefficients determined in this study agree well with the values in the 1996 HITRAN database; ratios and standard deviations of the ratios of the present air-broadening measurements to the 1996 HITRAN values for the two laser bands are: 1.005(15) for laser band I and 1.005(14) for laser band II. Broadening by nitrogen is 3 to 4% larger than that of air. The pressure-induced line shift coefficients are found to be transition dependent and different for the P- and R-branch lines with same J" value. No noticeable differences in the shift coefficients caused by air and nitrogen were found. The results obtained are compared with available values previously reported in the literature.

Devi, V. Malathy↗

Self-Broadening and Self-Shift Coefficients in the Fundamental Band of 12C 16O

High quality and precise measurements of self-broadened and self-shift coefficients in the fundamental band of C-12O-16 were made using spectra recorded at room temperature with the high-resolution (0.0027 cm(exp -1)) McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectral region under investigation (2008-2247 cm(exp -1)) contains the P(31) to R(31) transitions. The data were obtained using a high-purity natural isotopic sample ofcarbon monoxide and two absorption cells with pathlengths of 4.08 and 9.98 cm, respectively. Various pressures of CO were used, ranging between 0.25 and 201.2 Torr. The results were obtained by analyzing five spectra simultaneously, using a multispectrum nonlinear least-squares fitting technique. The self-broadened coefficients ranged from 0.0426(2) cm(exp -1) atm(exp -1) at 296 K to 0.0924(2) cm(exp -1) atm(exp -1) at 296 K, while the pressure-induced shift coefficients varied between -0.0042(3) cm(exp -1) atm(exp -1) at 296 K and +0.0005(l) cm(exp -1) atm(exp -1) at 296 K. The value in parentheses is the estimated uncertainty in units of the last digit. The self-broadened coefficients of lines with same values of m in the P and R branches agree close to within experimental uncertainties while the self-shift coefficients showed considerable variation within and between the two branches. The mean value of the ratios of P branch to R branch self-broadened coefficients was found to be 1.01 with a standard deviation of + or - 0.01. Comparisons of the results with other published data were made.

Devi, Malathy V.↗

Pressure Broadening and Pressure Shift Coefficients in the 2nu(sup 0, sub 2) and nu(sub 1) Bands of (16)O(13)C(18)O

In this study we report the first measurements of the pressure broadening and the pressure-induced line shift coefficients due to air and nitrogen for 93 individual rovibrational lines, P(46) to R(46) and P(50) to R(45), respectively, belonging to the 2nu(sup 0, sub 2) and nu(sub 1) bands of (16)O(13)C(18)O. The results were obtained by analyzing ten long path, high-resolution laboratory, absorption spectra using a multispectrum nonlinear least-squares technique. Broadening due to nitrogen was about 4% larger than by air. Similar to broadening coefficients, the pressure-shift coefficients were found to be transition dependent, but different for the P- and R-branch lines with the same rotational quantum number, J. Except for a few R-branch lines, the measured shift coefficients were negative. The shift coefficients varied from + 4 x 10(exp -3)/cm.atm at 296 K to -5.6 x 10(exp -3)/cm.atm at 296 K. Comparisons of the broadening and shift coefficients between the two bands, between the P and R branches, and between the two broadening gases are reported. No significant difference between shift coefficients of the two bands or the two broadening gases was observed. The results obtained were compared with those reported in the literature for the more abundant (12)C(16)O2 species.

Devi, V. Malathy↗

Retrieval of HCl and HNO3 Profiles from Ground-Based FTIR Data Using SFIT2

A recently developed algorithm, SFIT2, is used to assess profile information available in ground-based FTIR measurements of HCl and HNO3 and to analyze spectra recorded at Lauder, New Zealand, and Arrival Heights, Antarctica. It is shown that the altitude range of HCI retrievals may be extended by using multiple spectral lines. A preliminary analysis of a five year record of HNO3 at Lauder shows that the Pinatubo aerosol caused a large increase of HNO3 in a layer at about 20-30 km while having little effect at lower altitude.

Connor, Brian↗

Northern and Southern Hemisphere Ground-Based Infrared Spectroscopic Measurements of Tropospheric Carbon Monoxide and Ethane

Time series of CO and C2H6 measurements have been derived from high resolution infrared solar spectra recorded in Lauder, New Zealand (45.0 deg S, 169.7 deg E, altitude 0.37 km) and at the U. S. National Solar Observatory (31.90 deg N, 111.6 deg W, altitude 2.09 km) on Kitt Peak. Lauder observations were obtained between July 1993 and November 1997 while the Kitt Peak measurements were recorded between May 1977 and December 1997. Both databases were analyzed with spectroscopic parameters that included significant improvements for C2H6 relative to previous studies. Target CO and C2H6 lines were selected to achieve similar vertical samplings based on averaging kernels. These calculations show that partial columns from layers extending from the surface to the mean tropopause and from the mean tropopause to 100 km are nearly independent. Retrievals based on a semiempirical application of the Rodgers optimal estimation technique are reported for the lower layer, which has a broad maximum in sensitivity in the upper troposphere. The Lauder CO and C2H6 partial columns exhibit highly asymmetrical seasonal cycles with minima in austral autumn and sharp peaks in austral spring. The spring maxima are the result of tropical biomass burning emissions followed by deep convective vertical transport to the upper troposphere and long-range horizontal transport. Significant year-to-year variations are observed for both CO and C2H6, but the measured trends, (+0.37 +/- 0.57)%/ yr and (-0.64 +/- 0.79)%/ yr, 1 sigma, respectively, indicate no significant long-term changes. The Kitt Peak data also exhibit CO and C2H6 seasonal variations in the lower layer with trends equal to (-0.27 +/- 0.17)%/ yr and (-1.20 +/- 0.35)%/ yr, 1 sigma, respectively. Hence, a decrease in the Kitt Peak tropospheric C2H6 column has been detected, though the CO trend is not significant. Both measurement sets are compared with previous observations, reported trends, and three-dimensional model calculations.

Rinsland, Curtis P.↗

Absolute Rovibrational Intensities of C-12O2-16 Absorption Bands in the 3090-3850/ CM Spectral Region

A multispectrum nonlinear least-squares fitting technique has been used to determine the absolute intensities for approximately 1500 spectral lines in 36 vibration - rotation bands Of C-12O2-16 between 3090 and 3850/ cm. A total of six absorption spectra of a high- purity (99.995% minimum) natural sample of carbon dioxide were used in the analysis. The spectral data (0.01/cm resolution) were recorded at room temperature and low pressure (1 to 10 Torr) using the McMath-Pierce Fourier transform spectrometer of the National Solar Observatory (NSO) on Kitt Peak. The absorption path lengths for these spectra varied between 24.86 and 385.76 m. The first experimental determination of the intensity of the theoretically predicted 2(nu)(sub 2, sup 2) + nu(sub 3) "forbidden" band has been made. The measured line intensities obtained for each band have been analyzed to determine the vibrational band intensity, S(sub nu), in /cm/( molecule/sq cm) at 296 K, square of the rotationless transition dipole moment |R|(exp 2) in Debye, as well as the nonrigid rotor coefficients. The results are compared to the values listed in the 1996 HITRAN database which are obtained using the direct numerical diagonalization (DND) technique as well as to other published values where available.

Devi, V. Malathy↗

Airborne Infrared Spectroscopy of 1994 Western Wildfires

In the summer of 1994 the 0.07/ cm resolution infrared Airborne Emission Spectrometer (AES) acquired spectral data over two wildfires, one in central Oregon on August 3 and the other near San Luis Obispo, California, on August 15. The spectrometer was on board a NASA DC-8 research aircraft, flying at an altitude of 12 km. The spectra from both fires clearly show features due to water vapor, carbon dioxide, carbon monoxide, ammonia, methanol, formic acid, and ethylene at significantly higher abundance and temperature than observed in downlooking spectra of normal atmospheric and ground conditions. Column densities are derived for several species, and molar ratios are compared with previous biomass fire measurements. We believe that this is the first time such data have been acquired by airborne spectral remote sensing.

Worden, Helen↗

Airborne Infrared Spectroscopy of 1994 Western Wildfires

In the summer of 1994, the 0.07cm -1 resolution infrared Airborne Emission Spectrometer (AES) acquired spectral data over two wildfires, one in central Oregon on August 3 and the other near San Luis Obispo, California on August 15. The spectrometer was on board a NASA DC-8 research aircraft, flying at an altitude of 12 km.

Spectroscopy↗

Infrared spectroscopic measurements of the total column abundance of ethan (C2H6) above Lauder, New Zealand

Total vertical column aboundances of atmospheric ethane (C2H6) have been retrieved form more than 350 high-resolution infrared solar spectra recorded on 129 days between December 1992 and March 1994 at the Network for the Detection of Stratospheric Change (NDSC) station in Lauder, New Zealand (latitude 45.04 deg S, 169.68 deg E, 0.37 km altitude). The results are based on nonlinear least squares fits to narrow spectral intervals containing the unresolved C2H6 nu (sub 7) band (P)Q(sub 3) and (R)Q(sub 0) subbranches at 2976.8 and 2986.7/cm. The measured Lauder column abundances show a pronounced seasonal cycle with a maximum value of (8.6 +/- 0.5) x 10(exp 15) molecules/sq cm in September and a minimum value of (3.8 +/- 0.5) x 10 (exp 15) molecules/sq cm in February. Assuming a realistic vertical distribution for C2H6, these values correspond to surface level volume-mixing ratios of 0.52 and 0.23 ppbv (parts per billion by volume), respectively. The phase and relative amplitude of the Lauder C2H6 seasonal cycle are similar to corresponding values determined from infrared measurements at the Jungfraujoch (46.55 deg N, 7.98 deg E, 3.58 km altitude) and Mauna Loa (latitude 19.5 deg N, longitude 155.6 deg W, 3.5 km altitude) NDSC stations, but the inferred absolute magnitudes of the Lauder surface level mixing ratios during the same season are significantly lower. The Lauder C2H6 measurements are also compared with published southern hemisphere surface level sampling measurements and two-dimensional model calculations.

Rinsland, Curtis P.↗

The effect of the Mt. Pinatubo aerosol on the NHO3 column over Mauna Loa, Hawaii

A very high resolution infrared solar spectrometer system for the Network for Detection of Stratospheric Change has been routinely operated at the Mauna Loa Observatory in Hawaii since November, 1991. Solar absorption spectra are normally taken one day a week at sunrise. We report the analysis of these spectra for the vertical column amount of nitric acid (HNO3) vapor. The observations began four months after the arrival of volcanic aerosols from Mt. Pinatubo over the site. Although quite variable, total HNO3 columns were initially about 7 x 10(exp 15) molecules/sq cm and have decreased about 30% in the following two years.

David, Shelle J.↗

Southern hemisphere ground based measurements of Carbonyl Fluoride (COF2) and Hydrogen Fluoride (HF): Partitioning between Fluoride reservoir species

We report infrared ground based total column measurements of the stratospheric fluorine reservoir gases COF2 and HF above Lauder, New Zealand (45 deg S, 167.8 deg E) obtained between April 1993 and January 1994. The average retrieved COF2 and HF total columns are 2.81(+/- 0.56) x 10(exp 14) and 9.91(+/- 1.09) x 10(exp 14) molecules/sq cm respectively. The daily average COF2 and HF columns are correlated; this correlation is likely the result of dynamics. The average HF/COF2 column ratio on days with measurements of both HF and COF2 is 3.63 (+/- 0.55). Comparison of this ratio with model calculations implies that the quantum yield for COF2 photolysis is near unity. Our measured COF2 columns are higher than all previously reported values, but inconsistencies among the earlier measurements and uncertainty in the latitudinal gradient of the COF2 column preclude an accurate determination of the long-term COF2 trend.

Reisinger, Andreas R.↗

Seasonal cycle in atmospheric HCl at 45 deg S

High resolution Fourier transform infrared interferometric atmospheric solar absorption measurements have been performed at the National Institute for Water and Atmospheric Research Laboratory at Lauder, New Zealand on a routine basis since October 1989. This laboratory has been selected as the Mid-latitude Charter Site of the Network for the Detection of Stratospheric Change and is at a latitude of 45 deg S. Particular attention has been paid to the absorption by atmospheric hydrogen chloride at 2925.9 cm(exp -1) and in this paper the results of the seasonal cycle in CHl above Lauder will be presented. Because of the very clean troposphere at this site, the CHl column measured from the ground is essentially a stratospheric column measurement.

Matthews, W. Andrew↗

Air-, N2-, and O2-broadening and shift coefficients in the nu(3) spectral region of (C-12)H4

Results are presented of an analysis of 29 room-temperature laboratory absorption spectra of a dilute CH4 sample in dry air, N2, and O2 at total pressures ranging from 60 to 550 torr, yielding values of pressure-broadening and pressure-induced-shift coefficients for more than 450 vibration-rotation transitions in the nu(3), nu(2) + nu(4), and 2nu(2)-super-2 bands of (C-12)H4. Comparisons of the present results for the nu(3) and nu(2) + nu(4) bands with previous measurements on other bands and isotopes of CH4 show that, for a given transition, broadening by air and N2 are nearly equal, and broadening by O2 is smaller by less than 10 percent. It is also found that the pressure shift coefficients are more vibrational dependent than the pressure broadening coefficients.

Benner, D. C.↗

Atmospheric sulfur hexafluoride - Sources, sinks and greenhouse warming

An estimate is obtained of worldwide production of SF6, from which a global emission rate is derived and extrapolated for the next 20 years. The atmospheric lifetime of SF6 is then estimated based on a known mechanism (e.g., photolysis and atmospheric oxidation) and/or on the mass balance method. Finally, the radiative forcing of SF6 is calculated based on recent laboratory IR absorption data, and the expected warming over the time period 1950-2010 is computed for several emission scenarios. Calculations showed that SF6 is 3 times more effective as a greenhouse gas compared to CFC 11 on a per-molecule basis. However, based on projected emission scenarios, the expected warming from SF6 through 2010 is small (0.004 C), compared to the warming from CO2 and other trace gases (0.8 C).

Ko, Malcolm K. W.↗

Atmospheric Sulfur Hexafluoride: Sources, Sinks and Greenhouse Warming

Model calculations using estimated reaction rates of sulfur hexafluoride (SF6) with OH and 0('D) indicate that the atmospheric lifetime due to these processes may be very long (25,000 years). An upper limit for the UV cross section would suggest a photolysis lifetime much longer than 1000 years. The possibility of other removal mechanisms are discussed. The estimated lifetimes are consistent with other estimated values based on recent laboratory measurements. There appears to be no known natural source of SF6. An estimate of the current production rate of SF6 is about 5 kt/yr. Based on historical emission rates, we calculated a present-day atmospheric concentrations for SF6 of about 2.5 parts per trillion by volume (pptv) and compared the results with available atmospheric measurements. It is difficult to estimate the atmospheric lifetime of SF6 based on mass balance of the emission rate and observed abundance. There are large uncertainties concerning what portion of the SF6 is released to the atmosphere. Even if the emission rate were precisely known, it would be difficult to distinguish among lifetimes longer than 100 years since the current abundance of SF6 is due to emission in the past three decades. More information on the measured trends over the past decade and observed vertical and latitudinal distributions of SF6 in the lower stratosphere will help to narrow the uncertainty in the lifetime. Based on laboratory-measured IR absorption cross section for SF6, we showed that SF6 is about 3 times more effective as a greenhouse gas compared to CFC 11 on a per molecule basis. However, its effect on atmospheric warming will be minimal because of its very small concentration. We estimated the future concentration of SF6 at 2010 to be 8 and 10 pptv based on two projected emission scenarios. The corresponding equilibrium warming of 0.0035 C and 0.0043 C is to be compared with the estimated warming due to CO2 increase of about 0.8 C in the same period.

Sze, Nien Dak↗

Analysis of the upper atmosphere CO2(nu-2) vibrational temperatures retrieved from ATMOS/Spacelab 3 observations

An analysis of the upper atmospheric (80-116 km) CO2(nu-2) vibrational temperatures retrieved from atmospheric trace molecule spectroscopy (ATMOS) experiment Spacelab 3 spectra by using a nonlocal thermodynamic equilibrium (non-LTE) radiative transfer model is presented. Thermal collisions with atmospheric atomic oxygen keep this vibrational state very close to LTE up to around 100 km. Above this height, the different deviations from LTE retrieved from ATMOS/Spacelab 3 spectra for the Northern and the Southern Hemispheres are explained in terms of this collisional process and in terms of the different kinetic temperature profiles measured at those locations. From these simultaneous observations of the kinetic and CO2(nu-2) vibrational temperatures, a deactivation rate of CO2(nu-2) by O(3P) has been derived which leads to a rate coefficient value between 3 and 6 x 10 exp -12 cu cm/s and favors an independent or negative temperature dependence rate constant for the atmospheric temperature range. Cooling rates induced by the CO2 15-micron fundamental band in the upper mesosphere and lower thermosphere were derived from the simultaneous kinetic temperature, CO2(nu-2) vibrational temperature, and CO2 concentration, as measured by ATMOS/Spacelab 3, and found to be a factor of between 5 and 10 times larger than those generally accepted until very recently.

Lopez-Puertas, M.↗

Measurements of pressure broadening and pressure shifting by nitrogen in the 4.3-micron band of (C-12)(O-16)2

Lorentz-broadening coefficients and pressure-induced line-shift coefficients of 34 individual lines have been determined for the P(40) to R(40) vibration-rotation transitions in the nu(3) fundamental of CO2 using N2 as the buffer gas. The parameters were derived from 0.01/cm resolution infrared absorption spectra recorded using the McMath Fourier transform spectrometer and a nonlinear, least-squares fitting algorithm. It is concluded that the N2-broadening coefficients obtained in the present study agree well with recent high resolution measurements. The results are considered to be of importance not only for predicting the infrared spectrum of the atmosphere due to CO2 absorption or emission but also for verifying theoretical calculations.

Devi, V. M.↗