F. H. Murcray

Uncertainties in modeled and measured clear-sky surface shortwave irradiances

A comparison of five independent measurements of the clear-sky downward shortwave irradiance at the surface shows that they scatter within a 5% range depending on their calibration constants. When the measurements are corrected using data from two cavity radiometers, three of the five independent measurements agree within 3 W m−2 over three clear-sky days, which is well within the estimated error limit of ±1.5%. A comparison of these three sets of irradiance measurements with the computed irradiance by a δ2-stream model reveals that the model overestimates the irradiance by 5%. Detailed investigation of the approximations and uncertainties associated with the computations (including the measurement error in the water vapor and ozone amounts, neglecting the state of polarization and trace gas absorption, the 2-stream approximation, the neglect of the spectral dependence of the surface albedo, and the uncertainties associated with aerosols) demonstrates that the discrepancy is not due to these approximations. Further analysis of the modeled and measured irradiance shows that the discrepancy is almost entirely due to the difference between modeled and measured diffuse field irradiances. An analysis of narrow-band diffuse to total irradiance ratios shows that this discrepancy is the largest near 400 nm and decreases with wavelength. These results rely on the absolute calibrations of two cavity radiometers, two shaded pyranometers, and one unshaded pyranometer, as well as ratios of irradiances measured by a multifilter rotating shadow-band radiometer. Therefore, in order for instrumental error to account for the diffuse field discrepancy, three independent measurements of the diffuse field irradiance must be biased low by at least 40%. For an aerosol to account for this discrepancy, it must be highly absorbing with a single-scattering albedo as low as 0.3. The unlikelihood of instrumental errors of 40% and aerosol single-scattering albedos of 0.3 suggests a third possibility: the neglect of some gaseous absorption process at visible wavelengths.

Validation of CH4 and N2O measurements by the cryogenic limb array etalon spectrometer instrument on the Upper Atmosphere Research Satellite

CH 4 and N 2 O are useful as dynamical tracers of stratospheric air transport because of their long photochemical lifetimes over a wide range of altitudes. The cryogenic limb array etalon spectrometer (CLAES) instrument on the NASA UARS provided simultaneous global measurements of the altitude profiles of CH 4 and N 2 O mixing ratios in the stratosphere between October 1, 1991, and May 5, 1993. Data between January 9, 1992, and May 5, 1993 (388 days), have been processed using version 7 data processing software, and this paper is concerned with the assessment of the quality of this data set. CLAES is a limb-viewing emission instrument, and approximately 1200 profiles were obtained each 24-hour period for each constituent over a nominal altitude range of 100 to 0.1 mbar (16 to 64 km). Each latitude was sampled 30 times per day between latitudes 34°S and 80°N, or 34°N and 80°S depending on the yaw direction of the UARS, and nearly all local times were sampled in about 36 days. This data set extends the altitude, latitude, and seasonal coverage of previous experiments, particularly in relation to measurements at high winter latitudes. To arrive at estimates of experiment error, we compared CLAES profiles for both gases with a wide variety of correlative data from ground-based, rocket, aircraft, balloon, and space-borne sensors, looked at the repeatability of multiple profiles in the same location, and carried out empirical estimates of experiment error based on knowledge of instrument characteristics. These analyses indicate an average single-profile CH 4 systematic error of about 15% between 46 and 0.46 mbar, with CLAES biased high. The CH 4 random error over this range is 0.08 to 0.05 parts per million, which translates to about 7% in the midstratosphere. For N 2 O the indicated systematic error is less than 15% at all altitudes between 68 and 2 mbar, with CLAES tending to be high below 6.8 mbar and low above. The N 2 O random error is 20 to 5 ppb between 46 and 2 mbar, which also translates to 7% in the low to midstratosphere. Both tracers have useful profile information to as low as 68 mbar, excluding the tropics, and as high as 0.2 mbar (CH 4 ) and 1 mbar (N 2 O). The global fields show generally good spatial correlation and exhibit the major morphological and seasonal features seen in previous global field data. Several morphological features are pointed out for regions and conditions for which there have been essentially no previous data. These include the differential behavior of the tracer isopleths near and inside the Antarctic winter vortex, and local maxima in the tropics in 1992, probably associated with the Mount Pinatubo sulfate aerosol layer. Overall, the results of this validation exercise indicate that the version 7 CH 4 and N 2 O data sets can be used with good confidence for quantitative and qualitative studies of stratospheric and lower-mesospheric atmospheric structure and dynamics.

Presence of HNO 3 in the Upper Atmosphere

Observations of absorption of solar radiation by atmospheric nitric acid obtained on different balloon flights are presented. This absorption occurs in three different wavelength intervals. The use of the very long paths, occurring near sunset, for enhancing weak absorption is discussed.

Variation of the Infrared Solar Spectrum Between 700 cm −1 and 2240 cm −1 with Altitude

A grating spectrometer with a Ge: Cu detector was flown on three balloon flights. Spectra in the 4-14.3-micro region were obtained at various altitudes from the ground through 30 km with a resolution considerably better than that achieved in previous flights. Some of the spectra were obtained over long paths at float altitude, during the sunset. Data from these flights are presented with a discussion of the significant features of the observed absorptions. Special emphasis is put on the new features observed during the sunset.

Spectral least squares quantification of several atmospheric gases from high resolution infrared solar spectra obtained at the South Pole

Abstract Spectral least squares fitting has been used to analyze high resolution (0.02 cm -1 ) i.r. solar spectra obtained at the South Pole in 1980. The spectral regions analyzed allow the simultaneous quantification of CO 2 , H 2 O, N 2 O, CH 4 , and O 3 . Information is obtained on the column amount and on the vertical distribution.

Mt. Pinatubo SO2 Column Measurements From Mauna Loa

Absorption features of the v1 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) × 1016 molecules cm−2 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 × 1016 molecules cm−2 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.

Distribution of Nitric Acid Vapor in the Stratosphere as Determined from Infrared Atmospheric Emission Data

Abstract Infrared emission spectra were measured in the stratosphere at various altitudes and from various zenith angles by means of a balloon-borne Czerny-Turner spectrometer. The equation of radiative transfer was applied to the radiances measured at 11.2μ to yield a concentration profile of HNO3 vapor. The resulting HNO3 concentration profile was characterized by a negligible concentration below 14 km, a maximum concentration of ∼(1.5±0.5)×1010 molecules cm−3 at ∼(19±5) km, and a diminishing concentration above these altitudes.

Distribution of Water Vapor in the Stratosphere as Determined from Balloon Measurements of Atmospheric Emission Spectra in the 24–29-μm Region

The stratospheric water vapor mixing ratio altitude profile has been derived from spectral observations of the downward night emission from the pure rotation water vapor lines in the 24-29-microm region of the spectrum. The data were obtained during two balloon flights, made on 22 February 1971 and on 29 June 1971, using a balloon-borne spectral radiometer with ~2 cm(-1) resolution. The observed radiances have been fitted to line-by-line, layer-by-layer radiance calculations, from which the water vapor mixing ratio between 10 km and 30 km has been flights show a broad minimum around of 6 x 10(-7)g/g to 4 x 10(-6) g/g.

Upper limit for stratospheric CLONO2 from balloon-borne infrared measurements

Balloon-borne infrared sunset solar spectra in the 780 cm−1 region have been used to derive upper limits for the amount of ClONO2 in the stratosphere. These upper limits for the volume mixing ratio are 4 × 10−11 to 2 × 100−9 between 15 and 30 km with an error factor of 2. These values only show that the postulate that ClONO2 is a temporary reservoir for ClO and NO2 cannot be ruled out.

A balloon-borne grating spectrometer.

A balloon-borne, 0.5-m, Czerny-Turner grating spectrometer has been designed and constructed at the University of Denver and has measured atmospheric transmittance in several spectral regions between 2 micro and 14 micro. These data have been obtained on a series of eleven balloon flights at three geographic locations over a period of thirty months. The solar pointing system, spectrometer optics, electronics and recording system are described. The preflight and flight performance of the spectrometer is discussed and sample data presented.