Infrared measurements of atmospheric constituents

The objective of this program is to obtain data concerning the concentration versus altitude of various constituents of interest in the photochemistry of the stratospheric ozone layer. Data pertinent to this objective are obtained using balloon-borne instruments to measure the atmospheric transmission and emission in the mid infrared. In addition to obtaining constituent profile information, the spectral data obtained are also used to identify absorption or emission features which may interfere with the retrieval of constituent data from satellite instruments using lower spectral resolution. The spectral resolution obtained with the solar spectral system is 0.0025 cm(exp -1) and represents about a factor of 5 greater resolution than any solar spectra previously obtained in this spectral region. As a result of the increase in spectral resolution, a large number of features are observed in these spectra which were not observed in previous studies. Identification and analysis of these features is in progress. The results of this analysis to date shows a number of HNO3 features which have not been observed before, and these occur where they will interfere with the retrieval of other constituents. An example of the interference is the occurrence of features in the 780.2 cm(exp -1) region which overlap the ClONO2 feature which will be used for retrieval of ClONO2 by the CLAES instrument on UARS. A number of features due to COF2 were also identified in the 1250 cm(exp -1) region which may interfere with retrieval of N2O5

Analysis of atmospheric spectra for trace gases

The objective is the comprehensive analysis of high resolution atmospheric spectra recorded in the middle-infrared region to obtain simultaneous measurements of coupled parameters (gas concentrations of key trace constituents, total column amounts, pressure, and temperature) in the stratosphere and upper troposphere. Solar absorption spectra recorded at 0.002 and 0.02 cm exp -1 resolutions with the University of Denver group's balloon-borne, aircraft borne, and ground-based interferometers and 0.005 to 0.01 cm exp -1 resolution solar spectra from Kitt Peak are used in the analyses

Collecting, analyzing and archiving of ground based infrared solar spectra obtained from several locations

The infrared solar spectrum as observed from the ground under high resolution contains thousands of absorption lines. The majority of these lines are due to compounds that are present in the Earth's atmosphere. Ground based infrared solar spectra contain information concerning the composition of the atmosphere at the time the spectra were obtained. The objective of this program is to record solar spectra from various ground locations, and to analyze and archive these spectra. The analysis consists of determining, for as many of the absorption lines as possible, the molecular species responsible for the absorption, and to verify that current models of infrared transmission match the observed spectra. Archiving is an important part of the program, since a number of the features in the spectra have not been identified. At some later time, when the features are identified, it will be possible to determine the amount of that compound that was present in the atmosphere at the time the spectrum was taken

Measurements of stratospheric odd nitrogen at Arrival Heights, Antarctica, in 1991

An FTIR spectrometer was installed at Arrival Heights, Antarctica (78 deg S, 167 deg E) in February 1991 to measure the evolution of stratospheric HNO3 during the year. In particular, it was the intention to make the first observations of HNO3 trends during autumn, concurrently with ongoing measurements of column NO2 made with a grating spectrometer. The time-series of NO2 in the Antarctic shows a rapid decline in the column amount during autumn, and a slow recovery in spring, as the photochemical conditions move the species to and from higher storage reservoirs. The new nitric acid data show for the first time that during autumn the vertical column increases from approximately 1.9 x 10(exp 16) molecule cm(exp -2) at day 30 to approximately 3.1 x 10(exp 16) molecule cm(exp -2) by day 100. When the sun returns in spring, it is found that the column amount has fallen to about half the value at the end of autumn. Spring amounts are variable, but as found in the data from previous years remain low inside the vortex. The autumn increase is attributed to the heterogeneous conversion of N2O5 to gas-phase HNO3 on background aerosols. Low nitric acid column amounts at the start of spring suggest that the HNO3 has moved from the gas to the condensed phase on polar stratospheric clouds with the advent of low temperatures during the polar night

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

Multiyear infrared solar spectroscopic measurements of HCN, CO, C2H6,and C2H2 tropospheric columns above Lauder, New Zealand (45 degrees S latitude)

[1] Near-simultaneous, 0.0035 or 0.007 cm(-1) resolution infrared solar absorption spectra of tropospheric HCN, C2H2, CO, and C2H6 have been recorded from the Network for the Detection of Stratospheric Change station in Lauder, New Zealand (45.04degreesS, 169.68degreesE, 0.37 km altitude). All four molecules were measured on over 350 days with HCN and C2H2 reported for the first time based on a new analysis procedure that significantly increases the effective signal-to-noise of weak tropospheric absorption features in the measured spectra. The CO measurements extend by 2.5 years a database of measurements begun in January 1994 for CO with improved sensitivity in the lower and middle troposphere. The C2H6 measurements lengthen a time series begun in July 1993 with peak sensitivity in the upper troposphere. Retrievals of all four molecules were obtained with an algorithm based on the semiempirical application of the Rodgers optimal estimation technique. Columns are reported for the 0.37- to 12-km-altitude region, approximately the troposphere above the station. The seasonal cycles of all four molecules are asymmetric, with minima in March-June and sharp peaks and increased variability during August-November, which corresponds to the period of maximum biomass burning near the end of the Southern Hemisphere tropical dry season. Except for a possible HCN column decrease, no evidence was found for a statistically significant long-term trend

Correlation relationships of stratospheric molecular constituents from high spectral resolution, ground-based infrared solar absorption spectra

Comparisons of chemically active species with chemically inert tracers are useful to quantify transport and mixing and assess the accuracy of model predictions. We report measurements of chemically active species and chemically inert tracers in the stratosphere derived from the analysis of infrared solar absorption spectra recorded with a ground-based Fourier transform spectrometer operated typically at 0.005- to 0.01-cm(-1) spectral resolution. The measurements were recorded from Kitt Peak in southern Arizona (latitude 31.9 degrees N, 111.6 degrees W, 2.09 km altitude). Time series of N2O, CH4, O3, and HNO3 vertical profiles have been retrieved from measurements in microwindows. From these results, correlations between N2O and CH4 stratospheric mixing ratios and between O3 and HNO3 lower stratospheric mixing ratios have been derived. The measured correlations between N2O versus CH4 mixing ratios are compact and show little variability with respect to season in quantitative agreement with Atmospheric Trace Molecule Spectroscopy Experiment (ATMOS) spring and autumn measurements recorded near the same latitude. Lower stratospheric O3 versus HNO3 mixing ratios measured during low to moderate aerosol loading time periods also show a compact relations though the HNO3/O3 slope is a factor of 2 lower than obtained from November 1994 ATMOS measurements near the Same latitude. We also compare Kitt Peak and ATMOS N2O versus CH4 and O3 versus HNO3 relations obtained by averaging the measurements over two broad stratospheric layers. This comparison avoids bias from the a priori profiles and the limited vertical resolution of the ground-based observations

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 degrees S, 169.7 degrees E, altitude 0.37 km), and at the U.S. National Solar Observatory (31.9 degrees N, 111.6 degrees 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 laver, 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(-1) and (-0.64 +/- 0.79)% yr(-1), 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(-1) and (-1.20 +/- 0.35')% yr(-1), 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