M. C. Abrams

The Atmospheric Trace Molecule Spectroscopy (ATMOS) Experiment: Deployment on the ATLAS space shuttle missions

The ATMOS Fourier transform spectrometer was flown for a fourth time on the Space Shuttle as part of the ATLAS-3 instrument payload in November 1994. More than 190 sunrise and sunset occultation events provided measurements of more than 30 atmospheric trace gases at latitudes 3–49°N and 65–72°S, including observations both inside and outside the Antarctic polar vortex. The instrument configuration, data retrieval methodology, and mission background are described to place in context analyses of ATMOS data presented in this issue.

Stratospheric Observations of CH3D and HDO from ATMOS Infrared Solar Spectra: Enrichments of Deuterium in Methane and Implications for HD

Stratospheric mixing ratios of CH_3D from 100 mb to 17 mb (≈ 15 to 28 km) and HDO from 100 mb to 10 mb (≈ 15 to 32 km) have been inferred from high resolution solar occultation infrared spectra from the Atmospheric Trace MOlecule Spectroscopy (ATMOS) Fourier-transform interferometer. The spectra, taken on board the Space Shuttle during the Spacelab 3 and ATLAS-1, -2, and -3 missions, extend in latitude from 70°S to 65°N. We find CH_3D entering the stratosphere at an average mixing ratio of (9.9±0.8) × 10^(−10) with a D/H ratio in methane (7.1±7.4)% less than that in Standard Mean Ocean Water (SMOW) (1σ combined precision and systematic error). In the mid to lower stratosphere, the average lifetime of CH_3D is found to be (1.19±0.02) times that of CH_4, resulting in an increasing D/H ratio in methane as air “ages” and the methane mixing ratio decreases. We find an average of (1.0±0.1) molecules of stratospheric HDO are produced for each CH_3D destroyed (1σ combined precision and systematic error), indicating that the rate of HDO production is approximately equal to the rate of CH_3D destruction. Assuming negligible amounts of deuterium in species other than HDO, CH_3D and HD, this limits the possible change in the stratospheric HD mixing ratio below about 10 mb to be ±0.1 molecules HD created per molecule CH_3D destroyed.

Heavy ozone enrichments from ATMOS infrared solar spectra

Vertical enrichment profiles of stratospheric ^(16)O^(16)O^(18)O and ^(16)O^(18)O^(16)O (hereafter referred to as ^(668)O_3 and ^(686)O_3 respectively) have been derived from space-based solar occultation spectra recorded at 0.01 cm^(−1) resolution by the ATMOS (Atmospheric Trace MOlecule Spectroscopy) Fourier-transform infrared (FTIR) spectrometer. The observations, made during the Spacelab 3 and ATLAS-1, -2, and -3 shuttle missions, cover polar, mid-latitude and tropical regions between 26 to 2.6 mb inclusive (≈ 25 to 41 km). Average enrichments, weighted by molecular ^(48)O_3 density, of (15±6)% were found for ^(668)O_3 and (10±7)% for ^(686)O_3. Defining the mixing ratio of ^(50)O_3 as the sum of those for ^(668)O_3 and ^(686)O_3, an enrichment of (13±5)% was found for ^(50)O_3 (1σ standard deviation). No latitudinal or vertical gradients were found outside this standard deviation. From a series of ground-based measurements by the ATMOS instrument at Table Mountain, California (34.4°N), an average total column ^(668)O_3 enrichment of (17±4)% (1σ standard deviation) was determined, with no significant seasonal variation discernable. Possible biases in the spectral intensities that affect the determination of absolute enrichments are discussed.

Stratospheric chlorine partitioning: Constraints from shuttle‐borne measurements of [HCl], [ClNO3], and [ClO]

Measured stratospheric mixing ratios of HCl, ClNO3, and ClO from ATMOS and MAS are poorly reproduced by models using recommended kinetic parameters. This discrepancy is not resolved by new rates for the reactions Cl+CH4 and OH+HCl derived from weighted fits to laboratory measurements. A deficit in modeled [HCl] and corresponding overprediction of [ClNO3] and [ClO], which increases with altitude, suggests that production of HCl between 20 and 50 km is much faster than predicted from recommended rates.

ATMOS/ATLAS-3 Observations of Long-Lived Tracers and Descent in the Antarctic Vortex in November 1994

Observations of the long-lived tracers N2O, CH4 and HF obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument in early November 1994 are used to estimate average descent rates during winter in the Antarctic polar vortex of 0.5 to 1.5 km/month in the lower stratosphere, and 2.5 to 3.5 km/month in the middle and upper stratosphere. Descent rates inferred from ATMOS tracer observations agree well with theoretical estimates obtained using radiative heating calculations. Air of mesospheric origin (N2O < 5 ppbV) was observed at altitudes above about 25 km within the vortex. Strong horizontal gradients of tracer mixing ratios, the presence of mesospheric air in the vortex in early spring, and the variation with altitude of inferred descent rates indicate that the Antarctic vortex is highly isolated from midlatitudes throughout the winter from approximately 20 km to the stratopause. The 1994 Antarctic vortex remained well isolated between 20 and 30 km through at least mid-November.

Mid-infrared extinction by sulfate aerosols from the Mt Pinatubo eruption

Abstract Quantitative measurements of the wavelength dependence of aerosol extinction in the 750–3400 cm-1 spectral region have been derived from 0.01 cm-1 resolution stratospheric solar occultation spectra recorded by the ATMOS (Atmospheric Trace Molecule Spectroscopy) Fourier transform spectrometer about 9 1 2 months after the Mt Pinatubo volcanic eruption. Strong, broad aerosol features have been identified near 900, 1060, 1720, and 2900 cm-1 below a tangent height of ~30 km. Aerosol extinction measurements derived from ~0.05 cm-1 wide microwindows nearly free of telluric line absorption in the ATMOS spectra are compared with transmission calculations derived from aerosol size distribution profiles retrieved from correlative SAGE (Stratospheric Aerosol and Gas Experiment) II visible and near i.r. extinction measurements, seasonal and zonally averaged H2SO4 aerosol weight percentage profiles, and published sulfuric acid optical constants derived from room temperature laboratory measurements. The calculated shapes and positions of the aerosol features are generally consistent with the observations, thereby confirming that the aerosols are predominantly concentrated H2SO4-H2O droplets, but there are significant differences between the measured and calculated wavelength dependences of the aerosol extinction. We attribute these differences as primarily the result of errors in the calculated low temperature H2SO4-H2O optical constants. Errors in both the published room temperature optical constants and the limitations of the Lorentz-Lorenz relation are likely to be important.

A Comparison of Measurements from ATMOS and Instruments Aboard the ER-2 Aircraft: Tracers of Atmospheric Transport

We compare volume mixing ratio profiles of N2O, O3, NOy, H2O, CH4, and CO in the mid-latitude lower stratosphere measured by the ATMOS Fourier transform spectrometer on the ATLAS-3 Space Shuttle Mission with in situ measurements acquired from the NASA ER-2 aircraft during Nov 1994. ATMOS and ER-2 observations of [N2O] show good agreement, as do measured correlations of [O3], [NOy], [H2O], and [CH4] with [N2O]. Thus a consistent measure of the hydrogen (H2O, CH4) content of the lower stratosphere is provided by the two platforms. The similarity of [NOy] determined by detection of individual species by ATMOS and the total [NOy] measurement on the ER-2 provides strong corroboration for the accuracy of both techniques. A 25% discrepancy in lower stratospheric [CO] observed by ATMOS and the ER-2 remains unexplained. Otherwise, the agreement for measurements of long-lived tracers demonstrates the ability to combine ATMOS data with in situ observations for quantifying atmospheric transport.

On the assessment and uncertainty of atmospheric trace gas burden measurements with high resolution infrared solar occultation spectra from space by the ATMOS Experiment

The Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument is a high resolution Fourier transform spectrometer that measures atmospheric composition from low Earth orbit with infrared solar occultation sounding in the limb geometry. Following an initial flight in 1985, ATMOS participated in the Atmospheric Laboratory for Applications and Science (ATLAS) 1, 2, and 3 Space Shuttle missions in 1992, 1993, and 1994 yielding a total of 440 occultation measurements over a nine year period. The suite of more than thirty atmospheric trace gases profiled includes CO2, O3, N2O, CH4, H2O, NO, NO2, HNO3, HCl, HF, ClONO2, CCl3F, CCl2F2, CHF2Cl, and N2O5. The analysis method has been revised throughout the mission years culminating in the ‘version 2’ data set. The spectroscopic error analysis is described in the context of supporting the precision estimates reported with the profiles; in addition, systematic uncertainties assessed from the quality of the spectroscopic database are described and tabulated for comparisons with other experiments.

ATMOS Measurements of H2O + 2CH4 and Total Reactive Nitrogen in the November 1994 Antarctic Stratosphere: Dehydration and Denitrification in the Vortex

Simultaneous stratospheric volume mixing ratios (VMRs) measured inside and outside the Antarctic vortex by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument in November 1994 reveal previously unobserved features in the distributions of total reactive nitrogen (NO(y)) and total hydrogen (H2O + 2CH4). Maximum removal of NO(y) due to sedimentation of polar stratospheric clouds (PSCs) inside the vortex occurred at a potential temperature (Theta) of 500-525 K (approximately 20 km), where values were 5 times smaller than measurements outside. Maximum loss of H2O + 2CH4 due to PSCs occurred in the vortex at 425-450 K, approximately 3 km lower than the peak NO(y) loss. At that level, H2O + 2CH4 VMRs inside the vortex were approximately 70% of corresponding values outside. The Antarctic and April 1993 Arctic measurements by ATMOS show no significant differences in H2O + 2CH4 VMRs outside the vortices in the two hemispheres. Elevated NO(y) VMRs were measured inside the vortex near 700 K. Recent model calculations indicate that this feature results from downward transport of elevated NO(y) produced in the thermosphere and mesosphere.

Trace gas transport in the Arctic Vortex inferred from ATMOS ATLAS-2 observations during April 1993

Measurements of the long-lived tracers CH4, N2O, and HF from the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument during the Atmospheric Laboratory for Science and Applications-2 (ATLAS-2) Space Shuttle mission in April 1993 are used to infer average winter descent rates ranging from 0.8 km/month at 20 km to 3.2 km/month at 40 km in the Arctic polar vortex during the 1992–93 winter. Descent rates in the mid-stratosphere are similar to those deduced for the Antarctic vortex using ATMOS/ATLAS-3 measurements in November 1994, but the shorter time period of descent in the Arctic leads to smaller total distances of descent. Strong horizontal gradients observed along the vortex edge indicate that the Arctic vortex remains a significant barrier to transport at least until mid-April in the lower to middle stratosphere.