Using a speed-dependent Voigt line shape to retrieve O 2 from Total Carbon Column Observing Network solar spectra to improve measurements of XCO 2

Abstract

High-resolution, laboratory, absorption spectra of the a 1 Δ g X 3 Σ -g oxygen (O 2 ) band measured using cavity ring-down spectroscopy were fitted using the Voigt and speed-dependent Voigt line shapes. We found that the speeddependent Voigt line shape was better able to model the measured absorption coefficients than the Voigt line shape. We used these line shape models to calculate absorption coefficients to retrieve atmospheric total columns abundances of O 2 from ground-based spectra from four Fourier transform spectrometers that are a part of the Total Carbon Column Observing Network (TCCON). Lower O 2 total columns were retrieved with the speed-dependent Voigt line shape, and the difference between the total columns retrieved using the Voigt and speed-dependent Voigt line shapes increased as a function of solar zenith angle. Previous work has shown that carbon dioxide (CO 2 ) total columns are better retrieved using a speed-dependent Voigt line shape with line mixing. The column-averaged dry-air mole fraction of CO 2 (XCO 2 ) was calculated using the ratio between the columns of CO 2 and O 2 retrieved (from the same spectra) with both line shapes from measurements taken over a 1-year period at the four sites. The inclusion of speed dependence in the O 2 retrievals significantly reduces the air mass dependence of XCO 2 , and the bias between the TCCON measurements and calibrated integrated aircraft profile measurements was reduced from 1% to 0.4 %. These results suggest that speed dependence should be included in the forward model when fitting near-infrared CO 2 and O 2 spectra to improve the accuracy of XCO 2 measurements.