Person:

Miller, Christopher

We present an algorithm for the retrieval of glyoxal from backscattered solar radiation, and apply it to spectra measured by the Ozone Monitoring Instrument (OMI). The algorithm is based on direct spectrum fitting, and adopts a two-step fitting routine to account for liquid water absorption. Previous studies have shown that glyoxal retrieval algorithms are highly sensitive to the position of the spectral fit window. This dependence was systematically tested on real and simulated OMI spectra. We find that a combination of errors resulting from uncertainties in reference cross sections and spectral features associated with the Ring effect are consistent with the fit-window dependence observed in real spectra. This implies an optimal fitting window of 435–461 nm, consistent with previous satellite glyoxal retrievals. The results from the retrieval of simulated spectra also support previous findings that have suggested that glyoxal is sensitive to NO2 cross-section temperature. The retrieval window limits of the liquid water retrieval are also tested. A retrieval window 385–470 nm reduces interference with strong spectral features associated with sand. We show that cross-track dependent offsets (stripes) present in OMI can be corrected using offsets derived from retrieved slant columns over the Sahara, and apply the correction to OMI data. Average glyoxal columns are on average lower than those of previous studies likely owing to the choice of reference sector for offset correction. OMI VCDs (vertical column densities)are lower compared to other satellites over the tropics and Asia during the monsoon season, suggesting that the new retrieval is less sensitive to water vapour abundance. Consequently we do not see significant glyoxal enhancements over tropical oceans. OMI-derived glyoxal-to-formaldehyde ratios over biogenic and anthropogenic source regions are consistent with surface observations.

Glyoxal (CHOCHO) is produced in the atmosphere by the oxidation of volatile organic compounds (VOCs). Like formaldehyde (HCHO), another VOC oxidation product, it is measurable from space by solar backscatter. Isoprene emitted by vegetation is the dominant source of CHOCHO and HCHO in most of the world. We use aircraft observations of CHOCHO and HCHO from the SENEX campaign over the southeast US in summer 2013 to better understand the CHOCHO time-dependent yield from isoprene oxidation, its dependence on nitrogen oxides (NOx  ≡  NO + NO2), the behavior of the CHOCHO–HCHO relationship, the quality of OMI CHOCHO satellite observations, and the implications for using CHOCHO observations from space as constraints on isoprene emissions. We simulate the SENEX and OMI observations with the Goddard Earth Observing System chemical transport model (GEOS-Chem) featuring a new chemical mechanism for CHOCHO formation from isoprene. The mechanism includes prompt CHOCHO formation under low-NOx conditions following the isomerization of the isoprene peroxy radical (ISOPO2). The SENEX observations provide support for this prompt CHOCHO formation pathway, and are generally consistent with the GEOS-Chem mechanism. Boundary layer CHOCHO and HCHO are strongly correlated in the observations and the model, with some departure under low-NOx conditions due to prompt CHOCHO formation. SENEX vertical profiles indicate a free-tropospheric CHOCHO background that is absent from the model. The OMI CHOCHO data provide some support for this free-tropospheric background and show southeast US enhancements consistent with the isoprene source but a factor of 2 too low. Part of this OMI bias is due to excessive surface reflectivities assumed in the retrieval. The OMI CHOCHO and HCHO seasonal data over the southeast US are tightly correlated and provide redundant proxies of isoprene emissions. Higher temporal resolution in future geostationary satellite observations may enable detection of the prompt CHOCHO production under low-NOx conditions apparent in the SENEX data.