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Measurement of Glyoxal Using an Incoherent Broadband Cavity Enhanced Absorption Spectrometer

R. A. Washenfelder1,2, A. O. Langford2, H. Fuchs3, and S. S. Brown2

(1) CIRES (2) NOAA ESRL (3) Forschungszentrum Julich GmbH, Julich, Germany

Glyoxal (CHOCHO) is the simplest alpha-dicarbonyl and one of the most prevalent dicarbonyls in the atmosphere. It is formed from the photooxidation of anthropogenic hydrocarbons (e.g. aromatics and acetylene), and is a minor oxidation product of isoprene and other biogenic species. Photolysis of glyoxal is a significant source of HOx (OH + HO2), and there is growing evidence that heterogeneous reactions of glyoxal play an important role in the formation of secondary organic aerosol.

We present a novel technique for measurement of glyoxal using cavity enhanced absorption spectroscopy with a broadband light source (IBBCEAS). The output of a Xenon arc lamp is coupled into a 1 m optical cavity, and the spectrum of light exiting the cavity is recorded by a grating spectrometer with a charge-coupled device (CCD) array detector. The mirror reflectivity and effective path lengths are determined from the known Rayleigh scattering of He and dry zero air (N2 + O2). We use least-squares fitting with published reference spectra to simultaneous retrieve glyoxal, nitrogen dioxide (NO2), oxygen dimer (O4) and water (H2O) in the 441 to 469 nm spectral range. For a 1-min sampling time, the precision (±1σ) on signal for measurements of CHOCHO and NO2 is 29 pptv and 20 pptv respectively. We directly compare the incoherent broadband cavity enhanced absorption spectrometer to 404 and 532 nm cavity ringdown instruments for CHOCHO and NO2 detection, and find linear agreement over a wide range of concentrations. We present laboratory measurements of synthetic and real air samples containing CHOCHO and NO2, and discuss the potential for field measurements.