Instrument inter-comparison of glyoxal, methyl glyoxal and NO2 under simulated atmospheric conditions
Authors: Thalman R. , Baeza-Romero M. T. , Ball S. M. , Borrás E. , Daniels M. J. S. , Goodall I. C. A. , Henry S. B. , Karl T. , Keutsch F. N. , Kim S. , Mak J. , Monks P. S. , Muñoz A. , Orlando J. , Peppe S. , Rickard A. R. , Ródenas M. , Sánchez P. , Seco R. , Su L. , Tyndall G. , Vázquez M. , Vera T. , Waxman E. , Volkamer R. 
Published: August 2014

Abstract. The α-dicarbonyl compounds glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO) are produced in the atmosphere by the oxidation of hydrocarbons, and emitted directly from pyrogenic sources. Measurements of ambient concentrations inform about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation. We present results from a comprehensive instrument comparison effort at 2 simulation chamber facilities in the US and Europe that included 9 instruments, and 7 different measurement techniques: Broadband Cavity Enhanced Absorption Spectroscopy (BBCEAS), Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS), White-cell DOAS, Fourier Transform Infra-Red Spectroscopy (FTIR, two separate instruments), Laser Induced Phosphoresence (LIP), Solid Phase Micro Extraction (SPME), and Proton Transfer Reaction Mass Spectrometry (PTR-ToF-MS, two separate instruments; only methyl glyoxal as no significant response was observed for glyoxal). Experiments at the National Center for Atmospheric Research (NCAR) compare 3 independent sources of calibration as a function of temperature (293 K to 330 K). Calibrations from absorption cross-section spectra at UV-visible and IR wavelengths are found to agree within 2% for glyoxal, and 4% for methyl glyoxal at all temperatures; further calibrations based on ion-molecule rate constant calculations agreed within 5% for methyl glyoxal at all temperatures. At the EUropean PHOtoREactor (EUPHORE) all measurements are calibrated from the same UV-visible spectra (either directly or indirectly), thus minimizing potential systematic bias. We find excellent linearity under idealized conditions (pure glyoxal or methyl glyoxal, R2 > 0.96), and in complex gas mixtures characteristic of dry photochemical smog systems (o-xylene/NOx and isoprene/NOx, R2 > 0.95; R2 ~ 0.65 for offline SPME measurements of methyl glyoxal). The correlations are more variable in humid ambient air mixtures (RH > 45%) for methyl glyoxal (0.58 < R2 < 0.68) than for glyoxal (0.79 < R2 < 0.99). The intercepts of correlations were insignificant for the most part; slopes varied by less than 5% for instruments that also measure NO2. For glyoxal and methyl glyoxal the slopes varied by less than 12% and 17% (both 3-sigma) between inherently calibrated instruments (i.e., calibration from knowledge of the absorption cross-section). We find a larger variability among in situ techniques that employ external calibration sources (75% to 90%, 3-sigma), and/or techniques that employ offline analysis. Our inter-comparison reveal existing differences in reports about precision and detection limits in the literature, and enables comparison on a common basis by observing a common airmass. Finally, we evaluate the influence of interfering species (e.g., NO2, O3 and H2O) of relevance in field and laboratory applications. Techniques now exist to conduct fast and accurate measurements of glyoxal at ambient concentrations, and methyl glyoxal under simulated conditions. However, techniques to measure methyl glyoxal at ambient concentrations remain a challenge, and would be desirable.