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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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Volume 8, issue 4 | Copyright

Special issue: Marine trace gases and aerosols over tropical oceans (AMT/ACP...

Atmos. Meas. Tech., 8, 1835-1862, 2015
https://doi.org/10.5194/amt-8-1835-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 23 Apr 2015

Research article | 23 Apr 2015

Instrument intercomparison of glyoxal, methyl glyoxal and NO2 under simulated atmospheric conditions

R. Thalman1,2,*, M. T. Baeza-Romero3, S. M. Ball4, E. Borrás5, M. J. S. Daniels4, I. C. A. Goodall4, S. B. Henry6, T. Karl7,8, F. N. Keutsch6, S. Kim7,9, J. Mak10, P. S. Monks4, A. Muñoz5, J. Orlando7, S. Peppe11, A. R. Rickard12,**, M. Ródenas5, P. Sánchez5, R. Seco7,9, L. Su10, G. Tyndall7, M. Vázquez5, T. Vera5, E. Waxman1,2, and R. Volkamer1,2 R. Thalman et al.
  • 1Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, CO, USA
  • 2Cooperative Institute for Research in Environmental Sciences (CIRES), Boulder, CO, USA
  • 3Escuela de Ingeniería Industrial de Toledo, Universidad de Castilla la Mancha, Toledo, Spain
  • 4Department of Chemistry, University of Leicester, Leicester, LE1 7RH, UK
  • 5Instituto Universitario UMH-CEAM, Valencia, Spain
  • 6Department of Chemistry, University of Wisconsin, Madison, WI, USA
  • 7National Center for Atmospheric Research, Boulder, CO, USA
  • 8Institute for Meteorology and Geophysics, University of Innsbruck, Innsbruck, Austria
  • 9Department of Earth System Science, University of California Irvine, Irvine, CA, USA
  • 10School of Marine and Atmospheric Sciences, State University of New York, Stony Brook, NY, USA
  • 11School of Earth and Environment, University of Leeds, Leeds, UK
  • 12National Centre for Atmospheric Science, School of Chemistry, University of Leeds, Leeds, UK
  • *now at: Brookhaven National Laboratory, Upton, NY, USA
  • **now at: National Centre for Atmospheric Science, Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, UK

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 two simulation chamber facilities in the US and Europe that included nine instruments, and seven different measurement techniques: broadband cavity enhanced absorption spectroscopy (BBCEAS), cavity-enhanced differential optical absorption spectroscopy (CE-DOAS), white-cell DOAS, Fourier transform infrared spectroscopy (FTIR, two separate instruments), laser-induced phosphorescence (LIP), solid-phase micro extraction (SPME), and proton transfer reaction mass spectrometry (PTR-ToF-MS, two separate instruments; for methyl glyoxal only because no significant response was observed for glyoxal). Experiments at the National Center for Atmospheric Research (NCAR) compare three independent sources of calibration as a function of temperature (293–330 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 (below the instruments' experimentally determined detection limits); slopes further varied by less than 5% for instruments that could also simultaneously measure NO2. For glyoxal and methyl glyoxal the slopes varied by less than 12 and 17% (both 3-σ) between direct absorption techniques (i.e., calibration from knowledge of the absorption cross section). We find a larger variability among in situ techniques that employ external calibration sources (75–90%, 3-σ), and/or techniques that employ offline analysis. Our intercomparison reveals existing differences in reports about precision and detection limits in the literature, and enables comparison on a common basis by observing a common air mass. 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.

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Measurements of α-dicarbonyl compounds, like glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO), are informative about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation in the atmosphere. We have compared nine instruments and seven techniques to measure α-dicarbonyl, using simulation chamber facilities in the US and Europe. We assess our understanding of calibration, precision, accuracy and detection limits, as well as possible sampling biases.
Measurements of α-dicarbonyl compounds, like glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO),...
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