Articles | Volume 7, issue 12
Atmos. Meas. Tech., 7, 4417–4429, 2014
Atmos. Meas. Tech., 7, 4417–4429, 2014

Research article 12 Dec 2014

Research article | 12 Dec 2014

Online derivatization for hourly measurements of gas- and particle-phase semi-volatile oxygenated organic compounds by thermal desorption aerosol gas chromatography (SV-TAG)

G. Isaacman1, N. M. Kreisberg2, L. D. Yee1, D. R. Worton2,1, A. W. H. Chan*,1, J. A. Moss1, S. V. Hering2, and A. H. Goldstein3,1 G. Isaacman et al.
  • 1Department of Environmental Science, Policy, and Management, University of California, Berkeley, CA, USA
  • 2Aerosol Dynamics Inc., Berkeley, CA, USA
  • 3Department of Civil and Environmental Engineering, University of California, Berkeley, CA, USA
  • *now at: Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Canada

Abstract. Laboratory oxidation studies have identified a large number of oxygenated organic compounds that can be used as tracers to understand sources and oxidation chemistry of atmospheric particulate matter. Quantification of these compounds in ambient environments has traditionally relied on low-time-resolution collection of filter samples followed by offline sample treatment with a derivatizing agent to allow analysis by gas chromatography of otherwise non-elutable organic chemicals with hydroxyl groups. We present here an automated in situ instrument for the measurement of highly polar organic semi-volatile and low-volatility compounds in both the gas- and particle-phase with hourly quantification of mass concentrations and gas–particle partitioning. The dual-cell semi-volatile thermal desorption aerosol gas chromatograph (SV-TAG) with derivatization collects particle-only and combined particle-plus-vapor samples on two parallel sampling cells that are analyzed in series by thermal desorption into helium saturated with derivatizing agent. Introduction of MSTFA (N-methyl-N-(trimethylsilyl)trifluoroacetamide), a silylating agent, yields complete derivatization of all tested compounds, including alkanoic acids, polyols, diacids, sugars, and multifunctional compounds. In laboratory tests, derivatization is found to be highly reproducible (< 3% variability). During field deployment, a regularly injected internal standard is used to correct for variability in detector response, consumption of the derivatization agent, desorption efficiency, and transfer losses. Error in quantification from instrument fluctuations is found to be less than 10% for hydrocarbons and less than 15% for all oxygenates for which a functionally similar internal standard is available, with an uncertainty of 20–25% in measurements of particle fraction. After internal standard corrections, calibration curves are found to be linear for all compounds over the span of 1 month, with comparable response on both of the parallel sampling cells.

Short summary
We present here a new in situ instrument for ambient measurements of highly polar organic semi-volatile and low-volatility compounds in both the gas and particle phase by gas chromatography. Compounds previously measured only through filter collection and offline analysis can now be measured hourly with, in most cases, less than 20% uncertainty. This instrument provides unprecedented time resolution and the first ever observations of gas-particle partitioning for most of these compounds.