Atmos. Chem. Phys. Discuss., 9, 19641-19681, 2009
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Comparison of aromatic hydrocarbon measurements made by PTR-MS, DOAS and GC-FID in Mexico City during the MCMA 2003 field experiment
B. T. Jobson1, R. Volkamer2,4, E. Velasco3, G. Allwine1, H. Westberg1, B. Lamb1, M. L. Alexander5, C. M. Berkowitz5, and L. T. Molina3,4
1Department of Civil and Environmental Engineering, Washington State University, Pullman, WA, USA
2Department of Chemistry and Biochemistry and CIRES, University of Colorado, Boulder, CO, USA
3Molina Center for Energy and the Environment (MCE2), La Jolla, CA, USA
4Departmnet of Earth, Atmospheric, and Planetary Science, Massachusetts Institute of Technology, Cambridge, MA, USA
5Battelle Pacific Northwest, P.O. Box 999, Richland, WA, USA

Abstract. A comparison of aromatic hydrocarbon measurements is reported for the CENICA supersite in the district of Iztapalapa during the Mexico City Metropolitan Area field experiment in April 2003 (MCMA 2003). Data from three different measurement methods were compared, a proton transfer reaction mass spectrometer (PTR-MS), long path measurements using a UV differential optical absorption spectrometer (DOAS), and gas chromatography-flame ionization analysis (GC-FID) of canister samples. Lab tests established that the PTR-MS and DOAS calibrations were consistent for a suite of aromatic compounds including benzene, toluene, p-xylene, ethylbenzene, 1,2,4-trimethylbenzene, phenol, and styrene. The point sampling measurements by the PTR-MS and GC-FID showed good correlations (r=0.6), and were in reasonable agreement for toluene, C2-alkylbenzenes, and C3-alkylbenzenes. The PTR-MS benzene data were consistently high, indicating potential interference from fragmenting alkyl aromatics for the 145 Td drift field intensity used in the experiment. Correlations between the open-path data measured at 16-m height over a 860 m path length (retroreflector in 430 m distance), and the point measurements collected at 37-m sampling height were best for benzene (r=0.61), and reasonably good for toluene, C2-alkylbenzenes, naphthalene, styrene, cresols and phenol (r>0.5). While the DOAS data agreed within 20% with both point measurements for benzene, concentrations measured by DOAS were on average a factor of 1.7 times greater than the PTRMS data for toluene, C2-alkylbenzenes, naphthalene, and styrene. The level of agreement for the toluene data was a function of wind direction, establishing that spatial gradients – horizontal, vertical, or both – in VOC mixing ratios were significant, and up to a factor of 2 despite the fact that all measurements were conducted above roof level. Our analysis highlights a potential problem in defining a VOC sampling strategy that is meaningful for comparison with photochemical transport models: meaningful measurements require a spatial fetch that is comparable to the grid cell size of models, which is typically few 10 km2. Long-path DOAS measurements inherently average over a larger spatial scale than point measurements. The spatial representativeness can be further increased if observations are conducted outside the surface roughness sublayer, which might require measurements at altitudes as high as few 10 m above roof level.

Citation: Jobson, B. T., Volkamer, R., Velasco, E., Allwine, G., Westberg, H., Lamb, B., Alexander, M. L., Berkowitz, C. M., and Molina, L. T.: Comparison of aromatic hydrocarbon measurements made by PTR-MS, DOAS and GC-FID in Mexico City during the MCMA 2003 field experiment, Atmos. Chem. Phys. Discuss., 9, 19641-19681, doi:10.5194/acpd-9-19641-2009, 2009.
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