Air Quality Model Evaluation Data for Organics. 2. C₁−C₁₄ Carbonyls in Los Angeles Air

Abstract

As part of a larger experiment that provides a comprehensive set of observations to be used for testing air quality models for organic air pollutant transport and reaction, ambient air samples have been collected using DNPH-coated C18 cartridges at four urban locations and one background location in the Los Angeles area and have been analyzed for carbonyls as their DNPH derivatives. Twenty-three carbonyls have been identified and their concentrations measured:  14 aliphatic aldehydes (from formaldehyde to tetradecanal), two aromatics (benzaldehyde and m-tolualdehyde), three ketones (acetone, 2-butanone, and cyclohexanone), one unsaturated carbonyl (crotonaldehyde), and three dicarbonyls (glyoxal, methylglyoxal, and biacetyl). Another 19 carbonyls have been tentatively identified including 11 low molecular weight (MW) and intermediate MW carbonyls (of which four may be due to reactions of ambient NO, NO2, and ozone with DNPH on the sampling cartridge), four C4−C6 dicarbonyls present at trace levels, and four high MW aliphatic carbonyls (C15−C18). Total carbonyl concentrations (4-h samples) averaged 22 ppb at the urban locations and 3.5 ppb at the background location and were highest (29 ppb) at the Azusa, CA, monitoring site that is downwind of downtown Los Angeles. Formaldehyde (urban average 5.3 ppb), acetaldehyde, and acetone accounted for 24%, 18%, and 7%, respectively, of the total carbonyls on a ppbv basis. The nine high MW carbonyls (C8−C14) accounted for 11−14% of the total carbonyls. The acetaldehyde/formaldehyde concentration ratio averaged 0.75 at the urban locations. Ranking of the measured carbonyls with respect to removal of the hydroxyl radical showed acetaldehyde to be the most important followed by formaldehyde and nonanal. Diurnal and spatial variations in ambient carbonyls levels are briefly examined and appear to be consistent with both direct emissions and in-situ formation during eastward transport over the urban area