Measurement of airborne carbonyls using an automated sampling and analysis system

Based upon the well established method of derivitization with 2,4-dinitrophenylhydrazine, an instrument was developed for ambient measurement of carbonyls with significantly improved temporal resolution and detection limits through automation, direct injection, and continuous use of a single microsilica DNPH cartridge. Kinetic experiments indicate that the derivitization reaction on the cartridge is fast enough for continuous measurements with 50 min air sampling. Reaction efficiencies measured on the cartridge were 100% for the carbonyls tested, including formaldehyde, acetaldehyde, propanal, acetone, and benzaldehyde. Transmission of the carbonyls through an ozone scrubber (KI) were in the range of 97-101%. Blank levels and detection limits were lower than those obtainable with conventional DNPH methods by an order of magnitude or greater. Mixing ratio detection limits of carbonyls in ambient air were 38-73 ppt for a 50 min air sample (2.5 L). The instrument made continuous measurements of carbonyls on a 2 h cycle over a period of 10 days during a field study in southwestern Ontario. Median mixing ratios were 0.58 ppb formaldehyde; 0.29 ppb acetaldehyde; 1.14 ppb acetone; and 0.45 ppb glyoxal. Glyoxal shows a significant correlation with ozone and zero intercept, consistent with a secondary source and minor direct source to the atmosphere. The method should easily be extendable to the detection of other low molecular weight carbonyls that have been previously reported using the DNPH technique.