Determination of carbonyl compounds in air by electrochromatography

A new analytical procedure based on electrochromatography was developed for the separation and quantitation of 14 aldehydes and ketones (formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, butanone, crotonaldehyde, isobutyraldehyde/butyraldehyde, 2-pentenaldehyde, isovaleraldehyde, valeraldehyde, benzaldehyde and hexanaldehyde) in ambient air currently to be regulated by the Hong Kong Environmental Protection Department. A volatile mobile phase using ammonium acetate compatible with mass spectrometry detection was developed and optimized as follows. Methanol: acetonitrile: aqueous buffer (4 mM ammonium acetate) = 65:5:30% v/v. With electrokinetic injection at 5 kV for 2 s, aqueous buffer pH adjusted to 8, applied voltage controlled at 25 kV, and detection at 360 nm in a fused-silica column packed with 3 microm ODS, a satisfactory separation was obtained for the 14 carbonyl compounds investigated. The working ranges in acetonitrile solution were found to vary from 0.25 to 79 mg/L with a correlation coefficient greater than 0.99, detection limits from 0.10 to 0.63 mg/L, and precision (relative standard deviation, n = 3) from 2.3 to 9.2%. Under an air flow rate of 0.3 L/min for a sampling time of 1 h, the working ranges varied from 0.030 to 11,000 microg/m3 and detection limits from 0.011 to 0.084 microg/ m3. The method has been successfully applied to monitor three carbonyl compounds in four urban and rural sites in Hong Kong and gave hourly readings of three carbonyl compounds for all the sites investigated with a separation time less than 25 min.