Measurement of atmospheric hydroxyacetone, glycolaldehyde, and formaldehyde

A method has been modified and optimized for the measurements of hydroxyacetone as well as formaldehyde and glycolaldehyde, based on aqueous scrubbing using a coil sampler followed by DNPH derivatization and HPLC analysis. Derivatization equilibrium and kinetics were studied to optimize the hydroxyacetone-DNPH derivative yield. It was found that the low sensitivity of hydroxyacetone by this method is due to a relatively small equilibrium constant for the hydroxyacetone-DNPH derivatization reaction, and thus it can be improved by increasing DNPH reagent concentration. In a medium containing 500 microM DNPH and 50 mM HCl, the derivatization reaches equilibrium within 30 min. An online reagent purification procedure using a DNPH-saturated Sep-Pak C-18 cartridge effectively removed hydrazone impurities in the DNPH reagent solution, and a sample preconcentration procedure using a C-18 guard column greatly enhanced the sensitivity and lowered the detection limits. The lower detection limits of the system under optimized conditions are 30, 9, and 36 pptv for hydroxyacetone, glycolaldehyde, and formaldehyde, respectively, with a sampling/analysis cycle time of 30 min. The method has been successfully deployed at a rural site in Pinnacle State Park in Addison, NY, for a 5 week period during the summer of 1998. The ambient concentration means (medians) were 372 (332), 301 (323), and 2040 (2030) pptv for hydroxyacetone, glycolaldehyde, and formaldehyde, respectively. A late-afternoon maximum and an early morning minimum were observed in the diurnal concentration distributions of all three carbonyl compounds. Good correlations among the three carbonyl compounds suggest that they originated from a common source, i.e., photochemical oxidation of biogenic hydrocarbons. Formaldehyde photolysis accounted for about 23% of the total radical photoproduction, whereas contributionsfrom hydroxyacetone and glycolaldehyde photolysis were insignificant because of the much slower photolysis and lower concentrations of these compounds.