Environmental context. Carbonyl compounds, a class of oxygenated organic matter, are crucial participants in atmospheric processes. Recently, studies have shown that the aqueous-phase processes of carbonyls have an important contribution to the formation of secondary organic aerosol (SOA), which is considered to have a significant impact on global climate change and human health. We developed the classical DNPH/HPLC method to characterise the aqueous-phase carbonyls, especially methacrolein, methyl vinyl ketone, glyoxal, and methylglyoxal, which are important precursors of SOA, in order to better understand the pathways of SOA formation in the atmosphere.

Abstract. The DNPH/HPLC method for characterising monocarbonyls and dicarbonyls in the aqueous phase has been developed. A series of experiments have been carried out using eight atmospheric ubiquitous carbonyl compounds as model dissolved compounds in both acetonitrile and water solution to obtain the optimal derivatisation and analysis qualifications. Compared with the analysis of carbonyls dissolved in acetonitrile, the influence of acidity on the derivatisation efficiency should be carefully considered in determining carbonyls in water and the optimal acidity is pH 2.0. We find that methyl vinyl ketone (MVK) transforms to crotonaldehyde during the derivatisation reaction. This transformation can be controlled to a minor degree by increasing the mixing ratio of DNPH to MVK up to 100 : 1. This improved method has been satisfactorily applied to laboratory simulations and field measurements for better understanding the carbonyl chemistry in the atmosphere.