Determination of carbonyl compounds in the atmosphere by DNPH derivatization and LC–ESI-MS/MS detection

A method of determination of 32 carbonyl compounds by high performance liquid chromatography (HPLC) and electrospray ionization (ESI) tandem mass spectrometry (MS/MS) after derivatization with 2,4-dinitrophenylhydrazine (DNPH) was developed and successfully applied to the atmosphere sample of a residential area of Liwan District (S1) and a research institute of Tianhe District (S2) in Guangzhou, China. Some operation conditions of ESI-MS/MS in the negative ion mode including selection of parent and daughter ions, declustering potential (DP), entrance potential (EP), collision energy (CE), collision cell exit potential (CXP) and effect of buffer in ESI-MS/MS process were optimized. The regression coefficient of the calibration curves (R2), recovery, reproducibility (R.S.D., n = 5) and limit of detection (LOD) were in the range of 0.9938–0.9999, 90–104%, 1.7–11% and 0.4–9.4 ng/m3, respectively. Among most of the samples, acetone was the most abundant carbonyl in two sampling sites and formaldehyde, acetaldehyde and butyraldehyde/2-butanone were also abundant carbonyls. In contrast to LC–UV method, the LOD, the separation of some co-eluting compounds and the precision (mainly to higher molecular weight carbonyls) are all improved by LC–ESI-MS/MS.