A sensitive simultaneous detection approach for the determination of 30 atmospheric carbonyls by 2,4-dinitrophenylhydrazine derivatization with HPLC-MS technique and its preliminary application.

ABSTRACT

Atmospheric carbonyls are important precursors of PM2.5 and ground-level ozone, and some carbonyls are toxic and harmful; thus, it is crucial to obtain accurate information on the ambient levels of carbonyls. However, the detection of carbonyls is difficult due to their relatively higher reactivities and chemical instabilities; therefore, accurate determination of atmospheric carbonyls is important. In this study, an analytical method for atmospheric carbonyls with high concentration or reactivity was developed, the precursor ion of each carbonyl compound was selected, and the declustering potential (DP) and entrance potential (EP) for each precursor ion were optimized. A 2,4-dinitrophenylhydrazine cartridge derivatization-high performance liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry (DNPH-HPLC/APCI-MS) method for the determination of 30 carbonyls was established. The results showed that the linear range of 24 carbonyls was 1.2-600 ng/mL, while other 6 carbonyls was 1.2-300 ng/mL, and the detection limits of 30 carbonyls ranged from 0.092 to 0.947 ng/mL (0.005-0.049 µg/m3 with an ambient air sampling volume of 96 L). The intra-day and inter-day repeatability ranges were 0.55-4.20% and 1.40-12.48%, respectively. A preliminary application of the method was carried out in the urban area of Beijing in spring and summer of 2021, and it was found that the mean total mass concentration of 30 carbonyls was 35.894 µg/m3. This study provided additional concentration information for 14 atmospheric carbonyls, including mono-, di-, oxygen-containing and heterocyclic carbonyls, which accounted for 38% and 35% of the total mass concentration and OH radical reactivities of 30 carbonyls, respectively. This is the first investigation of simultaneous quantitative analysis of multiple atmospheric carbonyls based on commercial standard derivatives. The optimized method could provide more comprehensive information for atmospheric carbonyls and further support research concerning the role of chemical reaction processes and health effects than traditional measuring techniques.