LC-MS analysis of carbonyl compounds and their occurrence in diesel emissions

Liquid chromatography coupled with atmospheric pressure chemical ionization (APCI) ion trap mass spectrometry (ITMS) is applied to atmospheric aerosol relevant carbonyls. Characterization of positive and negative ion detection mass spectra are presented for 24 model compounds analyzed in their underivatized and O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) oxime forms. The addition of PFBHA derivatization enhanced the detection and sensitivity for many of the carbonyls investigated. For all but five of the carbonyls examined, a pseudomolecular (M + H)+ ion is the base peak in the APCI positive ion mass spectra of PFBHA oxime derivatives and is observed in four of the five exceptions. Application of the evaluated analysis methodology to heavy-duty diesel source emissions facilitated the quantification of 10 aliphatic carbonyls (5 C5-C9 ketones, 4 C6 unsaturated ketones, 1 C6 dicarbonyl) and 14 aromatic carbonyls (1 C9 aldehyde, 5 C8-C13 ketones, 8 C6-C14 quinones). Diesel truck engine emission factors spanning 0.55-540 microg km(-1) were measured for gas- and particle-phase carbonyls. Good agreement was observed for gas-phase emission factors with results obtained by gas chromatography with ITMS.