Carbonyl compounds play an important role in many environmental oxidat
ion processes, but the identification of unknown carbonyl compounds ca
n be difficult using existing techniques. We have developed an approac
h using derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylami
ne hydrochloride (PFBHA) followed by gas chromatography/mass spectrome
try (GC/MS) analysis for the identification of unknown carbonyl compou
nds. Electron ionization, electron-capture negative chemical ionizatio
n, and positive chemical ionization mass spectrometry have all been ex
amined using model compounds. Methods for identifying molecular weight
are described, as well as methods for differentiating between differe
nt types of carbonyl compounds. GC/MS analysis of compounds containing
carboxylic acid or hydroxyl groups in addition to the carbonyl group
can be conducted by using PFBHA derivatization in conjugation with met
hylation and silylation. Electron ionization mass spectrometric analys
is of the derivatives will usually provide for adequate molecular weig
ht and structural information. The methods developed are demonstrated
for three different types of samples.