We have demonstrated that negative ion-chemical ionization mass spectrometr
y (NI-CIMS) can be used to distinguish several isomeric volatile organic co
mpounds (VOCs) that are emitted from wounded plants. Reaction chemistry wit
h HO-, hydrogen/deuterium exchange patterns, and collision-induced dissocia
tion spectra allow identification of the isomers. Laboratory studies of emi
ssions from wounded clover using NI-CIMS show several previously detected V
OCs, but also clearly demonstrate the emission of HCN. This compound is pre
sumably formed by the decomposition of cyanogenic glycosides which also for
m aldehyde and ketone byproducts. These results suggest that NI-CIMS may be
a valuable tool for investigating VOCs and HCN release from vegetation.