We have demonstrated that negative ion-chemical ionization mass spectrometry (NI-CIMS) can be used to distinguish several isomeric volatile organic compounds (VOCs) that are emitted from wounded plants. Reaction chemistry with HO-, hydrogen/deuterium exchange patterns, and collision-induced dissociation spectra allow identification of the isomers. Laboratory studies of emissions from wounded clover using NI-CIMS show several previously detected VOCs, but also clearly demonstrate the emission of HCN. This compound is presumably formed by the decomposition of cyanogenic glycosides which also form aldehyde and ketone byproducts. These results suggest that NI-CIMS may be a valuable tool for investigating VOCs and HCN release from vegetation. ¿ 2000 American Geophysical Union