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We performed MS/MS investigations of biogenic volatile organic compounds(BVOC) using a triple quadrupole tandem mass spectrometer (QqQ-MS) equippedwith a Townsend Discharge ion source and a Proton Transfer Reaction LinearIon Trap (PTR-LIT) mass spectrometer. Both instruments use H<sub>2</sub>O chemicalionization to produce protonated molecules. Here we report a study of theapplication of these instruments to determine methyl vinyl ketone (MVK) andmethacrolein (MACR) and a series of monoterpenes (α-pinene, β-pinene, 3-carene, limonene, myrcene, ocimene)and sesquiterpenes (humulene and farnesene). Both instruments achieved sub-ppb detection limits in thesingle MS mode and in the MS/MS mode for differentiating MVK and MACR.Collision induced dissociation (CID) of protonated monoterpenes andsesquiterpenes was studied under the relatively high-energy, single-to-fewcollision conditions of the QqQ-MS instrument and under the low-energy,multiple collision conditions of the PTR-LIT. Differences and similaritiesin the breakdown curves obtained are discussed. In addition, we performedMS<sup>4</sup> of protonated limonene to illustrate the analytical power of thePTR-LIT. In spite of the progress we have made, the selective on-linemass-spectrometric detection of individual monoterpenes or sesquiterpenes incomplex mixtures currently does not yet seem to be possible

atmospheric measurement techniques

MS/MS studies for the selective detection of isomeric biogenic VOCs using a Townsend Discharge Triple Quadrupole Tandem MS and a PTR-Linear Ion Trap MS