A sensitive method for determining ultratrace volatile Se species produced from Brassica juncea seedlings is described. The use of a new commercially available GC/ ICPMS interface in conjunction with solid-phase micro-extraction is a promising way to perform these studies. The addition of optional gases (O2 and N2) to the argon discharge proved to increase the sensitivity for Se and S as well as for Xe, which as a trace contaminant gas, was used for ICPMS optimization studies. However, the optimization parameters differ when an optional gas is added. In the best conditions, limits of detection ranging from 1 to 10 ppt can be obtained depending on the Se compound and 30 to 300 ppt for the volatile S species. The use of GC/MS with similar sample introduction permits the characterization of several unknown species produced as artifacts from the standards. The method allows the virtually simultaneous monitoring of S and Se species from the headspace of several plants (e.g., onions, garlic, etc.) although the present work is focused on the B. juncea seedlings grown in closed vials and treated with Se. Dimethyl selenide and dimethyl diselenide were detected as the primary volatile Se components in the headspace. Sulfur species also were present as allyl (2-propenyl) isothiocyanate and 3-butenyl isothiocyanate as characterized by GC/MS.