The exceptional ability of alpha-tocopherol (alpha-TOH) for scavenging free radicals is believed to also underlie its protective functions in respiratory epithelia. Phenols, however, can scavenge other reactive species. Herein, we report that alpha-TOH/alpha-TO(-) reacts with closed-shell O(3)(g) on the surface of inert solvent microdroplets in < 1 ms to produce persistent alpha-TO-O(n)(-)(n = 1-4) adducts detectable by online thermospray ionization mass spectrometry. The prototype phenolate PhO(-), in contrast, undergoes electron transfer under identical conditions. These reactions are deemed to occur at the gas/liquid interface because their rates: (1) depend on pH, (2) are several orders of magnitude faster than within microdroplets saturated with O(3)(g). They also fail to incorporate solvent into the products: the same alpha-TO-O(n)(-) species are formed on acetonitrile or nucleophilic methanol microdroplets. alpha-TO-O(n = 1-3)(-) signals initially evolve with [O(3)(g)] as expected from first-generation species, but alpha-TO-O(-) reacts further with O(3)(g) and undergoes collisionally induced dissociation into a C(19)H(40) fragment (vs C(19)H(38) from alpha-TO(-)) carrying the phytyl side chain, whereas the higher alpha-TO-O(n > or = 2)(-) homologues are unreactive toward O(3)(g) and split CO(2) instead. On this basis, alpha-TO-O(-) is assigned to a chroman-6-ol (4a, 8a)-ene oxide, alpha-TO-O(2)(-) to an endoperoxide, and alpha-TO-O(3)(-) to a secondary ozonide. The atmospheric degradation of the substituted phenols detected in combustion emissions is therefore expected to produce related oxidants on the aerosol particles present in the air we breathe.