The first evidence and laboratory study of a peroxyacetyl nitrate (PAN) analogue produced by the photooxidation of a terpene, α-pinene, is presented. This PAN analogue, assigned to 3-acetyl-2,2-dimethyl-cyclobutane-acetyl peroxynitrate and referred to as α-pinonyl peroxynitrate (αP-PAN) was synthesized in the gas phase from the radical (OH, Cl, Br, or NO3) initiated oxidation of pinonaldehyde (3-acetyl-2,2-dimethyl-cyclobutyl-ethanal) in the presence of excess NO2 and evidenced by Fourier transform-infrared (FT-IR) spectroscopy. Another reaction channel producing PAN was also observed for some of the radical initiators. Of particular atmospheric interest, the experiments with OH radicals demonstrated that αP-PAN is the main product of pinonaldehyde under NOx-rich conditions with a yield of (81.3¿16)%, while an upper limit of the PAN yield for this reaction is around 8%. The further photooxidation of αP-PAN was also observed to produce PAN directly. The thermal stability of αP-PAN was studied between 303 and 281 K. The rate constant of thermal dissociation was found to be k-1=10(9.25¿0.33)¿exp<-(72.0¿1.9)/RT> where the activation energy is in kJ mol-1. Distortions of the kinetic profiles attributed to aerosol formation were observed and led to large errors in the above estimation of k-1. Within the uncertainties, the observed thermal stability of αP-PAN is comparable to that of PAN. The tropospheric importance of pinonaldehyde and of αP-PAN are discussed. ¿ 1998 American Geophysical Union