An automated system utilizing packed column gas chromatography and electron capture detection for the determination of peroxyacetyl nitrate (PAN) is described. The system was calibrated with a cryogenic PAN sublimation device, a molybdenum catalyst, and a chemiluminescent nitric oxide detector. Computer control of the analysis resulted in an analytical precision level of ∼1%. A total of 1178 PAN measurements were made from August 6 to September 5, 1988, in the marine boundary layer during the GCE/CASE/WATOX cruise (66°N to 7°N). Overall, PAN concentrations were highest at high latitudes (up to 40 ppt); PAN levels in the lower latitudes of the cruise track were usually <10 ppt. A number of episodes of elevated PAN are described which were characterized by elevated radon concentrations and a discernible diurnal cycle in the PAN concentration. These higher PAN levels are attributed to air masses with some continental influence, and to the enhanced stability of PAN at the cooler temperatures characteristic of the sub-Arctic region. In aged air masses of marine origin, PAN concentrations were significantly less and did not display diel changes; this is interpreted as a measure of the “background” PAN signal.