The applicability of a gas chromatograph coupled with a microwave plasma detector (GC-MPD) for the determination of tetraalkyllead species in the atmosphere is described. The tetraalkyllead species are collected by a cold trap containing SE-52 on Chromosorb-P at -80 °C and then are removed from the absorbent by a freeze-drying technique. The volatile lead species are concentrated within an organic solvent, separated by a GC column and determined by an MPD system which measures the emission intensity of the lead 405.78 nm spectral line. The effects of background correction using wavelength modulation techniques, doping gases, collection efficiency, and break-through volume are discussed. © 1978, American Chemical Society. All rights reserved.