Air and leaf-litter samples were collected from a rural site in southern Ontario under meteorologically stable conditions in the early spring, prior to bud burst, over a three-day period to measure the simultaneous diurnal variations in polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). PBDEs are used in a wide range of commercial products as flame retardants and are being assessed internationally as potential persistent organic pollutants. Total PBDE concentrations in the air ranged between 88 and 1250 pg m-3, and were dominated primarily by the lighter congeners PBDEs 17, 28, and 47, and concentrations of total PCBs ranged between 96 and 950 pg m-3, and were dominated by the lower chlorinated (tri- to tetra-) congeners. Slopes of Clausius−Clapeyron plots indicate that both PCBs and PBDEs are experiencing active air−surface exchange. Fugacities were estimated from concentrations in the air and leaf-litter and suggest near equilibrium conditions. Following the three-day intensive sampling period, 40 air samples were collected at 24-hour intervals in an attempt to evaluate the effect of bud burst on atmospheric concentrations. Total PBDE concentrations in the daily air samples ranged between 10 and 230 pg m-3, and were dominated by the lighter congeners PBDE 17, 28, and 47, whereas concentrations of total PCBs ranged between 30 and 450 pg m-3 during this period. It is hypothesized that the high PBDE concentrations observed at the beginning of the sampling period are the result of an “early spring pulse” in which PBDEs deposited in the snowpack over the winter are released with snowmelt, resulting in elevated concentrations in the surface and air. Later in the sampling period, following bud burst, PBDE concentrations in air fell to 10 to 20 pg m-3, possibly due to the high sorption capacity of this freshly emerging foliage compartment.