Dynamic measures of air and vegetation concentrations in an exposure chamber and a two-box mass balance model are used to quantify factors that control the rate and extent of chemical partitioning between vegetation and the atmosphere. A continuous stirred flow-through exposure chamber was used to investigate the gas-phase transfer of pollutants between air and plants. A probabilistic two-compartment mass balance model of plant/air exchange within the exposure chamber was developed and used with measured concentrations from the chamber to simultaneously evaluate partitioning (Kpa), overall mass transfer across the plant/air interface (Upa), and loss rates in the atmosphere (Ra) and aboveground vegetation (Rp). The approach is demonstrated using mature Capsicum annuum (bell pepper) plants exposed to phenanthrene (PH), anthracene (AN), fluoranthene (FL) and pyrene (PY). Measured values of log Kpa (V[air]/V[fresh plant]) were 5.7, 5.7, 6.0, and 6.2 for PH, AN, FL, and PY, respectively. Values of Upa (m d-1) under the conditions of this study ranged from 42 for PH to 119 for FL. After correcting for wall effects, the estimated reaction half-lives in air were 3, 9, and 25 h for AN, FL, and PY. Reaction half-lives in the plant compartment were 17, 6, 17, and 5 d for PH, AN, FL, and PY, respectively. The combined use of exposure chamber measurements and models provides a robust tool for simultaneously measuring several different transfer factors that are important for modeling the uptake of pollutants into vegetation.