The concurrent exchange of SO2 and H2O vapor between the atmosphere and foliage of Geraium caroinianun was investigated using a wholeplant gas exchange chamber. Total leaf flux of S02 was partitioned Into leaf surface and internal fractions. The emission rate of SOrinduced H2S was measured to develop a net leaf budget for atmospherically derived sulfur. Stomatal resistance to SO2 flux was estimated by two techniqe:(a) Rn' from 50 data using anaiog modeling techniques ad (b) R!% from analogy to H2O (Lc. 1.89 R?'O).The emission of H2S was positively correlated with the rate of SO flux into the leaf interior. An accounting of the simultaneou, bidirectonal flux of gaseous sulfur compounds during poUlutant exposure showed that sulfur accumulation in the leaf interior of G. caroliaumn was 7 to 15% lower than that estimated solely from mass-balance calculations of SO2 flux data (ie. ignoring HsS emissions).The esimate of stomatal resistance to poDutant flux from the SO, data (Rn) was consistently less than the simultaneous estimate derived from analogy to H20 vapor (Rn). The resultant of R?0' -R!, which was always negative, is indicative of a residual resistance to SO flux into the leaf interior. On a comparative basis, SOs molecules experienced less pathway resistance to diffusion than effluxing H2O molecules. It is proposed that the SO,:H1O path length ratio is less than unity, as a conquence of the pollutant's high water solubility and unique chemical reactivity in solution. Thus, the diffusive paths for H2O and SO2 in G. carominiauwn are not completely synonymous.resistance but rather to physicochemical properties of the mesophyll tissue that imparted a greater S02 sink capacity in pea as compared with corn (19). More recently, Hallgren et al (15) observed changes in S02 flux to needles of scots pine (Pinus sylvestris) that were not correlated with stomatal responses.Estimates of S02 flux into the leaf interior are frequently calculated from the ratio of the atmospheric S02 concentration to gas phase resistance to S02, the latter being derived from the sum of boundary layer and stomatal resistance to H20. This assumes (a) an S02 concentration ofzero in the leafinterior, (b) a combined gas and aqueous pathway resistance to S02 that is analogous to H20 including an identical path length, and (c) an accurate analytical measurement of S02 without interference from other sulfur-containing gases. Accurate S02 measurement is important because S02-exposed plants emit H2S in the light (5), which is indistinguishable from S02 by flame photometry (38), a common technique for measuring SO2. Because this technique measures all sulfur species in the air stream, the concentration gradient for SO2 is overestimated. Moreover, mass-balance calculations of SO2 flux to foliage would be in error (underestimated) because the true chamber/cuvette outlet SO2 concentration is less than the instrument reading. To investigate the factors controlling S02 flux into the leaf interior, the concurrent fluxes of H20, SO2, and H2S were meas...