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Vegetation plays an important role in the partitioning, transport, and fate of semivolatile hydrophobic organic chemicals (HOCs) in the environment. Leaf/air partition ratios (K-leaf/air) of HOCs are highly variable for different plant species. The differences cannot be fully explained by the fraction of lipids in the leaves or the thickness of the cuticle. Our goal was to elucidate the importance of non polymeric lipids in determining K-leaf/air To do this, we extracted organic matter from 7 plant species using solvents that do not extract the polymeric lipids cutin and cutan, to yield extractable organic matter (EOM). We used passive dosing to determine the partition ratios of selected HOCs between the EOM of the leaves and our reference lipid, olive oil (K-EOM/olive oil) In addition, we measured analogous partition ratios for three lipid standards. Proton nuclear magnetic resonance (NMR) spectroscopy was used to characterize the composition of lipids. Differences in K-EOM/olive oil of two polychlorinated biphenyls and four chlorinated benzenes were below a factor of 2 in the plant species studied, indicating that the reported differences in K-leaf/air are not caused by differences in the sorptive capacities of nonpolymeric lipids or that our EOM is not representative of all nonpolymeric leaf lipids.

Semi-volatile persistent organic pollutants (POPs) cycle between the atmosphere and terrestrial surfaces; however measuring fluxes of POPs between the atmosphere and other media is challenging. Sampling times of hours to days are required to accurately measure trace concentrations of POPs in the atmosphere, which rules out the use of eddy covariance techniques that are used to measure gas fluxes of major air pollutants. An alternative, the modified Bowen ratio (MBR) method, has been used instead. In this study we used data from FLUXNET for CO2 and water vapor (H2O) to compare fluxes measured by eddy covariance to fluxes measured with the MBR method using vertical concentration gradients in air derived from averaged data that simulate the long sampling times typically required to measure POPs. When concentration gradients are strong and fluxes are unidirectional, the MBR method and the eddy covariance method agree within a factor of 3 for CO2, and within a factor of 10 for H2O. To remain within the range of applicability of the MBR method, field studies should be carried out under conditions such that the direction of net flux does not change during the sampling period. If that condition is met, then the performance of the MBR method is neither strongly affected by the length of sample duration nor the use of a fixed value for the transfer coefficient.

The capacity of leaves to take up chemicals from the atmosphere and water influences how contaminants are transferred into food webs and soil. We provide a proof of concept of a passive dosing method to measure leaf/polydimethylsiloxane partition ratios (Kleaf/PDMS) for intact leaves, using polychlorinated biphenyls (PCBs) as model chemicals. Rhododendron leaves held in contact with PCB-loaded PDMS reached between 76 and 99% of equilibrium within 4 days for PCBs 3, 4, 28, 52, 101, 118, 138 and 180. Equilibrium Kleaf/PDMS extrapolated from the uptake kinetics measured over 4 days ranged from 0.075 (PCB 180) to 0.371 (PCB 3). The Kleaf/PDMS data can readily be converted to fugacity capacities of leaves (Zleaf) and subsequently leaf/water or leaf/air partition ratios (Kleaf/water and Kleaf/air) using partitioning data from the literature. Results of our measurements are within the variability observed for plant/air partition ratios (Kplant/air) found in the literature. Log Kleaf/air from this study ranged from 5.00 (PCB 3) to 8.30 (PCB 180) compared to log Kplant/air of 3.31 (PCB 3) to 8.88 (PCB 180) found in the literature. The method we describe could provide data to characterize the variability in sorptive capacities of leaves that would improve descriptions of uptake of chemicals by leaves in multimedia fate models.