Vegetation plays an important role in the partitioning, transport and fate of hydrophobic organic contaminants (HOCs) in the environment. This thesis aimed at addressing two key knowledge gaps in our understanding of how plants exchange HOCs with the atmosphere: (1) To improve our understanding of the uptake of HOCs into, and transfer through, leaves of different plant species which can significantly influence the transport and fate of HOCs in the environment; and (2) To evaluate an experimental approach to measure fluxes of HOCs in the field. The methods presented in papers I, II and III contribute to increasing our understanding of the fate and transport of HOCs in leaves by offering straightforward ways of measuring mass transfer coefficients through leaves and partition ratios of HOCs between leaves, leaf lipids and lipid standards and reference materials like water, air and olive oil. The passive dosing study in paper III in particular investigated the role of the composition of the organic matter extracted from leaves in determining the capacity of the leaves to hold chemicals and found no large differences between 7 different plant species, even though literature data on leaf/air partition ratios (Kleaf/air) varies over 1-3 orders of magnitude. In paper IV we demonstrated that the modified Bowen ratio method can be extended to measure fluxes of persistent organic pollutants (POPs) if the fluxes do not change direction over the course of the sampling period and are large enough to be measured. This approach thus makes it possible to measure fluxes of POPs that usually require sampling times of days to weeks to exceed method detection limits. The experimental methods described in this thesis have the potential to support improved parameterization of multimedia models, which can then be evaluated against fluxes measured in the field using the modified Bowen ratio approach. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.</p>

In urban areas, emissions of nitrogen oxide radicals (NOx ≡ NO + NO2) to the atmosphere from anthropogenic activities such as fossil fuel combustion contribute to poor air quality through the production of ozone and particulate matter. Soils are also a significant global source of NOx, but at downind forest environments the deposition of transported reactive nitrogen can be much more important than local emissions. Data from a government monitoring network in the Toronto area from 2000-2007 was used to explore the impact of long-term trends in NO2 and other ozone precursors on local ozone levels. Non-linear chemistry and the influence of meteorology explained why reductions in precursor levels during this period did not lead to significant improvements in ozone. Data from this network was also used to investigate the ability of a satellite-borne spectrometer to represent spatial patterns of ground-level NO2 in the same region. Selection biases, resulting from the need to discard satellite data on cloudy days, were shown to affect locations differently and were most severe at a receptor site. The sum of all reactive nitrogen oxides including NOx is known as NOy. A custom-built instrument for high precision and time resolution measurements of reactive nitrogen oxides was tested under various lab and field conditions, and used in field work where direct biosphere-atmosphere exchange of NOy was measured by eddy covariance above two comparable North American mixed forests (Haliburton Forest Wildlife Reserve and the University of Michigan Biological Station). While these forests were found to be small net sources of NOx, they were subject to elevated rates of NOy deposition overall, driven by the transport of polluted air from upwind source regions. Wet deposition measurements were used to show that dry deposition contributed a significant fraction of total deposition during the observation periods.

In urban areas, emissions of nitrogen oxide radicals (NOx ≡ NO + NO2) to the atmosphere from anthropogenic activities such as fossil fuel combustion contribute to poor air quality through the production of ozone and particulate matter. Soils are also a significant global source of NOx, but at downind forest environments the deposition of transported reactive nitrogen can be much more important than local emissions. Data from a government monitoring network in the Toronto area from 2000-2007 was used to explore the impact of long-term trends in NO2 and other ozone precursors on local ozone levels. Non-linear chemistry and the influence of meteorology explained why reductions in precursor levels during this period did not lead to significant improvements in ozone. Data from this network was also used to investigate the ability of a satellite-borne spectrometer to represent spatial patterns of ground-level NO2 in the same region. Selection biases, resulting from the need to discard satellite data on cloudy days, were shown to affect locations differently and were most severe at a receptor site. The sum of all reactive nitrogen oxides including NOx is known as NOy. A custom-built instrument for high precision and time resolution measurements of reactive nitrogen oxides was tested under various lab and field conditions, and used in field work where direct biosphere-atmosphere exchange of NOy was measured by eddy covariance above two comparable North American mixed forests (Haliburton Forest Wildlife Reserve and the University of Michigan Biological Station). While these forests were found to be small net sources of NOx, they were subject to elevated rates of NOy deposition overall, driven by the transport of polluted air from upwind source regions. Wet deposition measurements were used to show that dry deposition contributed a significant fraction of total deposition during the observation periods.