Ozone reactivity measurement of biogenic volatile organic compound emissions

Previous research on atmospheric chemistry in the forest environment has shown that the total reactivity from biogenic volatile organic compound (BVOC) emissions is not well considered in forest chemistry models. One possible explanation for this discrepancy is the unawareness and neglect of reactive biogenic emissions that have eluded common monitoring methods. This question motivated the development of a total ozone reactivity monitor (TORM) for the direct determination of the reactivity of foliage emissions. Emission samples drawn from a vegetation branch enclosure experiment are mixed with a known and controlled amount of ozone (resulting in, e.g., 100 ppb of ozone) and directed through a temperature-controlled glass flow reactor to allow reactive biogenic emissions to react with ozone during the approximately 2 min residence time in the reactor. The ozone reactivity is determined from the difference in the ozone mole fraction before and after the reaction vessel. An inherent challenge of the experiment is the influence of changing water vapor in the sample air on the ozone signal. Sample air was drawn through Nafion dryers to mitigate the water vapor interference, and a commercial UV absorption ozone monitor was modified to directly determine the ozone differential with one instrument. These two modifications significantly reduced interferences from water vapor and errors associated with the determination of the reacted ozone as the difference from two individual measurements, resulting in a much improved and sensitive determination of the ozone reactivity. This paper provides a detailed description of the measurement design, the instrument apparatus, and its characterization. Examples and results from field deployments demonstrate the applicability and usefulness of the TORM.