Atmos. Chem. Phys. Discuss., 11, 31819-31849, 2011
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Effect of chemical degradation on fluxes of reactive compounds
J. Rinne1, T. Markkanen2, T. M. Ruuskanen1, T. Petäjä1, P. Keronen1, M. J. Tang3, J. N. Crowley3, Ü. Rannik1, and T. Vesala1
1Department of Physics, University of Helsinki, Helsinki, Finland
2Finnish Meteorological Institute, Helsinki, Finland
3Max-Planck-Institute for Chemistry, Division of Atmospheric Chemistry, Mainz, Germany

Abstract. In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the emission at the surface. Thus one assumes the chemical degradation to be much slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPA-COPEC-2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a~major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters.

Citation: Rinne, J., Markkanen, T., Ruuskanen, T. M., Petäjä, T., Keronen, P., Tang, M. J., Crowley, J. N., Rannik, Ü., and Vesala, T.: Effect of chemical degradation on fluxes of reactive compounds, Atmos. Chem. Phys. Discuss., 11, 31819-31849, doi:10.5194/acpd-11-31819-2011, 2011.
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