Abstract

Dry deposition velocities (Vd) for peroxyacetyl nitrate (PAN) calculated using two community dry deposition models with different treatments of both stomatal and nonstomatal uptakes were evaluated using measurements of PAN eddy covariance fluxes over a Loblolly pine forest in July 2003. The observed daytime maximum of Vd(PAN) was ∼1.0 cm s−1on average, while the estimates by the WRF‐Chem dry deposition module (WDDM) and the Noah land surface model coupled with a photosynthesis‐based Gas Exchange Model (Noah‐GEM) were only 0.2 cm s−1 and 0.6 cm s−1, respectively. The observations also showed considerable PAN deposition at night with typical Vd values of 0.2–0.6 cm s−1, while the estimated values from both models were less than 0.1 cm s−1. Noah‐GEM modeled more realistic stomatal resistance (Rs) than WDDM, as compared with observations of water vapor exchange fluxes. The poor performance of WDDM for stomatal uptake is mainly due to its lack of dependence on leaf area index. Thermal decomposition was found to be relatively unimportant for measured PAN fluxes as shown by the lack of a relationship between measured total surface conductance and temperature. Thus, a large part of the underprediction in Vd from both models should be caused by the underestimation of nonstomatal uptake, in particular, the cuticle uptake. Sensitivity tests on both stomatal and nonstomatal resistances terms were conducted and some recommendations were provided.

Highlights

  • [2] Peroxyacetyl nitrate (PAN, CH3C(O)OONO2) is an abundant secondary pollutant of photochemical oxidation, which is produced in the atmosphere by reactions 1 and 2f: The reverse reaction (R2r) represents the thermal decomposition of PAN, a process highly sensitive to temperature

  • We previously evaluated the performance of WDDM and Noah-GEM in simulating Vd(O3) and Vd(NOy) [Wu et al, 2011] and found that a large WDDM measurement discrepancy was attributed to the minimum canopy stomatal resistance (Ri) based treatment of the canopy and Noah-GEM shows a better ability to capture the variations of canopy stomatal uptake than WDDM

  • The increase of Vd(PAN) because of wetness enhancement during the daytime was smaller than that during nighttime, which should be due to the offset effect of stomatal blocking under daytime wet conditions, similar to what was found for O3 [Zhang et al, 2002]

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Summary

Introduction

[2] Peroxyacetyl nitrate (PAN, CH3C(O)OONO2) is an abundant secondary pollutant of photochemical oxidation, which is produced in the atmosphere by reactions 1 and 2f: The reverse reaction (R2r) represents the thermal decomposition of PAN, a process highly sensitive to temperature. Reliable fast response sensors for PAN have been developed and the EC fluxes of PAN to canopy were measured over two U.S pine forests at Duke Forest, North Carolina [Turnipseed et al, 2006] and at Blodgett Forest, California [Wolfe et al, 2009]. Both data sets showed net downward PAN flux and similar diurnal trends that peaked around midday and remained at smaller values throughout the night. This model-measurement disagreement was attributed to the underestimation of nonstomatal uptake, or uncertainties in gas phase chemistry and vertical mixing [Wolfe et al, 2011]

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