Three-Dimensional Model Analysis of Tropospheric Photochemical Processes in the Arctic and Northern Mid_Latitudes

Abstract

Halogen-driven ozone and nonmethane hydrocarbon losses in springtime Arctic boundary layer are investigated using a regional chemical transport model (CTM). Surface observation of O3 at Alert and Barrow and aircraft observations of O3 and hydrocarbons during the TOPSE experiment from February to May in 2000 are analyzed. We prescribe halogen radical distributions based on GOME BrO observations and calculated or observed other halogen radical to BrO ratios. GOME BrO shows an apparent anti-correlation with surface temperature over high BrO regions. At its peak, area of simulated near-surface O3 depletions (O3 LT 20ppbv) covers GT 50% of the north high latitudes. Model simulated O3 losses are in agreement with surface and aircraft O3 observations. Simulation of halogen distributions are constrained using aircraft hydrocarbon measurements. We find the currently chemical mechanism overestimate the Cl/BrO ratios. The model can reproduce the observed halogen loss of NMHCs using the empirical Cl/BrO ratios. We find that the hydrocarbon loss is not as sensitive to the prescribed boundary layer height of halogen as that of O3, therefore producing a more robust measure for evaluating satellite column measurement. Tropospheric tracer transport and chemical oxidation processes are examined on the basis of the observations at northern mid-high latitudes and over the tropical Pacific and the corresponding global 3D CTM (GEOS-CHEM) simulations. The correlation between propane and ethane/propane ratio is employed using a finite mixing model to examine the mixing in addition to the OH oxidations. At northern mid-high latitudes the model agrees with the observations before March. The model appears to overestimate the transport from lower to middle latitudes and the horizontal transport and mixing at high latitudes in May. Over the tropical Pacific the model reproduces the observed two-branch slope values reflecting an underestimate of continental convective transport at northern mid-latitudes and an overestimate of latitudinal transport into the tropics. Inverse modeling using the subsets of observed and simulated data is more reliable by reducing (systematic) biases introduced by systematic model transport model transport errors. On the basis of this subset we find the model underestimates the emissions of ethane and propane by 14 5%.