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[1] We assess the impact of transport of pollution from midlatitudes on the abundance of ozone in the Arctic in summer 2006 using the GEOS-Chem global chemical transport model and its adjoint. We find that although the impact of midlatitude emissions on ozone abundances in the Arctic is at a maximum in fall and winter, in July transport from North America, Asia, and Europe together contributed about 25% of surface ozone abundances in the Arctic. Throughout the summer, the dominant source of ozone in the Arctic troposphere was photochemical production within the Arctic, which accounted for more than 50% of the ozone in the Arctic boundary layer and as much as 30%–40% of the ozone in the middle troposphere. An adjoint sensitivity analysis of the impact of NOx emissions on ozone at Alert shows that on synoptic time scales in both the lower and middle troposphere, ozone abundances are more sensitive to emissions between 50°N and 70°N, with important influences from anthropogenic, biomass burning, soil, and lightning sources. Although local surface NOx emissions contribute to ozone formation, transport of NOx in the form of peroxyacetyl nitrate (PAN) from outside the Arctic and from the upper troposphere also contributed to ozone production in the lower troposphere. We find that in late May and June the release of NOx from PAN decomposition accounted for 93% and 55% of ozone production at the Arctic surface, respectively.

[1] Airborne trace gas measurements from Transport and Chemical Evolution over the Pacific (TRACE-P), Pacific Exploratory Mission (PEM)-Tropics B, and Intercontinental Chemical Transport Experiment-North America (INTEX-NA) experiments are analyzed to examine the major source factors contributing to the observed variabilities of oxygenated volatile organic compounds and cyanides. The positive matrix factorization method is applied to coincident measurements of 11 chemicals including CH3OH, CH3COCH3, CH3CHO, C2H2, C2H6, i-C5H12, CO, CH3Cl, and CHBr3. Measurements of HCN and CH3CN are available for TRACE-P and INTEX-NA. We identify major source contributions from the terrestrial biosphere, biomass burning, industry/urban regions, and oceans. Spatial and back trajectory characteristics of these factors are examined. On the basis of TRACE-P and PEM-Tropics B data, we find a factor that explains 80–88% of the CH3OH variability, 20–40% of CH3COCH3, 7–35% of CH3CHO, and 41% of HCN, most likely representing the emissions from terrestrial biosphere. Our analysis suggested that biogenic emissions of HCN may be significant. Cyanogenesis in plants is likely a major emission process for HCN, which was not fully accounted for previously. Larger contributions than previous global estimations to CH3COCH3 and CH3CHO by biomass burning and industry/urban sources likely reflect significant secondary production from volatile organic compound oxidation. No evidence was found for large emissions of CH3COCH3 from the ocean. The oceanic CH3CHO contribution implies large regional variations.

[1] Observations (0–8 km) from the Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiment are analyzed to examine air masses contributing to the observed variability of springtime O3 and its seasonal increase at 40°–85°N over North America. Factor analysis using the positive matrix factorization and principal component analysis methods is applied to the data set with 14 chemical tracers (O3, NOy, PAN, CO, CH4, C2H2, C3H8, CH3Cl, CH3Br, C2Cl4, CFC-11, HCFC-141B, Halon-1211, and 7Be) and one dynamic tracer (potential temperature). Our analysis results are biased by the measurements at 5–8 km (70% of the data) due to the availability of 7Be measurements. The identified tracer characteristics for seven factors are generally consistent with the geographical origins derived from their 10 day back trajectories. Stratospherically influenced air accounts for 14 ppbv (35–40%) of the observed O3 variability for data with O3 concentrations