Toluene and benzene are used for assessing the ability to measure disjunct eddy covariance (DEC) fluxes of Volatile Organic Compounds (VOC) using Proton Transfer Reaction Mass Spectrometry (PTR-MS) on aircraft. Statistically significant correlation between vertical wind speed and mixing ratios suggests that airborne VOC eddy covariance (EC) flux measurements using PTR-MS are feasible. City-median midday toluene and benzene fluxes are calculated to be on the order of 14.1 +/- 4.0 mg/m(2)/h and 4.7 +/- 2.3 mg/m(2)/h, respectively. For comparison the adjusted CAM2004 emission inventory estimates toluene fluxes of 10 mg/m(2)/h along the footprint of the flight-track. Wavelet analysis of instantaneous toluene and benzene measurements during city overpasses is tested as a tool to assess surface emission heterogeneity. High toluene to benzene flux ratios above an industrial district (e. g. 10-15 g/g) including the International airport (e. g. 3-5 g/g) and a mean flux (concentration) ratio of 3.2 +/- 0.5 g/g (3.9 +/- 0.3 g/g) across Mexico City indicate that evaporative fuel and industrial emissions play an important role for the prevalence of aromatic compounds. Based on a tracer model, which was constrained by BTEX (BTEX Benzene/Toluene/Ethylbenzene/ m, p, o-Xylenes) compound concentration ratios, the fuel marker methyl-tertiary-butylether (MTBE) and the biomass burning marker acetonitrile (CH3CN), we show that a combination of industrial, evaporative fuel, and exhaust emissions account for > 87% of all BTEX sources. Our observations suggest that biomass burning emissions play a minor role for the abundance of BTEX compounds in the MCMA (2-13%).

During the National Aeronautics and Space Administration (NASA) Intercontinental Chemical Transport Experiment, Phase B (INTEX-B), in the spring of 2006, airborne measurements were made in the United States Pacific Northwest of the major inorganic ions and the water-soluble organic carbon (WSOC) of submicron (PM1.0) aerosol. An atmospheric trajectory (HYSPLIT) and a Lagrangian particle dispersion model (Flexpart) quantifying source contributions for carbon monoxide (CO) were used to segregate air masses into those of primarily Asian influence (>75% Asian CO) or North American influence (>75% North American CO). Of the measured compounds, fine particle mass mostly consisted of water-soluble organic carbon and sulfate, with median sulfate and WSOC concentrations in two to four times higher, respectively, in North American air masses versus transported Asian air masses. The fraction of WSOC to sulfate in transported Asian air masses was significantly lower than one at altitudes above 3 km due to depleted organic aerosol, opposite to what has been observed closer to Asia and in the northeastern United States, where organic components were at higher concentrations than sulfate in the free troposphere. The observations could be explained by loss of sulfate and organic aerosol by precipitation scavenging, with reformation of mainly sulfate during advection from Asia to North America. In contrast to free tropospheric measurements, for all air masses below approximately 2 km altitude median WSOC-sulfate ratios were consistently between one and two. WSOC sources were investigated by multivariate linear regression analyses of WSOC and volatile organic compounds (VOCs). In Asian air masses, of the WSOC variability that could be explained (49%), most was related to fossil fuel combustion VOCs, compared to North American air masses, where 75% of the WSOC variability was explained through a nearly equal combination of fossil fuel combustion and biogenic VOCs. Distinct WSOC plumes encountered during the experiment were also studied. A plume observed near the California Central Valley at 0.6 km altitude was related to both fossil fuel combustion and biogenic VOCs. Another Central Valley plume observed over Nevada at 3 to 5 km, in a region of cloud detrainment, was mostly related to biogenic VOCs.

The volatile organic compound (VOC) distribution in the Mexico City Metropolitan Area (MCMA) and its evolution as it is uplifted and transported out of the MCMA basin was studied during the 2006 MILAGRO/MIRAGE-Mex field campaign. The results show that in the morning hours in the city center, the VOC distribution is dominated by non-methane hydrocarbons (NMHCs) but with a substantial contribution from oxygenated volatile organic compounds (OVOCs), predominantly from primary emissions. Alkanes account for a large part of the NMHC distribution in terms of mixing ratios. In terms of reactivity, NMHCs also dominate overall, especially in the morning hours. However, in the afternoon, as the boundary layer lifts and air is mixed and aged within the basin, the distribution changes as secondary products are formed. The WRF-Chem (Weather Research and Forecasting with Chemistry) model and MOZART (Model for Ozone and Related chemical Tracers) were able to approximate the observed MCMA daytime patterns and absolute values of the VOC OH reactivity. The MOZART model is also in agreement with observations showing that NMHCs dominate the reactivity distribution except in the afternoon hours. The WRF-Chem and MOZART models showed higher reactivity than the experimental data during the nighttime cycle, perhaps indicating problems with the modeled nighttime boundary layer height. A northeast transport event was studied in which air originating in the MCMA was intercepted aloft with the Department of Energy (DOE) G1 on 18 March and downwind with the National Center for Atmospheric Research (NCAR) C130 one day later on 19 March. A number of identical species measured aboard each aircraft gave insight into the chemical evolution of the plume as it aged and was transported as far as 1000 km downwind; ozone was shown to be photochemically produced in the plume. The WRF-Chem and MOZART models were used to examine the spatial extent and temporal evolution of the plume and to help interpret the observed OH reactivity. The model results generally showed good agreement with experimental results for the total VOC OH reactivity downwind and gave insight into the distributions of VOC chemical classes. A box model with detailed gas phase chemistry (NCAR Master Mechanism), initialized with concentrations observed at one of the ground sites in the MCMA, was used to examine the expected evolution of specific VOCs over a 1-2 day period. The models clearly supported the experimental evidence for NMHC oxidation leading to the formation of OVOCs downwind, which then become the primary fuel for ozone production far away from the MCMA.

We determine enhancement ratios for NOx, PAN, and other NO y species from boreal biomass burning using aircraft data obtained during the ARCTAS-B campaign and examine the impact of these emissions on tropospheric ozone in the Arctic. We find an initial emission factor for NO x of 1.06 g NO per kg dry matter (DM) burned, much lower than previous observations of boreal plumes, and also one third the value recommended for extratropical fires. Our analysis provides the first observational confirmation of rapid PAN formation in a boreal smoke plume, with 40% of the initial NOx emissions being converted to PAN in the first few hours after emission. We find little clear evidence for ozone formation in the boreal smoke plumes during ARCTAS-B in either aircraft or satellite observations, or in model simulations. Only a third of the smoke plumes observed by the NASA DC8 showed a correlation between ozone and CO, and ozone was depleted in the plumes as often as it was enhanced. Special observations from the Tropospheric Emission Spectrometer (TES) also show little evidence for enhanced ozone in boreal smoke plumes between 15 June and 15 July 2008. Of the 22 plumes observed by TES, only 4 showed ozone increasing within the smoke plumes, and even in those cases it was unclear that the increase was caused by fire emissions. Using the GEOS-Chem atmospheric chemistry model, we show that boreal fires during ARCTAS-B had little impact on the median ozone profile measured over Canada, and had little impact on ozone within the smoke plumes observed by TES. © 2010 Author(s).