Abstract.A single particle soot photometer (SP2) was operated on the NCAR C-130 during the MIRAGE campaign (part of MILAGRO), sampling black carbon (BC) over Mexico. The highest BC concentrations were measured over Mexico City (sometimes as much as 2 µg/m 3 ) and over hillfires to the south of the city. The age of plumes outside of Mexico City was determined using a combination of HYS-PLIT trajectories, WRF-FLEXPART modeling and CMET balloon tracks. As expected, older, diluted air masses had lower BC concentrations. A comparison of carbon monoxide (CO) and BC suggests a CO background of around 65 ppbv, and a background-corrected BC/CO net ratio of 2.89±0.89 (ng/m 3 -STP)/ppbv (average ± standard deviation). This ratio is similar for fresh emissions over Mexico City, as well as for aged airmasses. Comparison of light absorption measured with a particle soot absorption photometer (PSAP) and the SP2 BC suggests a BC mass-normalized absorption cross-section (MAC) of 10.9±2.1 m 2 /g at 660 nm (or 13.1 m 2 /g @ 550 nm, assuming MAC is inversely dependent on wavelength). This appears independent of aging and similar to the expected absorption cross-section for aged BC, but values, particularly in fresh emissions, could be biased high due to instrument artifacts. SP2-derived BC coating indicators show a prominent thinly-coated BC mode over the Mexico City Metropolitan Area (MCMA), while older air masses show both thinly-coated and thickly-coated BC.Correspondence to: R. Subramanian (randomsubu@gmail.com) Some 2-day-old plumes do not show a prominent thicklycoated BC mode, possibly due to preferential wet scavenging of the likely-hydrophilic thickly-coated BC.

Abstract. 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/MIRAGEMex 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 abCorrespondence to: E. C. Apel (apel@ucar.edu) solute 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 Published by Copernicus Publications on behalf of the European Geosciences Union. 2354 E. C. Apel et al.: Chemical evolution of volatile organic compounds 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.

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[1] During the summer of 2004, five altitude-controlled tracking balloons were flown as part of the International Consortium for Atmospheric Research on Transport and Transformations (ICARTT) campaign. These Controlled Meteorological (CMET) balloons, newly developed at the University of Massachusetts, are notable for their light weight ($1 kg mass), efficient altitude control, ease of launch, long-duration flight capability, and ability to perform repeated quasi-Lagrangian soundings. The balloons were embedded in urban plumes from New York and Boston which they tracked over New England, eastern Canada, and the Atlantic Ocean while maintaining a nearly constant altitude. The flights ranged from 10 to 111 hours and covered a maximum distance of 3000 km. Balloon flight tracks are used here to assess the accuracy of trajectory models during intensive aircraft sampling periods. A new method is presented for increasing the number of available reference trajectories by dividing the balloon flights into shorter segments for statistical analysis. For trajectory durations between 2 and 12 hours, mean trajectory errors are found to be approximately 26% and 34% of the flight distance for ECMWF-based and GFS-based trajectories, respectively. Anomalously large model errors observed during three of the flights are found to be the result of a narrow low-level jet (15 July) and synoptic-scale flow patterns (9 and 10 August). The results from this study should be useful to researchers evaluating the performance of trajectory models and chemical transport models during the ICARTT campaign. Complete CMET balloon and model trajectory data sets are available as a supplement to this paper.