Abstract. Data from a recent field campaign in Mexico City are used to evaluate the performance of the EPA Federal Reference Method for monitoring the ambient concentrations of NO 2 . Measurements of NO 2 from standard chemiluminescence monitors equipped with molybdenum oxide converters are compared with those from Tunable Infrared Laser Differential Absorption Spectroscopy (TILDAS) and Differential Optical Absorption Spectroscopy (DOAS) instruments. A significant interference in the chemiluminescence measurement is shown to account for up to 50% of ambient NO 2 concentration during afternoon hours. As expected, this interference correlates well with non-NO x reactive nitrogen species (NO z ) as well as with ambient O 3 concentrations, indicating a photochemical source for the interfering species. A combination of ambient gas phase nitric acid and alkyl and multifunctional alkyl nitrates is deduced to be the primary cause of the interference. Observations at four locations at varying proximities to emission sources indicate that the percentage contribution of HNO 3 to the interference decreases with time as the air parcel ages. Alkyl and multifunctional alkyl nitrate concentrations are calculated to reach concenCorrespondence to: E. J. Dunlea (edward.dunlea@colorado.edu) trations as high as several ppb inside the city, on par with the highest values previously observed in other urban locations. Averaged over the MCMA-2003 field campaign, the chemiluminescence monitor interference resulted in an average measured NO 2 concentration up to 22% greater than that from co-located spectroscopic measurements. Thus, this interference has the potential to initiate regulatory action in areas that are close to non-attainment and may mislead atmospheric photochemical models used to assess control strategies for photochemical oxidants.

Abstract. The MILAGRO field campaign was a multi-agency international collaborative project to evaluate the regional impacts of the Mexico City air pollution plume as a means of understanding urban impacts on the global climate. Mexico City lies on an elevated plateau with mountains on three sides and has complex mountain and surface-driven wind flows. This paper asks what the wind transport was in the basin during the field campaign and how representative it was of the climatology. Surface meteorology and air quality data, radiosondes and radar wind profiler data were collected at sites in the basin and its vicinity. Cluster analysis was used to identify the dominant wind patterns both during the campaign and within the past 10 years of operational data from the warm dry season. Our analysis shows that March 2006 was representative of typical flow patterns experienced in the basin. Six episode types were identified for the basin-scale circulation providing a way of interpreting atmospheric chemistry and particulate data collected during the campaign. Decoupling between surface winds and those aloft had a strong influence in leading to convection and poor air quality episodes. Hourly characterisation of wind circulation during the MILAGRO, MCMA-2003 and IMADA field campaigns enables the comparisons of similar air pollution episodes and the evaluation of the impact of wind transport on measurements of the atmospheric chemistry taking place in the basin.

Abstract. Surface pollutant concentrations in México Cityshow a distinct pattern of weekly variations similar to that observed in many other cities of the world. Measurements of the concentrations of carbon monoxide (CO), nitrogen oxides (NO x =NO+NO 2 ), particulate matter smaller than 10 µm (PM 10 ), and ozone (O 3 ) collected hourly over 22 years at 39 urban monitoring locations were analyzed. Morning concentrations of CO, NO x , and PM 10 are lower on Saturdays and even more so on Sundays, compared to workdays (Monday-Friday), while afternoon O 3 concentrations change minimally and are occasionally even higher. This weekend effect is empirical evidence that photochemical O 3 production is NO x -inhibited, and to the extent that emissions of CO are proportional to those of reactive volatile organic compounds (VOCs), it is VOC-limited, at least in the urban areas for which the monitoring stations are representative. The VOC-limitation has increased in the past decade, due to decreases in the concentrations of CO (and presumably VOCs) and consequent decreases in the CO/NO x and VOC/NO x ratios. Enhancements of photolysis frequencies resulting from smaller weekend aerosol burdens are not negligible, but fall short of being an alternate explanation for the observed weekend effect. The strength of the weekend effect indicates that local radical termination occurs primarily via formation of nitric acid and other NO x -related compounds, some of which (e.g. peroxy acyl nitrates) can contribute to the regional NO x budget. While VOC emission reductions would be most effective in reducing local O 3 production, NO x emission reduction may be more important for controlling regional oxidants.

Abstract. MCMA-2003 was a major field campaign investigating the atmospheric chemistry of the Mexico City Metropolitan Area (MCMA) in April of 2003. This paper describes the wind circulation patterns during the campaign both within the Mexico City basin and on the regional scale. ''Time roses'' are introduced to concisely analyze the diurnal wind patterns. Three episode types were identified that explain the conditions encountered: ''O3-South'', ''Cold Surge'' and ''O3-North''. These can be diagnosed from a combination of synoptic and basin observations based on whether the day was predominantly cloudy, or whether the O3 peak was in the north or south of the basin. O3-South days have weak synoptic forcing due to an anti-cyclone over the eastern Pacific. Strong solar heating leads to northerly flows in the basin and an evening shift due to a gap flow from the south-east. Peak ozone concentrations are in the convergence zone in the south of the city. Cold Surge days are associated with ''El Norte'' events, with strong surface northerlies bringing cold moist air and rain. Stable conditions lead to high concentrations of primary pollutants and peak ozone in the city center. O3-North days occur when the sub-tropical jet is closer to Mexico City. With strong westerlies aloft, the circulation pattern is the same as O3-South days except for a wind shift in the mid-afternoon leading to ozone peaks in the north of the city. This classification is proposed as a means of understanding pollutant transport in the Mexico City basin and as a basis for future meteorological and chemical analysis. Furthermore, model evaluation and design of policy recommendations will need to take into account the three episode types.

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