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International audience; In June 2009, 22 spectrometers from 14 institutes measured tropospheric and stratospheric NO2 from the ground for more than 11 days during the Cabauw Intercomparison Campaign of Nitrogen Dioxide measuring Instruments (CINDI), at Cabauw, NL (51.97° N, 4.93° E). All visible instruments used a common wavelength range and set of cross sections for the spectral analysis. Most of the instruments were of the multi-axis design with analysis by differential spectroscopy software (MAX-DOAS), whose non-zenith slant columns were compared by examining slopes of their least-squares straight line fits to mean values of a selection of instruments, after taking 30-min averages. Zenith slant columns near twilight were compared by fits to interpolated values of a reference instrument, then normalised by the mean of the slopes of the best instruments. For visible MAX-DOAS instruments, the means of the fitted slopes for NO2 and O4 of all except one instrument were within 10% of unity at almost all non-zenith elevations, and most were within 5%. Values for UV MAX-DOAS instruments were almost as good, being 12% and 7%, respectively. For visible instruments at zenith near twilight, the means of the fitted slopes of all instruments were within 5% of unity. This level of agreement is as good as that of previous intercomparisons, despite the site not being ideal for zenith twilight measurements. It bodes well for the future of measurements of tropospheric NO2, as previous intercomparisons were only for zenith instruments focussing on stratospheric NO2, with their longer heritage.

International audience; Exploratory field measurements in the Mexico City Metropolitan Area (MCMA) in February 2002 set the stage for a major air quality field measurement campaign in the spring of 2003 (MCMA-2003). Involving over 100 scientists from more than 30 institutions in Mexico, the United States and Europe, MCMA-2003 revealed important new insights into the meteorology, primary pollutant emissions, ambient secondary pollutant precursor concentrations, photochemical oxidant production and secondary aerosol particle formation in North America's most populated and polluted megacity. A description of meteorological and atmospheric chemistry and aerosol microphysics measurements performed during MCMA-2003 is presented. More than 40 published or submitted MCMA-2003 research papers are reviewed and key discoveries pertinent to understanding and improving air quality in Mexico City and similar megacities in the developing world are summarized.

A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Five distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that some, but not all, VOC classes are underestimated in the emissions inventory by factors of 1.1 to 3.

International audience; The performance of the EPA Federal Equivalent Method (FEM) technique for monitoring ambient concentrations of O3 via ultraviolet absorption (UV) has been evaluated using data from the Mexico City Metropolitan Area (MCMA-2003) field campaign. Comparisons of UV O3 monitors with open path Differential Optical Absorption Spectroscopy (DOAS) and open path Fourier Transform Infrared (FTIR) spectroscopy instruments in two locations revealed average discrepancies in the measured concentrations of +13% to ?10%. Excellent agreement of two separate open path DOAS measurements at one location indicated that spatial and temporal inhomogeneities were not substantially influencing comparisons of the point sampling and open path instruments. The poor agreement between the UV O3 monitors and the open path instruments was attributed to incorrect calibration factors for the UV monitors, although interferences could not be completely ruled out. Applying a linear correction to these calibration factors results in excellent agreement of the UV O3 monitors with the co-located open path measurements; regression slopes were 0.94 to 1.04 and associated R2 values were >0.89. A third UV O3 monitor suffered from large spurious interferences, which were attributed to extinction of UV radiation within the monitor by fine particles (3 monitors and recommendations for future testing are made.