Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and complementary instrumentation. Mass concentrations, diurnal cycles, and size distributions of inorganic and organic species are similar to results from the CENICA supersite in April 2003 with organic aerosol (OA) comprising about half of the fine PM mass. Positive Matrix Factorization (PMF) analysis of the high resolution OA spectra identified three major components: chemically-reduced urban primary emissions (hydrocarbon-like OA, HOA), oxygenated OA (OOA, mostly secondary OA or SOA), and biomass burning OA (BBOA) that correlates with levoglucosan and acetonitrile. BBOA includes several very large plumes from regional fires and likely also some refuse burning. A fourth OA component is a small local nitrogen-containing reduced OA component (LOA) which accounts for 9% of the OA mass but one third of the organic nitrogen, likely as amines. OOA accounts for almost half of the OA on average, consistent with previous observations. OA apportionment results from PMF-AMS are compared to the PM_2.5 chemical mass balance of organic molecular markers (CMB-OMM, from GC/MS analysis of filters). Results from both methods are overall consistent. Both assign the major components of OA to primary urban, biomass burning/woodsmoke, and secondary sources at similar magnitudes. The 2006 Mexico City emissions inventory underestimates the urban primary PM_2.5 emissions by a factor of ~4, and it is ~16 times lower than afternoon concentrations when secondary species are included. Additionally, the forest fire contribution is at least an order-of-magnitude larger than in the inventory.

MILAGRO (Megacity Initiative: Local And Global Research Observations) is an international collaborative project to examine the behavior and the export of atmospheric emissions from a megacity. The Mexico City Metropolitan Area (MCMA) – one of the world's largest megacities and North America's most populous city – was selected as the case study to characterize the sources, concentrations, transport, and transformation processes of the gases and fine particles emitted to the MCMA atmosphere and to evaluate the regional and global impacts of these emissions. The findings of this study are relevant to the evolution and impacts of pollution from many other megacities. The measurement phase consisted of a month-long series of carefully coordinated observations of the chemistry and physics of the atmosphere in and near Mexico City during March 2006, using a wide range of instruments at ground sites, on aircraft and satellites, and enlisting over 450 scientists from 150 institutions in 30 countries. Three ground supersites were set up to examine the evolution of the primary emitted gases and fine particles. Additional platforms in or near Mexico City included mobile vans containing scientific laboratories and mobile and stationary upward-looking lidars. Seven instrumented research aircraft provided information about the atmosphere over a large region and at various altitudes. Satellite-based instruments peered down into the atmosphere, providing even larger geographical coverage. The overall campaign was complemented by meteorological forecasting and numerical simulations, satellite observations and surface networks. Together, these research observations have provided the most comprehensive characterization of the MCMA's urban and regional atmospheric composition and chemistry that will take years to analyze and evaluate fully. In this paper we review over 120 papers resulting from the MILAGRO/INTEX-B Campaign that have been published or submitted, as well as relevant papers from the earlier MCMA-2003 Campaign, with the aim of providing a road map for the scientific community interested in understanding the emissions from a megacity such as the MCMA and their impacts on air quality and climate. This paper describes the measurements performed during MILAGRO and the results obtained on MCMA's atmospheric meteorology and dynamics, emissions of gases and fine particles, sources and concentrations of volatile organic compounds, urban and regional photochemistry, ambient particulate matter, aerosol radiative properties, urban plume characterization, and health studies. A summary of key findings from the field study is presented.

Organic aerosol (OA) represents approximately half of the submicron aerosol in Mexico City and the Central Mexican Plateau. This study uses the high time resolution measurements performed onboard the NCAR/NSF C-130 aircraft during the MILAGRO/MIRAGE-Mex field campaign in March 2006 to investigate the sources and chemical processing of the OA in this region. An examination of the OA/ΔCO ratio evolution as a function of photochemical age shows distinct behavior in the presence or absence of substantial open biomass burning (BB) influence, with the latter being consistent with other studies in polluted areas. In addition, we present results from Positive Matrix Factorization (PMF) analysis of 12-s High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) OA spectra. Four components were resolved. Three of the components contain substantial organic oxygen and are termed semivolatile oxygenated OA (SV-OOA), low-volatility OOA (LV-OOA), and biomass burning OA (BBOA). A reduced "hydrocarbon-like OA" (HOA) component is also resolved. LV-OOA is highly oxygenated (atomic O/C~1) and is aged organic aerosol linked to regional airmasses, with likely contributions from pollution, biomass burning, and other sources. SV-OOA is strongly correlated with ammonium nitrate, O_x, and the Mexico City Basin. We interpret SV-OOA as secondary OA which is nearly all (>90%) anthropogenic in origin. In the absence of biomass burning it represents the largest fraction of OA over the Mexico City basin, consistent with other studies in this region. BBOA is identified as arising from biomass burning sources due to a strong correlation with HCN, and the elevated contribution of the ion C₂H₄O₂⁺ (m/z 60, a marker for levoglucosan and other primary BB species). WRF-FLEXPART calculated fire impact factors (FIF) show good correlation with BBOA mass concentrations within the basin, but show location offsets in the far field due to model transport errors. This component is small or absent when forest fires are suppressed by precipitation. Since PMF factors represent organic species grouped by chemical similarity, additional postprocessing is needed to more directly apportion OA amounts to sources, which is done here based on correlations to different tracers. The postprocessed AMS results are similar to those from an independent source apportionment based on multiple linear regression with gas-phase tracers. During a flight with very high forest fire intensity near the basin OA arising from open BB represents ~66% of the OA mass in the basin and contributes similarly to OA mass in the outflow. Aging and SOA formation of BB emissions is estimated to add OA mass equivalent to about ~32–42% of the primary BBOA over several hours to a day.

Continuous ambient measurements with aerosol time-of-flight mass spectrometry (ATOFMS) were made in an industrial/residential section in the northern part of Mexico City as part of the Mexico City Metropolitan Area-2006 campaign (MCMA-2006). Results are presented for the period of 15–27 March 2006. The submicron size mode contained both fresh and aged biomass burning, aged organic carbon (OC) mixed with nitrate and sulfate, elemental carbon (EC), nitrogen-organic carbon, industrial metal, and inorganic NaK inorganic particles. Overall, biomass burning and aged OC particle types comprised 40% and 31%, respectively, of the submicron mode. In contrast, the supermicron mode was dominated by inorganic NaK particle types (42%) which represented a mixture of dry lake bed dust and industrial NaK emissions mixed with soot. Additionally, aluminosilicate dust, transition metals, OC, and biomass burning contributed to the supermicron particles. Early morning periods (2–6 a.m.) showed high fractions of inorganic particles from industrial sources in the northeast, composed of internal mixtures of Pb, Zn, EC and Cl, representing up to 73% of the particles in the 0.2–3μm size range. A unique nitrogen-containing organic carbon (NOC) particle type, peaking in the early morning hours, was hypothesized to be amines from local industrial emissions based on the time series profile and back trajectory analysis. A strong dependence on wind speed and direction was observed in the single particle types that were present during different times of the day. The early morning (3:30–10 a.m.) showed the greatest contributions from industrial emissions. During mid to late mornings (7–11 a.m.), weak northerly winds were observed along with the most highly aged particles. Stronger winds from the south picked up in the late morning (after 11 a.m.), resulting in a decrease in the concentrations of the major aged particle types and an increase in the number fraction of fresh biomass particles. The highest wind speeds were correlated with the highest number fraction of fresh biomass particles (up to 76% of the submicron number fraction) when winds were coming directly from fires that were located south and southeast of the city based on MODIS fire count data. This study provides a unique clock of hourly changes in single particle mixing state and sources as a function of meteorology in Mexico City. These new findings indicate that biomass burning and industrial emissions can make significant contributions to primary particle loadings in Mexico City that are strongly coupled with local meteorology.