In March 2006 two instrumented aircraft made the first detailed field measurements of biomass burning (BB) emissions in the Northern Hemisphere tropics as part of the MILAGRO project. The aircraft were the National Center for Atmospheric Research C-130 and a University of Montana/US Forest Service Twin Otter. The initial emissions of up to 49 trace gas or particle species were measured from 20 deforestation and crop residue fires on the Yucatan peninsula. This included two trace gases useful as indicators of BB (HCN and acetonitrile) and several rarely, or never before, measured species: OH, peroxyacetic acid, propanoic acid, hydrogen peroxide, methane sulfonic acid, and sulfuric acid. Crop residue fires emitted more organic acids and ammonia than deforestation fires, but the emissions from the main fire types were otherwise fairly similar. The Yucatan fires emitted unusually high amounts of SO2 and particle chloride, likely due to a strong marine influence on this peninsula. As smoke from one fire aged, the ratio ΔO3/ΔCO increased to ̃15% in <̃1 h similar to the fast net production of O3 in BB plumes observed earlier in Africa. The rapid change in O3 occurs at a finer spatial scale than is employed in global models and is also faster than predicted by microscale models. Fast increases in PAN, H 2O2, and two organic acids were also observed. The amount of secondary organic acid is larger than the amount of known precursors. Rapid secondary formation of organic and inorganic aerosol was observed with the ratio ΔPM2.5/ΔCO more than doubling in ̃ 1.4±0.7 h. The OH measurements revealed high initial levels (> 1 x 107 molecules/cm3) that were likely caused in part by high initial HONO (̃10% of NOy). Thus, more research is needed to understand critical post emission processes for the second-largest trace gas source on Earth. It is estimated that ̃44 Tg of biomass burned in the Yucatan in the spring of 2006. Mexican BB (including Yucatan BB) and urban emissions from the Mexico City area can both influence the March-May air quality in much of Mexico and the US.