The Mexico City Metropolitan Area (MCMA) study in April 2003 had measurements of many atmospheric constituents, including OH and HO₂. It provided the first opportunity to examine atmospheric oxidation in a megacity in a developing country that has more pollution than typical U.S. and European cities. At midday, OH typically reached 0.35 pptv (~7×10⁶ cm⁻³), comparable to amounts observed in U.S. cities, but HO₂ reached 40 pptv, more than observed in most U.S. cities. The OH reactivity was also measured, even during the highly polluted morning rush hour. MCMA's OH reactivity was 25 s⁻¹ during most of the day and 120 s⁻¹ at morning rush hour, which was several times greater than has been measured in any U.S. city. Median measured and modeled OH and HO₂ agreed to within combined uncertainties, although for OH, the model exceeded the measurement by more than 30% during midday. OH production and loss, which were calculated from measurements, were in balance to within uncertainties, although production exceeded loss during morning rush hour. This imbalance has been observed in other cities. The HO₂/OH ratio from measurements and steady-state analyses have essentially the same dependence on NO, except when NO was near 100 ppbv. This agreement is unlike other urban studies, in which HO₂/OH ratio decreased much less than expected as NO increased. As a result of the active photochemistry in MCMA 2003, the median calculated ozone production from measured HO₂ reached 50 ppb h⁻¹, a much higher rate than observed in U.S. cities.

Increasing urbanization is likely to intensify the urban heat island effect, decrease outdoor thermal comfort, and enhance runoff generation in cities. Urban green spaces are often proposed as a mitigation strategy to counteract these adverse effects, and many recent developments of urban climate models focus on the inclusion of green and blue infrastructure to inform urban planning. However, many models still lack the ability to account for different plant types and oversimplify the interactions between the built environment, vegetation, and hydrology. In this study, we present an urban ecohydrological model, Urban Tethys-Chloris (UT&C), that combines principles of ecosystem modelling with an urban canopy scheme accounting for the biophysical and ecophysiological characteristics of roof vegetation, ground vegetation, and urban trees. UT&C is a fully coupled energy and water balance model that calculates 2 m air temperature, 2 m humidity, and surface temperatures based on the infinite urban canyon approach. It further calculates the urban hydrological fluxes in the absence of snow, including transpiration as a function of plant photosynthesis. Hence, UT&C accounts for the effects of different plant types on the urban climate and hydrology, as well as the effects of the urban environment on plant well-being and performance. UT&C performs well when compared against energy flux measurements of eddy-covariance towers located in three cities in different climates (Singapore, Melbourne, and Phoenix). A sensitivity analysis, performed as a proof of concept for the city of Singapore, shows a mean decrease in 2 m air temperature of 1.1 ^∘C for fully grass-covered ground, 0.2 ^∘C for high values of leaf area index (LAI), and 0.3 ^∘C for high values of V_c,max (an expression of photosynthetic capacity). These reductions in temperature were combined with a simultaneous increase in relative humidity by 6.5 %, 2.1 %, and 1.6 %, for fully grass-covered ground, high values of LAI, and high values of V_c,max, respectively. Furthermore, the increase of pervious vegetated ground is able to significantly reduce surface runoff.

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. Four 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 in addition to meteorological processes. 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 alkanes are underestimated in the emissions inventory, while some olefins and aromatics are overestimated.