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[1] The nitrate radical (NO3) is the dominant atmospheric oxidant during the night in most environments. During the day, however, NO3 has thus far been considered insignificant. Here we present daytime measurements of NO3 by Differential Optical Absorption Spectroscopy near Houston, Texas, during the Texas Air Quality Study 2000. On 3 consecutive days in August/September 2000, NO3 reached levels from ∼5 ppt 3 hours before sunset to 31 ppt around sunset. Daytime NO3 had a negligible effect on the photostationary state (PSS) between O3 and NOx, with the exception of the last hour before sunset, when it significantly accelerated NO-to-NO2 conversion. On August 31, chemical reactions involving NO3 destroyed 8 (±4) ppb Ox (= O3 + NO2) during the day and 27 (±6) ppb at night. NO3 chemistry contributed 10 (±7)% to the total Ox loss during the daytime, and 28% (±18%) integrated over a 24-hour period. It therefore played an important role in the Ox budget. NO3 also contributed significantly to the daytime oxidation of hydrocarbons such as monoterpenes and phenol in Houston. The observed daytime NO3 mixing ratios can be described as a function of O3 and NOx. Above [NOx]/[O3] ratios of 3%, daytime NO3 becomes independent of NOx and proportional to the square of O3. Our calculations indicate that elevated (>1 ppt) NO3 levels can be present whenever ozone mixing ratios exceed typical urban smog levels of 100 ppb.

Toluene and benzene are used for assessing the ability to measure disjunct eddy covariance (DEC) fluxes of Volatile Organic Compounds (VOC) using Proton Transfer Reaction Mass Spectrometry (PTR-MS) on aircraft. Statistically significant correlation between vertical wind speed and mixing ratios suggests that airborne VOC eddy covariance (EC) flux measurements using PTR-MS are feasible. City-median midday toluene and benzene fluxes are calculated to be on the order of 14.1±4.0 mg/m2/h and 4.7±2.3 mg/m2/h, respectively. For comparison the adjusted CAM2004 emission inventory estimates toluene fluxes of 10 mg/m2/h along the footprint of the flight-track. Wavelet analysis of instantaneous toluene and benzene measurements during city overpasses is tested as a tool to assess surface emission heterogeneity. High toluene to benzene flux ratios above an industrial district (e.g. 10–15 g/g) including the International airport (e.g. 3–5 g/g) and a mean flux (concentration) ratio of 3.2±0.5 g/g (3.9±0.3 g/g) across Mexico City indicate that evaporative fuel and industrial emissions play an important role for the prevalence of aromatic compounds. Based on a tracer model, which was constrained by BTEX (BTEX– Benzene/Toluene/Ethylbenzene/m, p, o-Xylenes) compound concentration ratios, the fuel marker methyl-tertiary-butyl-ether (MTBE) and the biomass burning marker acetonitrile (CH3CN), we show that a combination of industrial, evaporative fuel, and exhaust emissions account for >87% of all BTEX sources. Our observations suggest that biomass burning emissions play a minor role for the abundance of BTEX compounds in the MCMA (2–13%).