Radical precursors and related species from traffic as observed and modeled at an urban highway junction.

Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals and are believed to favor ozone formation significantly. Traffic emission data for both compounds are scarce and mostly outdated. A better knowledge of today's HCHO and HONO emissions related to traffic is needed to refine air quality models. Here the authors report results from continuous ambient air measurements taken at a highway junction in Houston, Texas, from July 15 to October 15, 2009. The observational data were compared with emission estimates from currently available mobile emission models (MOBILE6; MOVES [MOtor Vehicle Emission Simulator]). Observations indicated a molar carbon monoxide (CO) versus nitrogen oxides (NO(x)) ratio of 6.01 +/- 0.15 (r2 = 0.91), which is in agreement with other field studies. Both MOBILE6 and MOVES overestimate this emission ratio by 92% and 24%, respectively. For HCHO/CO, an overall slope of 3.14 +/- 0.14 g HCHO/kg CO was observed. Whereas MOBILE6 largely underestimates this ratio by 77%, MOVES calculates somewhat higher HCHO/CO ratios (1.87) than MOBILE6, but is still significantly lower than the observed ratio. MOVES shows high HCHO/CO ratios during the early morning hours due to heavy-duty diesel off-network emissions. The differences of the modeled CO/NO(x) and HCHO/CO ratios are largely due to higher NO(x) and HCHO emissions in MOVES (30% and 57%, respectively, increased from MOBILE6 for 2009), as CO emissions were about the same in both models. The observed HONO/NO(x) emission ratio is around 0.017 +/- 0.0009 kg HONO/kg NO(x) which is twice as high as in MOVES. The observed NO2/NO(x) emission ratio is around 0.16 +/- 0.01 kg NO2/kg NO(x), which is a bit more than 50% higher than in MOVES. MOVES overestimates the CO/CO2 emission ratio by a factor of 3 compared with the observations, which is 0.0033 +/- 0.0002 kg CO/kg CO2. This as well as CO/NO(x) overestimation is coming from light-duty gasoline vehicles.