Analysis of High Wintertime Ozone Events in the Upper Green River Basin, Wyoming

During recent years, elevated ozone (O3) values have been observed repeatedly in the Upper Green River Basin (UGRB), Wyoming during wintertime. This paper presents an analysis of high ozone days in late winter 2011 (1-hour average up to 166 ppbv). Intensive Observational Periods (IOPs) were performed which included comprehensive surface and boundary layer measurements. Low windspeeds in combination with low mixing layer heights (~50 m agl) are essential for accumulation of pollutants. Air masses contain substantial amounts of reactive nitrogen (NOx) and non-methane hydrocarbons (NMHC) emitted from fossil fuel exploration activities in the Pinedale Anticline. On IOP days in the morning hours reactive nitrogen (up to 69%), then aromatics and alkanes (each ~10-15%; mostly ethane and propane) are major contributors to the hydroxyl (OH) reactivity. This time frame largely coincides with lowest NMHC/NOx ratios (~50), reflecting a relatively low NMHC mixture, and a change from a NOx-limited regime towards a NMHC limited regime as indicated by photochemical indicators, e.g. O3/NOy, O3/NOz, and O3/HNO3 and the EOR (Extent of Reaction). OH production on IOP days is mainly due to nitrous acid (HONO).which contributes between 74-98%. Ozone photolysis (contributing 2-24%) is second to HONO photolysis. However, both reach about the same magnitude in the early afternoon (close to 50%). Photolysis of formaldehyde (HCHO) is not important (2-7%). High HONO levels (maximum hourly median on IOP days: 1,096 pptv) are favored by a combination of shallow boundary layer conditions and enhanced photolysis rates due to the high albedo of the snow surface. HONO is most likely formed through (i) abundant nitric acid (HNO3) produced in atmospheric oxidation of NOx, deposited onto the snow surface and undergoing photo-enhanced heterogeneous conversion to HONO and (ii) combustion related emission of HONO. HONO in turn will serve as the most important precursor for OH, strongly enhanced due to the high albedo of the snow cover.