Strong wintertime ozone events in the Upper Green River basin, Wyoming

During recent years, elevated ozone (O-3) 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 h average up to 166 ppbv - parts per billion by volume). Intensive operational periods (IOPs) of ambient monitoring were performed, which included comprehensive surface and boundary layer measurements. On IOP days, maximum O-3 values are restricted to a very shallow surface layer. Low wind speeds in combination with low mixing layer heights (similar to 50 m above ground level around noontime) are essential for accumulation of pollutants within the UGRB. 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 particularly in the morning hours, reactive nitrogen (up to 69%), aromatics and alkanes (similar to 10-15%; mostly ethane and propane) are major contributors to the hydroxyl (OH) reactivity. Measurements at the Boulder monitoring site during these time periods under SW wind flow conditions show the lowest NMHC / NOx ratios (similar to 50), reflecting a relatively low reactive NMHC mixture, and a change from a NOx-limited regime towards a NMHC-limited regime as indicated by photochemical indicators, e.g., O-3 /NOy, O-3 /NOz, and O-3 / HNO3 and the EOR (extent of reaction). OH production on IOP days is mainly due to nitrous acid (HONO). On a 24 h basis and as determined for a measurement height of 1.80 m above the surface HONO photolysis on IOP days can contribute similar to 83% to OH production on average, followed by alkene ozonolysis (similar to 9%). Photolysis by ozone and HCHO photolysis contribute about 4% each to hydroxyl formation. High HONO levels (maximum hourly median on IOP days: 1096 pptv - parts per trillion by volume) 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 (estimated HONO production: 10.2 +/- 40% ppbv h(-1)) and (ii) combustion-related emission of HONO (estimated HONO production: similar to 0.1 +/- 30% ppbv h(-1)). HONO production is confined to the lowermost 10 m of the boundary layer. HONO, serves as the most important precursor for OH, strongly enhanced due to the high albedo of the snow cover (HONO photolysis rate 10.7 +/- 30% ppbv h(-1)). OH radicals will oxidize NMHCs, mostly aromatics (toluene, xylenes) and alkanes (ethane, propane), eventually leading to an increase in ozone.