Measurement of Organic and Inorganic Acids in the Uintah Basin, Utah during UBWOS 2012 and 2013

Recently, high concentrations of ozone in winter have occurred in the winter in the Uintah Basin in Utah, a region with intensive oil and gas extraction activities. Two field campaigns (Uintah Basin Winter Ozone Study, UBWOS 2012 and 2013) aiming to understand the formation mechanisms of winter ozone were conducted in Jan.-Feb. in the two years. Snow cover and temperature were the main difference between the two campaigns: the winter in 2013 had a snow cover and several cold-pool conditions, whereas the winter of 2012 did not. As a result, only the winter of 2013 saw extensive ozone build-up during several episodes. A chemical ionization mass spectrometer (CIMS) using acetate as reagent ion was deployed to measure organic and inorganic acids. Concentrations of formic acid in 2013 were much higher (a factor of 4.0) than those in 2012, consistent with higher concentrations of other VOCs species and ozone in 2013. Enhancement ratios of formic acid to acetone in Uintah Basin are comparable to those measured in Los Angeles (LA), even though Uintah Basin has much higher alkanes and lower alkenes mixing ratios compared to those in LA. The results are in contrast with the dominant role of alkenes in secondary formation of formic acid in state-of-art chemical mechanisms. The comparisons of these datasets can provide insight into missing secondary sources of formic acid. HONO concentrations measured with the CIMS were also significantly elevated in 2013, especially during daytime. The high daytime HONO measured by CIMS could be caused by three reasons: (1) photolysis of nitrate in snow and aerosol that generates HONO photochemically; (2) evolution of HONO from snow due to acidification and warming during the daytime; (3) potential interferences of other reactive nitrogen species to form NO2- (m/z 46), the ion for quantification of HONO in CIMS. The potential interferences will be explored through laboratory experiments and from the results of box model calculations. The HONO source from nitrate photolysis will be compared to current understanding of this process. The continuous increase of nitrate and nitrite in snow during the episodes of high ozone concentration indicates that air-snow exchange may have contributed to the budget of reactive nitrogen species during UBWOS 2013.