1Cooperative Institute for Research in Environmental Sciences, Univ. of Colorado, Boulder, CO, USA
2NOAA Earth System Research Laboratory, Chemical Sciences Division, Boulder, CO, USA
3Joint Institute for the Study of the Atmosphere and Ocean, University of Washington, Seattle, WA, USA
4NOAA/Pacific Marine Environmental Laboratory, Seattle, WA, USA
*now at: Institute of Meteorology and Geophysics, Innsbruck University, Innsbruck, Austria
**now at: Department of Chemistry, University of York, York, YO10 5DD, UK
Received: 05 Feb 2015 – Discussion started: 05 Mar 2015
Abstract. High concentrations of volatile organic compounds (VOCs) associated with oil and natural gas extraction were measured during a strong temperature inversion in the winter of 2013 at a rural site in the Uintah Basin, Utah. During this period, photochemistry enhanced by the stagnant meteorological conditions and concentrated VOCs led to high ozone mixing ratios (150 ppbv). A simple analysis of aromatic VOCs measured by proton-transfer-reaction mass-spectrometry (PTR-MS) is used to estimate (1) VOC emission ratios (the ratio of two VOCs at the time of emission) relative to benzene, (2) aromatic VOC emission rates, and (3) ambient OH radical concentrations. These quantities are determined from a best fit to VOC : benzene ratios as a function of time. The main findings are that (1) emission ratios are consistent with contributions from both oil and gas producing wells; (2) the emission rate of methane (27–57 × 103 kg methane h−1), extrapolated from the emission rate of benzene (4.1 ± 0.4 × 105 molecules cm−3 s−1), agrees with an independent estimate of methane emissions from aircraft measurements in 2012; and (3) calculated daily OH concentrations are low, peaking at 1 × 106 molecules cm−3, and are consistent with Master Chemical Mechanism (MCM) modeling. The analysis is extended to photochemical production of oxygenated VOCs measured by PTR-MS and is able to explain daytime variability of these species. It is not able to completely reproduce nighttime behavior, possibly due to surface deposition. Using results from this analysis, the carbon mass of secondary compounds expected to have formed by the sixth day of the stagnation event was calculated, then compared to the measured mass of primary and secondary compounds. Only 17% of the expected secondary carbon mass is accounted for by gas phase, aerosol, and snow organic carbon measurements. The disparity is likely due to substantial amounts of unquantified oxygenated products.
Revised: 04 May 2015 – Accepted: 05 May 2015 – Published: 26 May 2015
Koss, A. R., de Gouw, J., Warneke, C., Gilman, J. B., Lerner, B. M., Graus, M., Yuan, B., Edwards, P., Brown, S. S., Wild, R., Roberts, J. M., Bates, T. S., and Quinn, P. K.: Photochemical aging of volatile organic compounds associated with oil and natural gas extraction in the Uintah Basin, UT, during a wintertime ozone formation event, Atmos. Chem. Phys., 15, 5727-5741, doi:10.5194/acp-15-5727-2015, 2015.