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Acyl Peroxy Nitrates Link Oil and Natural Gas Emissions to High Ozone Abundances in the Colorado Front Range During Summer 2015

2019; Wiley; Volume: 124; Issue: 4 Linguagem: Inglês

10.1029/2018jd028825

2169-8996

Jakob Lindaas, Delphine K. Farmer, I. B. Pollack, Andrew Abeleira, F. Flocke, Emily V. Fischer,

Air Quality Monitoring and Forecasting

Abstract We present measurements of ozone (O 3 ), acyl peroxy nitrates (APNs), and a suite of O 3 precursors made at the Boulder Atmospheric Observatory in Erie, Colorado, during summer 2015. We employ an empirical analysis of the APNs and a previously described positive matrix factorization of the volatile organic compounds (VOCs) to investigate the contribution of different VOC sources to high O 3 abundances at Boulder Atmospheric Observatory. Based on the ratio of peroxypropionyl nitrate (PPN) to peroxyacetyl nitrate (PAN), we find that anthropogenic VOC precursors dominate APN production when O 3 is most elevated. Propane and larger alkanes, primarily from oil and natural gas emissions in the Colorado Front Range, drive these elevated PPN to PAN ratios during high O 3 events. The percentage of OH reactivity associated with oil and gas emissions is also positively correlated with O 3 and PPN/PAN. Idealized box model simulations are used to probe the chemical mechanisms potentially responsible for these observations. We find that observed abundances of long‐lived oil and natural gas‐related VOCs are likely high enough such that the oxidation of these VOCs in a single photochemical day produces sufficient peroxy radicals to contribute to O 3 formation in the northern Colorado Front Range. Based on our empirical observations and box model simulations, we conclude that oil and natural gas emissions contribute to O 3 production on high O 3 days in this region during summer 2015.