We report on the sensitivity of enhanced ozone (O3) production, observed during lake breeze circulation along the coastline of Lake Michigan, to the concentrations of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs). We assess the sensitivity of O3 production to NOx and VOC on a high O3 day during the Lake Michigan Ozone Study 2017 using an observationally constrained chemical box model that implements the Master Chemical Mechanism (MCM v3.3.1) and recent emission inventories for NOx and VOCs. The Master Chemical Mechanism model is coupled to a backward air mass trajectory analysis from a ground supersite in Zion, IL, where an extensive series of measurements of O3 precursors and their oxidation products, including hydrogen peroxide (H2O2), nitric acid (HNO3), and particulate nitrates (NO3 −) serve as model constraints. We evaluate the chemical evolution of the Chicago-Gary urban plume as it advects over Lake Michigan and demonstrate how modeled indicators of VOC- versus NOx-sensitive regimes can be constrained by measurements at the trajectory endpoint. Using the modeled ratio of the instantaneous H2O2 and HNO3 production rates (PH2O2/PHNO3), we suggest that O3 production over the urban source region is strongly VOC sensitive and progresses towards a more NOx-sensitive regime as the plume advects north along the Lake Michigan coastline on this day. We also demonstrate that ground-based measurements of the mean concentration ratio of H2O2 to HNO3 describe the sensitivity of O3 production to VOC and NOx as the integral of chemical production along the plume path.
Bibliographical noteFunding Information:
The authors thank everyone involved with the Zion Supersite and LMOS 2017. We also thank Glenn Wolfe for developing his F0AM model and making it publicly available on his Github repository. This work was funded by the National Science Foundation under Grants AGS‐1713001, AGS‐1712828, and AGS‐1712909. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. The authors declare no competing interests. All field data from LMOS 2017 including the chemical and meteorological measurements presented in this manuscript are available on the NASA LaRC data archive (https://www‐air.larc.nasa.gov/cgi‐bin/ArcView/lmos). F0AM model outputs are available online (https://minds.wisconsin.edu/handle/1793/76304).