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Sensitivity of Ozone Production to NO x and VOC Along the Lake Michigan Coastline
Author(s) -
Vermeuel Michael P.,
Novak Gordon A.,
Alwe Hariprasad D.,
Hughes Dagen D.,
Kaleel Rob,
Dickens Angela F.,
Kenski Donna,
Czarnetzki Alan C.,
Stone Elizabeth A.,
Stanier Charles O.,
Pierce R. Bradley,
Millet Dylan B.,
Bertram Timothy H.
Publication year - 2019
Publication title -
journal of geophysical research: atmospheres
Language(s) - English
Resource type - Journals
eISSN - 2169-8996
pISSN - 2169-897X
DOI - 10.1029/2019jd030842
Subject(s) - ozone , plume , environmental science , hydrogen peroxide , nitric acid , environmental chemistry , box model , particulates , air mass (solar energy) , atmospheric sciences , atmospheric chemistry , meteorology , chemistry , geology , inorganic chemistry , geography , physics , organic chemistry , boundary layer , thermodynamics
We report on the sensitivity of enhanced ozone (O 3 ) production, observed during lake breeze circulation along the coastline of Lake Michigan, to the concentrations of nitrogen oxides (NO x = NO + NO 2 ) and volatile organic compounds (VOCs). We assess the sensitivity of O 3 production to NO x and VOC on a high O 3 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 NO x 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 O 3 precursors and their oxidation products, including hydrogen peroxide (H 2 O 2 ), nitric acid (HNO 3 ), and particulate nitrates (NO 3 − ) 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 NO x ‐sensitive regimes can be constrained by measurements at the trajectory endpoint. Using the modeled ratio of the instantaneous H 2 O 2 and HNO 3 production rates ( P H2O2 / P HNO3 ), we suggest that O 3 production over the urban source region is strongly VOC sensitive and progresses towards a more NO x ‐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 H 2 O 2 to HNO 3 describe the sensitivity of O 3 production to VOC and NO x as the integral of chemical production along the plume path.