Exploring the potential for spatio-temporal mapping of VOC-OH reactions from column measurements of CH2O and NO2

Wednesday, 17 December 2014
Lukas C Valin, Lamont -Doherty Earth Observatory, Palisades, NY, United States, Arlene M Fiore, Columbia University, Palisades, NY, United States, Kelly Chance, Harvard-Smithsonian, Cambridge, MA, United States, Caroline R Nowlan, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, United States, Gonzalo Gonzalez Abad, Center for Astrophysics, Cambridge, MA, United States and Eleanor C Browne, Massachusetts Institute of Technology, Cambridge, MA, United States
Reactions of OH with volatile organic compounds (VOC) such as CH4 and isoprene produce formaldehyde (CH2O). The concentration of OH and the chemistry of peroxy radicals, a reactive intermediate of VOC + OH reactions, depend strongly on the concentration of NOx. Here, we investigate the influence of NOx on the formation of CH2O in an isoprene-rich atmosphere (Martin Lake Power Plant, NE Texas) and in a “background” atmosphere (Navajo Power Plant, N Arizona) using conceptual models and the WRF-Chem regional chemistry-transport model alongside satellite-based (Aura-OMI) and flight-based (ARCTAS) measurements. In the conceptual model, the enhancement of CH2O in an NO2 plume is large and depends on the magnitude of the OH enhancement, the lifetime of the parent VOC, the concentration of intermediate oxidation products, and the impact of NOx on the branching ratios of peroxy radicals. Preliminary analysis of WRF-Chem results supports these findings. For a large point source of NOx in a low NOx-background, the enhancement of the CH2O concentration in the NOx plume is more than two times that of the surrounding region in both the isoprene-rich and the “background” WRF-Chem simulations. Furthermore, the spatial correlation of OH and CH2O in these simulated plumes suggests that simultaneous measurement of CH2O and NO2 offers the potential to better constrain the processes affecting the reaction of VOC with OH, and thus the factors controlling O3 production and the NOx lifetime. The precision of UV/Visible spectrometers planned for future geostationary missions, such as TEMPO, suggest that the routine measurement of these relationships will be possible.