Abstract. The hydroxyl (OH), hydroperoxy (HO2), and organic peroxy (RO2)radicals play important roles in atmospheric chemistry. In the presence ofnitrogen oxides (NOx), reactions between OH and volatile organiccompounds (VOCs) can initiate a radical propagation cycle that leads to theproduction of ozone and secondary organic aerosols. Previous measurements ofthese radicals under low-NOx conditions in forested environmentscharacterized by emissions of biogenic VOCs, including isoprene andmonoterpenes, have shown discrepancies with modeled concentrations. During the summer of 2016, OH, HO2, and RO2 radical concentrationswere measured as part of the Program for Research on Oxidants:Photochemistry, Emissions, and Transport – Atmospheric Measurements ofOxidants in Summer (PROPHET-AMOS) campaign in a midlatitude deciduousbroadleaf forest. Measurements of OH and HO2 were made by laser-inducedfluorescence–fluorescence assay by gas expansion (LIF-FAGE) techniques,and total peroxy radical (XO2) mixing ratios were measured by the Ethane CHemical AMPlifier (ECHAMP) instrument. Supporting measurements ofphotolysis frequencies, VOCs, NOx, O3, and meteorological datawere used to constrain a zero-dimensional box model utilizing either theRegional Atmospheric Chemical Mechanism (RACM2) or the Master ChemicalMechanism (MCM). Model simulations tested the influence of HOxregeneration reactions within the isoprene oxidation scheme from the LeuvenIsoprene Mechanism (LIM1). On average, the LIM1 models overestimated daytimemaximum measurements by approximately 40 % for OH, 65 % for HO2,and more than a factor of 2 for XO2. Modeled XO2 mixing ratioswere also significantly higher than measured at night. Addition of RO2 + RO2 accretion reactions for terpene-derived RO2 radicals tothe model can partially explain the discrepancy between measurements andmodeled peroxy radical concentrations at night but cannot explain thedaytime discrepancies when OH reactivity is dominated by isoprene. Themodels also overestimated measured concentrations of isoprene-derivedhydroxyhydroperoxides (ISOPOOH) by a factor of 10 during the daytime,consistent with the model overestimation of peroxy radical concentrations.Constraining the model to the measured concentration of peroxy radicalsimproves the agreement with the measured ISOPOOH concentrations, suggestingthat the measured radical concentrations are more consistent with themeasured ISOPOOH concentrations. These results suggest that the models maybe missing an important daytime radical sink and could be overestimating therate of ozone and secondary product formation in this forest.
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Explicit modeling of isoprene chemical processing in polluted air masses in suburban areas of the Yangtze River Delta region: radical cycling and formation of ozone and formaldehyde
Abstract. In recent years, ozone pollution has become one of the most severeenvironmental problems in China. Evidence from observations have showedincreased frequency of high O3 levels in suburban areas of the YangtzeRiver Delta (YRD) region. To better understand the formation mechanism oflocal O3 pollution and investigate the potential role of isoprenechemistry in the budgets of ROx (OH+HO2+RO2) radicals,synchronous observations of volatile organic compounds (VOCs), formaldehyde(HCHO), and meteorological parameters were conducted at a suburban site ofthe YRD region in 2018. Five episodes with elevated O3 concentrationsunder stagnant meteorological conditions were identified; anobservation-based model (OBM) with the Master Chemical Mechanism was appliedto analyze the photochemical processes during these high O3 episodes.The high levels of O3, nitrogen oxides (NOx), and VOCs facilitatedstrong production and recycling of ROx radicals with the photolysis ofoxygenated VOCs (OVOCs) being the primary source. Our results suggest thatlocal biogenic isoprene is important in suburban photochemical processes.Removing isoprene could drastically slow down the efficiency of ROx recyclingand reduce the concentrations of ROx. In addition, the absence of isoprenechemistry could further lead to a decrease in the daily average concentrationsof O3 and HCHO by 34 % and 36 %, respectively. Therefore, thisstudy emphasizes the importance of isoprene chemistry in the suburbanatmosphere, particularly with the participation of anthropogenic NOx.Moreover, our results provide insights into the radical chemistry thatessentially drives the formation of secondary pollutants (e.g., O3 andHCHO) in suburban areas of the YRD region.
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- Award ID(s):
- 1743401
- PAR ID:
- 10315316
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 21
- Issue:
- 8
- ISSN:
- 1680-7324
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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