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.
Total OH reactivity was measured during the California Research at the Nexus of Air Quality and Climate Change field campaign at the Pasadena ground site using a turbulent flow tube reactor with laser‐induced fluorescence detection of the OH radical. Collocated measurements of volatile organic compounds (VOCs), inorganic species, and meteorological parameters were made and used to calculate the total OH reactivity, which was then compared to the measured values. An analysis of the OH reactivity measurements finds that although the measured reactivity correlated well with the calculated reactivity, the measurements were consistently greater than the calculations for all times during the day, with an average missing OH reactivity of 8–10 s−1, accounting for approximately 40% of the measured total OH reactivity. An analysis of correlations with both anthropogenic tracers of combustion and oxygenated VOCs as well as air trajectories during the campaign suggest that the missing OH reactivity was likely due to a combination of both unmeasured local emissions and unmeasured oxidation products transported to the site. Approximately 50% of the missing OH reactivity may have been due to emissions of unmeasured volatile chemical products, such as pesticides, cleaning agents, and personal care products.
more » « less- NSF-PAR ID:
- 10446529
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Journal of Geophysical Research: Atmospheres
- Volume:
- 126
- Issue:
- 11
- ISSN:
- 2169-897X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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