Kinetics and nitro-products of the gas-phase OH and NO3 radical-initiated reactions of naphthalene-d8, Fluoranthene-d10, and pyrene

Authors

  • Roger Atkinson,

    Corresponding author
    1. Statewide Air Pollution Research Center, University of California, Riverside, California 92521
    • Statewide Air Pollution Research Center, University of California, Riverside, California 92521
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  • Janet Arey,

    Corresponding author
    1. Statewide Air Pollution Research Center, University of California, Riverside, California 92521
    • Statewide Air Pollution Research Center, University of California, Riverside, California 92521
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  • Barbara Zielinska,

    1. Statewide Air Pollution Research Center, University of California, Riverside, California 92521
    Current affiliation:
    1. Energy and Environmental Engineering Center, Desert Research Institute, P.O. Box 60220, Reno, Nevada 89506
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  • Sara M. Aschmann

    1. Statewide Air Pollution Research Center, University of California, Riverside, California 92521
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Abstract

The kinetics and nitroarene product yields of the gas-phase reactions of naphthalene-d8, fluoranthene-d10, and pyrene with OH radicals in the presence of NOx and in N2O5[BOND]NO3[BOND]NO2[BOND]air mixtures have been investigated at 296 ± 2 K and atmospheric pressure of air. Using a relative rate method, naphthalene-d8 was shown to react in N2O5[BOND]NO3[BOND]NO2[BOND]air mixtures a factor of 1.22 ± 0.10 times faster than did naphthalene, with the 1- and 2-nitronaphthalene-d7 product yields being similar to those of 1- and 2-nitronaphthalene from naphthalene. From the measured PAH concentrations and the nitroarene product yields, formation yields of 2-, 7-, and 8-nitrofluoranthene-d9 and 2- and 4-nitropyrene of 0.03, 0.01, 0.003, 0.005, and 0.0006, respectively, were determined from the OH radical-initiated reactions. Effective rate constants for the reactions of fluoranthene-d10 and pyrene with N2O5 in N2O5[BOND];NO3[BOND]NO2[BOND]air mixtures of ca. 1.8 × 10−17 cm3 molecule−1 s−1 and ca. 5.6 × 10−17 cm3 molecule−1 s−1, respectively, were derived. Formation yields of 2-nitrofluoranthene-d9 and 4-nitropyrene of ca. 0.24 and ca. 0.0006, respectively, were estimated for these reaction systems. 2-Nitropyrene was also observed to be formed in these N2O5[BOND]NO3[BOND]NO2 reactions, but was found to be a function of the NO2 concentration and, therefore, would be a negligible product under ambient NO2 concentrations. These product and kinetic data are consistent with ambient air measurements of the nitroarene concentrations.

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