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  • Spatial Variability in Alkyl Nitrates in The Los Angeles Basin and San Joaquin Valley

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    jpeterson1
    106 vizualizări14 pagini
    Ariana Tribby, Pomona College - Abstract: Tropospheric ozone is harmful to human health, a greenhouse gas, and a major source of the hydroxyl radical, the leading atmospheric radical oxidant. Nitrogen oxides, known as NOx (NO + NO2), enter the troposphere primarily as nitrogen oxide (NO) due to combustion processes, are transformed in part to NO2, and go on to drive the nonlinear radical chemistry of atmospheric oxidation and ozone production. The formation of RONO2, called alkyl nitrates, terminates this ozone producing chemistry. For example, a 10% transformation of NOx into alkyl nitrates can decrease the NOx lifetime by nearly a factor of three and ozone production efficiency by almost an order of magnitude. Thus, understanding the RONO2 production, as well as characterizing spatial variability in alkyl nitrate chemistry, is important in order to make effective controls aimed at improving ozone air quality in the Los Angeles Basin and San Joaquin Valley, the two most polluted regions in the United States.

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    Spatial Variability in Alkyl Nitrates in the Los Angeles Basin and San Joaquin Valley

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    Ariana Tribby, Pomona College - Abstract: Tropospheric ozone is harmful to human health, a greenhouse gas, and a major source of the hydroxyl radical, the leading atmospheric radical oxidant. Nitrogen oxides, known as NOx (NO + NO2), enter the troposphere primarily as nitrogen oxide (NO) due to combustion processes, are transformed in part to NO2, and go on to drive the nonlinear radical chemistry of atmospheric oxidation and ozone production. The formation of RONO2, called alkyl nitrates, terminates this ozone producing chemistry. For example, a 10% transformation of NOx into alkyl nitrates can decrease the NOx lifetime by nearly a factor of three and ozone production efficiency by almost an order of magnitude. Thus, understanding the RONO2 production, as well as characterizing spatial variability in alkyl nitrate chemistry, is important in order to make effective controls aimed at improving ozone air quality in the Los Angeles Basin and San Joaquin Valley, the two most polluted regions in the United States.

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    106 vizualizări14 pagini

    Spatial Variability in Alkyl Nitrates in The Los Angeles Basin and San Joaquin Valley

    Încărcat de

    jpeterson1
    Ariana Tribby, Pomona College - Abstract: Tropospheric ozone is harmful to human health, a greenhouse gas, and a major source of the hydroxyl radical, the leading atmospheric radical oxidant. Nitrogen oxides, known as NOx (NO + NO2), enter the troposphere primarily as nitrogen oxide (NO) due to combustion processes, are transformed in part to NO2, and go on to drive the nonlinear radical chemistry of atmospheric oxidation and ozone production. The formation of RONO2, called alkyl nitrates, terminates this ozone producing chemistry. For example, a 10% transformation of NOx into alkyl nitrates can decrease the NOx lifetime by nearly a factor of three and ozone production efficiency by almost an order of magnitude. Thus, understanding the RONO2 production, as well as characterizing spatial variability in alkyl nitrate chemistry, is important in order to make effective controls aimed at improving ozone air quality in the Los Angeles Basin and San Joaquin Valley, the two most polluted regions in the United States.

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    din 14

    Spatial Variability of Alkyl Nitrates in the

    Los Angeles Basin and San Joaquin Valley

    Ariana Tribby1 and Sally Pusede2


    1Department
    2Department

    of Chemistry, Pomona College

    of Environmental Sciences, University of


    Virginia

    Source: latimes.com

    What is that brown haze?


    Caused by nitrogen oxide emissions
    NOx= NO + NO2

    Source: latimes.com

    Formation of Ozone
    NOx= NO + NO2

    A. E. Perring, S.E.Pusede, R.C.Cohen,.An Observational Perspective on the Atmospheric Impacts of Alkyl and Multifunctional Nitrates on Ozone
    and Secondary Organic Aerosol. Chem. Rev. 2013, 113, 5848-5870.

    FD

    Higher oxides trace the age of emissions

    Alkyl Nitrates
    Hinder
    Serve
    as Catalytic
    NO
    Peroxy
    Nitrates
    x sink
    Ozone
    Production
    Nitric Acid
    NOy= NOx + HNO3 + RONO2 +
    RO2NO2

    A. E. Perring, S.E.Pusede, R.C.Cohen,.An Observational Perspective on the Atmospheric Impacts of Alkyl and Multifunctional Nitrates on Ozone
    and Secondary Organic Aerosol. Chem. Rev. 2013, 113, 5848-5870.

    Formation and Decomposition of Alkyl


    Nitrates (RONO2)
    Favorability of pathway = Branching Ratio

    - 1
    RO2 + NO

    RO + NO2

    hv
    O2

    O3

    RONO2

    Odd Oxygen = P(Ox) = NO2+ O3

    Impact of () on P(Ox)

    Project Goals
    Characterize the spatial variability of alkyl
    nitrates found in LA and SJV
    Quantify ozone production or loss due to
    alkyl nitrate branching ratios
    Policy changes to improve air quality
    7

    *Pie

    chart size corresponds to


    relative magnitudes of NOy mixing
    ratio (pptv)

    Spatial Distribution of for San Joaquin Valley

    10

    Experimental versus Estimated differences


    in P(Ox) for San Joaquin Valley

    EPA Standard = 70ppb


    At P(O3)= 4ppb/hr for 6 hours= 34%
    11

    Experimental versus Estimated differences


    in P(Ox) for San Joaquin Valley

    12

    Conclusions
    Unique spatial variability and speciation of higher oxides between
    LA Basin and SJV
    Alkyl nitrates with low branching ratios cannot effectively act as a
    NOx sink and therefore result in increased ozone production

    Alkyl nitrates with small branching ratios contribute to


    increased ozone production in the San Joaquin Valley, and lead
    to a 30% increase in ozone production over the course of 6 hours

    NOx and carbon-based emissions that lead to alkyl nitrates with


    small branching ratio should be lowered in order to effectively
    reduce ozone exceedances in the valley
    13

    Acknowledgements
    Sally Pusede, Ph.D.
    Alex Kotsakis
    Jessica Sagona, Ph.D
    Emily Schaller, Ph.D.
    NSERC

    14

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