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  • Total and Bottom Up OH Reactivity Characterization of The LA Basin and San Joaquin Valley

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    Chase Grieves, Augsburg College - Abstract: The OH reactivity describes, in large part, the importance of any individual gas-phase species in the daytime oxidative chemistry of the atmosphere. In most locations in the continental boundary layer on Earth, there are significant gaps in our understanding of which species contribute to the total atmospheric OH reactivity. During two research flights over the LA basin and San Joaquin Valley, air samples were taken with the comprehensive suite of instruments in the KORUS-AQ mission payload. These data were used to test our understanding of the OH reactivity budget in locations with distinct sources of atmospheric emissions. A bottom up analysis of OH reactivity was conducted for various regions throughout the two flights in order to gain more information on the key species responsible for the total OH reactivity as measured by the ATHOS instrument. This allowed for the identification of possible missing chemical species not detected by the suite of instruments on board the DC-8. The missing component can be potentially attributed to the breakdown products of oxidized VOCs, which were approximated for in calculations presented here aimed at closing the total OH reactivity gap. These findings present a comprehensive evaluation of the calculated OH reactivity compared to the total measured as well as the spatial variability in these budgets. These findings are useful in understanding the sources of emissions that contribute to the formation of the ozone in the LA basin and San Joaquin Valley.

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    Chase Grieves, Augsburg College - Abstract: The OH reactivity describes, in large part, the importance of any individual gas-phase species in the daytime oxidative chemistry of the atmosphere. In most locations in the continental boundary layer on Earth, there are significant gaps in our understanding of which species contribute to the total atmospheric OH reactivity. During two research flights over the LA basin and San Joaquin Valley, air samples were taken with the comprehensive suite of instruments in the KORUS-AQ mission payload. These data were used to test our understanding of the OH reactivity budget in locations with distinct sources of atmospheric emissions. A bottom up analysis of OH reactivity was conducted for various regions throughout the two flights in order to gain more information on the key species responsible for the total OH reactivity as measured by the ATHOS instrument. This allowed for the identification of possible missing chemical species not detected by the suite of instruments on board the DC-8. The missing component can be potentially attributed to the breakdown products of oxidized VOCs, which were approximated for in calculations presented here aimed at closing the total OH reactivity gap. These findings present a comprehensive evaluation of the calculated OH reactivity compared to the total measured as well as the spatial variability in these budgets. These findings are useful in understanding the sources of emissions that contribute to the formation of the ozone in the LA basin and San Joaquin Valley.

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    © All Rights Reserved
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    119 views36 pages

    Total and Bottom Up OH Reactivity Characterization of The LA Basin and San Joaquin Valley

    Uploaded by

    jpeterson1
    Chase Grieves, Augsburg College - Abstract: The OH reactivity describes, in large part, the importance of any individual gas-phase species in the daytime oxidative chemistry of the atmosphere. In most locations in the continental boundary layer on Earth, there are significant gaps in our understanding of which species contribute to the total atmospheric OH reactivity. During two research flights over the LA basin and San Joaquin Valley, air samples were taken with the comprehensive suite of instruments in the KORUS-AQ mission payload. These data were used to test our understanding of the OH reactivity budget in locations with distinct sources of atmospheric emissions. A bottom up analysis of OH reactivity was conducted for various regions throughout the two flights in order to gain more information on the key species responsible for the total OH reactivity as measured by the ATHOS instrument. This allowed for the identification of possible missing chemical species not detected by the suite of instruments on board the DC-8. The missing component can be potentially attributed to the breakdown products of oxidized VOCs, which were approximated for in calculations presented here aimed at closing the total OH reactivity gap. These findings present a comprehensive evaluation of the calculated OH reactivity compared to the total measured as well as the spatial variability in these budgets. These findings are useful in understanding the sources of emissions that contribute to the formation of the ozone in the LA basin and San Joaquin Valley.

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    Bottom Up and Total OH Reactivity

    Characterization of the LA Basin and San


    Joaquin Valley
    Chase Grieves

    Chemistry of OH in the Atmosphere

    Chemistry of OH in the Atmosphere


    VOC

    VOC + OH

    k Isoprene + OH >

    kCH4 + OH

    k Isoprene + OH >

    kCH4 + OH

    100 ppt Isoprene :

    2.2 s-1

    2 ppm CH4 :

    0.3 s-1

    MeONO2
    EtONO2
    i-PrONO2
    n-PrONO2
    2-BuONO2
    3-PeONO2
    2-PeONO2
    3-Methyl-2-BuONO2
    Ethane
    Ethene
    Ethyne
    Propane
    Propene
    i-Butane
    n-Butane
    1-Butene
    trans-2-Butene
    cis-2-Butene
    i-Pentane
    n-Pentane
    1,3-Butadiene

    Isoprene
    n-Hexane
    n-Heptane
    n-Octane
    n-Nonane
    n-Decane
    2,3-Dimethylbutane
    2-Methylpentane
    3-Methylpentane
    2,4-Dimethylpentane
    2,3-Dimethylpentane
    2,2,4-Trimethylpentane
    Cyclopentane
    Methylcyclopentane
    Cyclohexane
    Methylcylohexane
    Benzene
    Toluene
    Ethylbenzene
    m/p-Xylene
    o-Xylene

    Styrene
    i-Propylbenzene
    n-Propylbenzene
    3-Ethyltoluene
    4-Ethyltoluene
    2-Ethyltoluene
    1,3,5-Trimethylbenzene
    1,2,4-Trimethylbenzene
    1,2,3-Trimethylbenzene
    alpha-Pinene
    beta-Pinene
    Acetaldehyde
    Methanol
    Ethanol
    Acetone
    MAC
    MVK
    Butanal
    Butanone
    Formaldehyde
    Methane

    Measuring OH reactivity

    Total Reactivity
    ATHOS

    Sample air in

    Air out

    Measuring OH reactivity

    Total Reactivity
    ATHOS
    OH Inlet

    Sample air in

    Detector of OH

    Air out

    OH reactivity CalNex-LA ground site

    Figure 2: Average measured OH reactivity (red) and RACM2 modeled OH reactivity


    (blue).( Source: Griffith, S. et al. 2016. Measurements of hydroxyl and hydroperoxy
    radicals during CalNex-LA: Model comparisons and radical budgets. Journal of
    Geophysical Research. Vol. 121.

    OH reactivity CalNex-LA ground site

    Total OH
    reactivity

    OH reactive Species
    50%

    Missing OH
    50%

    Figure 2: Average measured OH reactivity (red) and RACM2 modeled OH reactivity


    (blue).( Source: Griffith, S. et al. 2016. Measurements of hydroxyl and hydroperoxy
    radicals during CalNex-LA: Model comparisons and radical budgets. Journal of
    Geophysical Research. Vol. 121.

    Missing

    OH reactivity always present

    Other campaigns all contain variable


    missing reactivity

    Dolgorouky, C. et al. 2012. Total OH reactivity measurements in


    Paris during the 2010 MEGAPOLI winter campaign. Atmos. Chem. Phys.

    SJV Flight
    Path

    LA Basin Flight
    Path

    LA Basin Flight Path

    LA Basin Flight Path

    Rancho Mirage

    Indio

    Salton Sea

    Average Calculated OH
    reactivity: 1.55 s-1
    NOx
    9%

    Rancho Mirage

    CO
    27%

    VOCs
    47%

    Indio

    CH4
    18%

    Salton Sea

    Alkenes & Alkanes


    Aromatics 8%
    2%
    Biogenics
    12%
    Rancho Mirage

    Indio

    Oxygenated VOCs
    78%
    Salton Sea

    Total OH reactivity
    Rancho Mirage
    VOC OH
    27%

    Indio
    Nox OH
    2%
    Missing OH
    71%
    Salton Sea

    SJV Flight Path

    SJV Flight Path

    Hill area
    Trees

    Crops
    Agriculture
    Hill area
    Trees

    Crops
    Agriculture
    Hill area
    Trees

    Oil
    Industry

    Crops
    Agriculture
    Hill area
    Trees

    Agriculture

    Oil
    Industry

    Fresno

    Bakersfield

    VOC OH
    21%

    VOC OH
    31%

    Nox OH
    3%
    Missing OH
    76%

    Missing OH
    67%

    VOC OH
    24%

    VOC OH
    26%
    Nox OH
    2%

    Missing OH
    74%

    Nox OH
    2%

    Missing OH
    71%

    Nox OH
    3%

    Bakersfield Ozone Production

    6.02 ppbh

    7.3 ppbh

    Summary
    OH

    reactivity and its missing


    components are vital to fully
    understanding the mechanics of
    pollution production and its cycle.

    More

    work is required to map areas of


    missing reactivity and quantify its
    chemical identity

    Acknowledgements
    Dr.

    Sally Pusede
    Alex Kotsakis
    Dr. Emily Schaller
    The NOx Box crew

    Questions?

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