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  • Discerning Alkyl Nitrate Abundance in Bakersfield, CA

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    Joshua Clark, DePauw University - Abstract: During the 2016 summer NASA Student Airborne Research Program (SARP), the NASA DC-8 flew over Bakersfield, CA because it consistently ranks in the top three U.S. cities with the worst air quality. Analysis of whole air samples collected during the Bakersfield airport missed approach indicated elevated concentrations of alkyl nitrates (RONO2). It is imperative that we study the source of alkyl nitrates as they lead to nitrogen oxide (NOx), an ozone precursor. High alkane (RH) concentrations were also measured, indicating the alkyl nitrates were most likely photochemically produced. NOAA HYSPLIT was used to determine whether emissions were localized or transported and found to mostly originate in the San Joaquin Valley, which coincides with the calculated mean air mass age of about 19 ± 5 hours. However, the age varied greatly from 8 to 31 hours, which is indicative of local emissions as well. Based on i/n pentane ratios of 2.3 ± 0.6, it was estimated that the sources of the emissions are mostly urban. This is significant because a combination of aged and fresh pollution suggests that a more in-depth analysis of local emissions is needed and should be compared to the central valley emissions in an attempt to improve the air quality in Bakersfield.

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    Joshua Clark, DePauw University - Abstract: During the 2016 summer NASA Student Airborne Research Program (SARP), the NASA DC-8 flew over Bakersfield, CA because it consistently ranks in the top three U.S. cities with the worst air quality. Analysis of whole air samples collected during the Bakersfield airport missed approach indicated elevated concentrations of alkyl nitrates (RONO2). It is imperative that we study the source of alkyl nitrates as they lead to nitrogen oxide (NOx), an ozone precursor. High alkane (RH) concentrations were also measured, indicating the alkyl nitrates were most likely photochemically produced. NOAA HYSPLIT was used to determine whether emissions were localized or transported and found to mostly originate in the San Joaquin Valley, which coincides with the calculated mean air mass age of about 19 ± 5 hours. However, the age varied greatly from 8 to 31 hours, which is indicative of local emissions as well. Based on i/n pentane ratios of 2.3 ± 0.6, it was estimated that the sources of the emissions are mostly urban. This is significant because a combination of aged and fresh pollution suggests that a more in-depth analysis of local emissions is needed and should be compared to the central valley emissions in an attempt to improve the air quality in Bakersfield.

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    150 просмотров29 страниц

    Discerning Alkyl Nitrate Abundance in Bakersfield, CA

    Загружено:

    jpeterson1
    Joshua Clark, DePauw University - Abstract: During the 2016 summer NASA Student Airborne Research Program (SARP), the NASA DC-8 flew over Bakersfield, CA because it consistently ranks in the top three U.S. cities with the worst air quality. Analysis of whole air samples collected during the Bakersfield airport missed approach indicated elevated concentrations of alkyl nitrates (RONO2). It is imperative that we study the source of alkyl nitrates as they lead to nitrogen oxide (NOx), an ozone precursor. High alkane (RH) concentrations were also measured, indicating the alkyl nitrates were most likely photochemically produced. NOAA HYSPLIT was used to determine whether emissions were localized or transported and found to mostly originate in the San Joaquin Valley, which coincides with the calculated mean air mass age of about 19 ± 5 hours. However, the age varied greatly from 8 to 31 hours, which is indicative of local emissions as well. Based on i/n pentane ratios of 2.3 ± 0.6, it was estimated that the sources of the emissions are mostly urban. This is significant because a combination of aged and fresh pollution suggests that a more in-depth analysis of local emissions is needed and should be compared to the central valley emissions in an attempt to improve the air quality in Bakersfield.

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    Discerning Alkyl Nitrate

    Abundance in Bakersfield, CA
    Joshua Clark1, Stacey Hughes2, Don R. Blake2, Rafe Day2
    1

    Dept. of Physics and Astronomy, DePauw University, Greencastle, IN


    2Dept. of Chemistry, University of California-Irvine, Irvine, CA

    Flight 2

    2 missed approaches Bakersfield, Santa


    Barbara

    Methane

    Gas Chromatography
    Flame Ionization Detector (FID)
    Injector

    Integrator
    FID
    Column

    Oven

    Alkyl Nitrates

    RONO2

    Directly emitted from ocean and biomass


    burning
    Indirectly emitted when RH oxidize in
    presence of NO

    Indirect production

    RONO2 is less dominant path of RO2 + NO


    < 15 % for C1 C5

    (1) RH + OH R + H2O
    (2) R + O2 RO2
    (3a) RO2+ NO RO + NO2
    (3b) RO2+ NO RONO2

    RONO2 Create Ozone

    Break down of RONO2 compounds produce


    NOx
    Photolysis < C4
    Oxidation with OH > C4

    Motivation

    HYSPLIT Forward Trajectory

    Alkyl Nitrate Abundance

    Isopropyl Nitrate

    <<Bakersfield

    Alkyl Nitrate Abundance

    2 Pentyl Nitrate

    <<Bakersfield

    Alkyl Nitrate Abundance

    2 Pentyl Nitrate - Bakersfield

    <<Bakersfield

    Alkyl Nitrate Abundance

    2 Pentyl Nitrate - Bakersfield

    <<Bakersfield

    Goals
    Why is the abundance as great, if not
    greater, at higher altitudes?
    Where are the alkyl nitrates coming from?
    What is the primary source?

    Isoprene -> boundary layer

    Isoprene has a lifetime of ~ 3 hrs

    <<Bakersfield

    Isoprene -> boundary layer

    Isoprene has a lifetime of ~ 3 hrs

    <<Bakersfield

    Alkyl Nitrate Abundance

    2 Pentyl Nitrate - Bakersfield

    <<Bakersfield

    HYSPLIT Backward
    Trajectory

    Wind blown from ocean and CV

    Transported Gases from Flight


    2

    Very little marine impact, but possible


    dairy influence

    Tracer

    Gas

    Mean
    (pptv)

    Max (pptv)

    Bakersfield
    (pptv)

    Marine

    Carbonyl
    Sulfide

    541

    750

    518

    Marine

    Methyl
    Bromide

    7.8

    145

    7.1

    Marine/Dairy

    Dimethyl
    Sulfide

    2.5

    107

    0.9

    Dairy

    Ethanol

    696

    37150

    832

    Alkane Presence

    Increase in alkanes in Bakersfield

    Lifetime

    Daughter to parent ratios determine lifetime

    Bertman, S. B.:Evolution Of Alkyl Nitrates With Air-Mass Age

    2 Pentyl Nitrate

    Min lifetime
    (Hr)

    Max
    lifetime(Hr)

    Mean
    lifetime( Hr)

    8.5

    31

    19.5

    Source Determination

    Source Determination

    Source Determination

    Source Determination

    Source Determination

    Fitting data to a Gaussian model with a


    mean of 2.0 implies urban emissions as the
    most abundant

    Conclusions
    The samples were collected in a well mixed
    boundary layer
    Air is being trapped in Bakersfield by the
    Sierra Nevada
    Some of the trapped air came from outside
    sources, but a majority was local, urban
    pollution
    Bakersfield both traps and produces alkanes
    judging by the air mass lifetimes

    Future Work
    Collect and analyze whole air samples via
    airborne and ground cans in Bakersfield and
    in the Central Valley
    Improve the air quality of Bakersfield
    Positive matrix factorization (PMF) to
    determine source percentage

    Acknowledgments
    Don R. Blake, Ph. D.
    Stacey Hughes, Ph. D. candidate
    Rowland-Blake Lab
    Rafe Day
    WAS group
    Jessie Sagona, Ph. D.
    Emily Schaller, Ph. D.
    NSERC

    Questions?

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