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  • Estimation of Tropospheric OH and CL Concentrations Inferred From NMHC Ratios Over Southern California

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    jpeterson1
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    Karimar Ledesma, University of Puerto Rico at Mayagüez Non Methane Hydrocarbons (NMHC) play an important role as chemical precursors to ozone and secondary organic aerosol (SOA) in the troposphere via their photochemical oxidation. In turn, ozone and SOA affect global climate, air quality, and human health. Though oxidation of NMHCs generally occurs via reaction with the hydroxyl radical (OH), oxidation can also occur via reaction with atomic chlorine (Cl), often at rates that are orders of magnitude greater than with OH. During the 2015 NASA Student Airborne Research Program (SARP), whole air samples (WAS) were collected onboard the NASA DC-8 over Southern California. In this study, four regions were focused on: The Los Angeles area, the Central Valley, the Salton Sea, and Santa Barbara (which also include samples collected on the ground). Using ratios of select NMHCs that react with OH and Cl at different rates, Cl concentrations over the four study regions were estimated to be 1.49 X 104, 1.1 X 104 , 8.83X 103 , 1.23 X 104 and 1.77X 104 molecules cm-3 respectively. These results were used to calculate theoretical OH radical concentration, which were in the range of 1.1 X105 to 9.053 X105 molecules cm-3 over the whole study region. These values were compared with WAS collected during the 2014 NASA SARP project and the concentration of OH and Cl vary considerably. Despite of this variability, the magnitude of OH and Cl concentrations for both years has reasonable impact on ozone formation. Although the Central valley is far away from the ocean we estimated a relatively high Cl concentration, indicating the importance of Cl in ozone production even in inland regions of California.

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    Estimation of Tropospheric OH and Cl Concentrations Inferred from NMHC ratios over Southern California

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    Karimar Ledesma, University of Puerto Rico at Mayagüez Non Methane Hydrocarbons (NMHC) play an important role as chemical precursors to ozone and secondary organic aerosol (SOA) in the troposphere via their photochemical oxidation. In turn, ozone and SOA affect global climate, air quality, and human health. Though oxidation of NMHCs generally occurs via reaction with the hydroxyl radical (OH), oxidation can also occur via reaction with atomic chlorine (Cl), often at rates that are orders of magnitude greater than with OH. During the 2015 NASA Student Airborne Research Program (SARP), whole air samples (WAS) were collected onboard the NASA DC-8 over Southern California. In this study, four regions were focused on: The Los Angeles area, the Central Valley, the Salton Sea, and Santa Barbara (which also include samples collected on the ground). Using ratios of select NMHCs that react with OH and Cl at different rates, Cl concentrations over the four study regions were estimated to be 1.49 X 104, 1.1 X 104 , 8.83X 103 , 1.23 X 104 and 1.77X 104 molecules cm-3 respectively. These results were used to calculate theoretical OH radical concentration, which were in the range of 1.1 X105 to 9.053 X105 molecules cm-3 over the whole study region. These values were compared with WAS collected during the 2014 NASA SARP project and the concentration of OH and Cl vary considerably. Despite of this variability, the magnitude of OH and Cl concentrations for both years has reasonable impact on ozone formation. Although the Central valley is far away from the ocean we estimated a relatively high Cl concentration, indicating the importance of Cl in ozone production even in inland regions of California.

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    108 просмотров30 страниц

    Estimation of Tropospheric OH and CL Concentrations Inferred From NMHC Ratios Over Southern California

    Загружено:

    jpeterson1
    Karimar Ledesma, University of Puerto Rico at Mayagüez Non Methane Hydrocarbons (NMHC) play an important role as chemical precursors to ozone and secondary organic aerosol (SOA) in the troposphere via their photochemical oxidation. In turn, ozone and SOA affect global climate, air quality, and human health. Though oxidation of NMHCs generally occurs via reaction with the hydroxyl radical (OH), oxidation can also occur via reaction with atomic chlorine (Cl), often at rates that are orders of magnitude greater than with OH. During the 2015 NASA Student Airborne Research Program (SARP), whole air samples (WAS) were collected onboard the NASA DC-8 over Southern California. In this study, four regions were focused on: The Los Angeles area, the Central Valley, the Salton Sea, and Santa Barbara (which also include samples collected on the ground). Using ratios of select NMHCs that react with OH and Cl at different rates, Cl concentrations over the four study regions were estimated to be 1.49 X 104, 1.1 X 104 , 8.83X 103 , 1.23 X 104 and 1.77X 104 molecules cm-3 respectively. These results were used to calculate theoretical OH radical concentration, which were in the range of 1.1 X105 to 9.053 X105 molecules cm-3 over the whole study region. These values were compared with WAS collected during the 2014 NASA SARP project and the concentration of OH and Cl vary considerably. Despite of this variability, the magnitude of OH and Cl concentrations for both years has reasonable impact on ozone formation. Although the Central valley is far away from the ocean we estimated a relatively high Cl concentration, indicating the importance of Cl in ozone production even in inland regions of California.

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    Estimation of Tropospheric OH and Cl

    concentrations inferred from NonMethane Hydrocarbons ratios over


    Southern California

    Karimar Ledesma-Maldonado(1), Jason Schroeder(2) , Donald R. Blake(2)


    (1)University of Puerto Rico, Mayagez Campus, Mayagez Puerto Rico
    (2) University of California, Irvine, Irvine California
    NASA SARP 2015
    Whole Air Sample(WAS) Group

    What is the importance of studying OH and Cl?


    Oxidation of Non-Methane Hydrocarbons (NMHC) via:
    Reaction with Cl

    Reaction with OH
    CH3CH3 + OH

    CH3CH2 + H2O

    CH3CH3 + Cl

    CH3CH2 + O2

    CH3CH2 O2

    CH3CH2 O2 + NO

    CH3CH2 O + N O2

    VOC + NO2 + h

    O3
    SOA

    CH3CH2 + HCl

    Is Ozone (O3) bad?


    Impact in three areas of concern:

    Is Secondary Organic Aerosols(SOA)


    bad?

    SOA

    Typical Tropospheric Concentration


    OH

    Cl

    105-107 molecules cm-3

    102 -104 molecules cm-3

    kOH

    kCl >> kOH

    Cl reacts with VOCs much faster than OH does !

    Study Objective
    Compared the variability of NMHC oxidation via
    reaction with OH and Cl through different
    location in the Southern of California.

    Methodology
    Santa Barbara Field Trip

    Methodology

    Methodology
    Calculate
    i-butane: n-butane
    ratio

    Cl

    Calculate
    ln(n-butane:
    benzene) ratio
    Cl:OH
    Calculate
    ln(n-pentane:
    benzene)
    ratio

    Cl

    Cl:OH

    OH

    1
    []=[](
    [])

    [1]/[]=(()())+(
    ) ()/(()())+(
    ) ()

    1
    1/ 2=[]

    1
    2
    3

    Four regions were focused on


    Los Angeles
    Santa Barbara
    Central Valley
    Salton Sea
    All samples taken below 1.5km

    i-Butane vs. n-Butane?

    i-Butane

    Central Valley

    m=0.58

    i-Butane

    n-Butane

    m=0.57

    Salton Sea

    n-Butane

    i-Butane

    LA

    m=0.67

    i-Butane

    n-Butane

    m=0.63

    n-Butane

    Santa Barbara

    i-Butane

    Santa Barbara

    m=0.63

    samples
    collected on
    the plane

    i-Butane

    n-Butane

    samples
    collected on
    the ground
    m=0.73

    n-Butane

    []=[](
    [])

    Cl

    Cl:OH

    OH

    [1]/[]=(()())+(
    ) ()/(()())+(
    ) ()

    1/ 2=[]

    1
    2
    3

    Comparison of the four regions


    Locations

    Average
    Cl

    Cl (molecules cm-3 )

    (molecules
    cm-3 )

    Los
    Angeles

    1.5 X104

    Santa
    Barbara
    (Plane)

    1.2 X104

    Santa
    Barbara
    (Ground)

    1.8X104

    Central
    Valley

    8.2 X103

    Salton
    Sea

    7.5 X103

    1
    [
    ]=[](
    [])

    Cl

    Cl:OH

    []/[]=(()())+(
    ) ()/(()())+(
    ) ()
    1

    OH

    1/ 2=[]

    1
    2
    3

    ln(n-butane/benzene) vs. ln(n-pentane/


    benzene)?

    ln(n-butane/benzene)
    ln(n-butane/benzene)

    Central Valley

    m=0.64

    ln(n-pentane/benzene)

    m=0.91 ???

    ln(n-pentane/benzene)

    Salton Sea

    ln(n-butane/benzene)
    ln(n-butane/benzene)

    LA

    m=0.87

    ln(n-pentane/benzene)

    m=0.88
    Santa Barbara

    ln(n-pentane/benzene)

    ln(n-butane/benzene)
    ln(n-butane/benzene)

    Santa Barbara

    m=0.88

    samples
    collected on
    the plane

    ln(n-pentane/benzene)

    m=0.89

    ln(n-pentane/benzene)

    samples
    collected on
    the ground

    1
    []=[](
    [])

    Cl

    Cl:OH

    OH

    []/[]=(()())+(
    ) ()/(()())+(
    ) ()
    1
    1/ 2=[]

    1
    2
    3

    Cl
    Locations

    (molecules

    cm-3

    Cl:OH
    Ratio

    OH
    (molecules cm-3 )

    1.9 X10-2

    8.2 X105

    2.2 X10-2

    5.5X105

    Los Angeles

    1.5 X104

    Santa Barbara
    (Plane)

    1.2 X104

    Santa Barbara
    (Ground)

    1.8 X104

    2.5 X10-2

    6.4 X105

    Central Valley

    8.2 X103

    1.5 X10-2

    4.9 X105

    Salton Sea

    7.5 X103

    2 X10-2

    2.5 X105

    OH
    Cl

    9
    8
    7
    6
    5
    4
    3
    2
    1
    0

    Los Angeles

    Santa
    Santa
    Barbara(Plane) Barbara(Ground)

    Central Valley

    Salton Sea

    Cl concentration (X104molecules cm-3 )

    OH concentration (X105molecules cm-3 )

    OH and Cl Concentrations

    Summary
    Concentrations of OH and Cl were calculated
    Cl levels impact SoCal oxidation of NMHCs and
    in some cases are 1.5-1.8 X104
    Under certain conditions Cl could be
    significantly affecting ozone formation in LA and
    Santa Barbara.

    Future Work
    Use more combination of NMHCs
    Compare with models to see how our results
    compare.
    Compare with other SARP years.
    Estimate the amount of Cl above 1.5km

    References
    Arsene C., Bougiatioti A. et.al, 2007: Tropospheric OH and Cl
    levels deduced from non-methane hydrocarbon measurements in a
    marine site. Atmos.Chem. Phys., 7,4661-4673.
    Gorham K.A., Blake N.J., et.al, 2010: Seasonal and diurnal
    measurements of carbon monoxide and nonmethane hydrocarbons
    at. Mt. Wilson, California:Indirect evidence of atomic Cl in the Los
    Angeles basin. Atmospheric Environment 44, 2271-2279
    Finlayson B.J. and Pitts J.N., 2000: Chemistry of the Upper and
    Lower Atmosphere. Chapter 6, p. 179-263.

    Acknowledgements
    Dr. Jason Schroeder
    Dr. Donald R. Blake
    Sean Freeman
    WAS Snake n Blake Group
    Rowland-Blake Lab
    Dr. Emily Schaller
    Rick Shetter
    Ocean Group
    NSERC
    SARP
    NASA

    Thanks for you attention!

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