Hydrogen Peroxide Methylhydroperoxide Formaldehyde Peroxide Methylhydroperoxide Formaldehyde (Peroxyacetic Acid) ... OOH, ppt CH 2 O(NCAR), ppb Formaldehyde Acetaldehyde, Acetone, Methanol,

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  • Hydrogen PeroxideMethylhydroperoxide

    Formaldehyde & (Peroxyacetic Acid)

    Brian G. Heikes & Haiwei Shen, URIDaniel W. OSullivan, USNA

    Julie A. Snow, Slippery Rock U.

  • Tropospheric Ozone Radical Oxidants: HO, HO2, CH3OO, CH3C(O)OO ? Carbon Processing:

    HCs -> CH2O -> CO ; CH2O lifetime and carbon flux through CH2O CH3OOH or CH2O ; methane world vs nonmethane world CH3C(O)OOH (HO2 vs NO2) ;

    Extension of Trop-Chem Measurements by Satellite: CH2O directly Combined with other compounds and campaigns

    Vertical Transport & Mixing Tracers, Yes Working on being quantitative

    Instrument Development & Comparison H2O2 : URI, CIT & BAE146 CH2O: URI, NCAR & WP3

    Our INTEX ObjectivesIn Measuring Title Compounds

  • Instrument Changes and Comparison

    CH2O pre-mission, during, & prototype Simplified FIA system; improved noise Modified signal processing; noise vs response time Stability allows for continuous measurements

    Last Five Flights (16-20; 8/6,7,11,13 &14) 1 minute resolution with continuous sampling 25 pptv level of detection

    CH2O Relationships with Other Compounds

  • 0 1 2 3 4 5 6 7

    0

    1

    2

    3

    4

    5

    6

    7

    CH2O, ppb (URI)

    CH

    2O, p

    pb (N

    CA

    R)

    DC-8 Flt06 07/10/04

    Major Axis Reg.(All); DottedIntercept = -7.7781 16.4423 Slope = 1.4846 0.016654corr-coef = 0.95706

    MatLab Robust Fit; Solidb(robfit) = 58.048m(robfit) = 1.4183

    0 1 2 3 4 5 6 7

    0

    1

    2

    3

    4

    5

    6

    7

    CH2O, ppb (URI)

    CH

    2O, p

    pb (N

    CA

    R)

    DC-8 Flt19 08/13/04

    Major Axis Reg.(All); DottedIntercept = -97.5188 9.0237 Slope = 1.1835 0.01175corr-coef = 0.95563

    MatLab Robust Fit; Solidb(robfit) = -54.7793m(robfit) = 1.0647

    Direct comparison, URI & NCAR, 10-s Merge Product

    red ascent/descent green level blue Xw > 1%

    ~1.1~1.5

  • Formaldehyde Robust Fit Regression: NCAR = URI*slope + intercept

    0.00

    0.20

    0.40

    0.60

    0.80

    1.00

    1.20

    1.40

    1.60

    1.80

    6/22/2004 7/2/2004 7/12/2004 7/22/2004 8/1/2004 8/11/2004 8/21/2004

    Date of Flight

    Slop

    e

    -80

    -60

    -40

    -20

    0

    20

    40

    60

    80

    100

    120

    Inte

    rcep

    t

    m-robust

    b-robust

    Linear (m-robust)

  • Formaldehyde Relationships with Parents & Daughter Carbon Monoxide, Ethane, Propane, & Benzene

    0 200 4000

    1

    2

    3

    4

    CO, ppb

    CH

    2O(U

    RI),

    ppb

    DC-8 Flt6 07/10/04

    0 5000 100000

    1

    2

    3

    4

    C2H6, ppt

    CH

    2O(U

    RI),

    ppb

    0 2000 40000

    1

    2

    3

    4

    C3H8, ppt

    CH

    2O(U

    RI),

    ppb

    0 100 2000

    1

    2

    3

    4

    benzene, ppt

    CH

    2O(U

    RI),

    ppb

    0 200 400-2

    0

    2

    4

    6

    8

    CO, ppb

    CH

    2O(N

    CA

    R),

    ppb

    0 5000 10000-2

    0

    2

    4

    6

    8

    C2H6

    CH

    2O(N

    CA

    R),

    ppb

    0 2000 4000-2

    0

    2

    4

    6

    8

    C3H8, ppt

    CH

    2O(N

    CA

    R),

    ppb

    0 100 200-2

    0

    2

    4

    6

    8

    benzene, pptC

    H2O

    (NC

    AR

    ), pp

    b

  • 0 5000

    1

    2

    3

    4

    C2H2, ppb

    CH

    2O(U

    RI),

    ppb

    DC-8 Flt6 07/10/04

    0 200 4000

    1

    2

    3

    4

    C2H4, ppt

    CH

    2O(U

    RI),

    ppb

    0 2000 40000

    1

    2

    3

    4

    isoprene, ppt

    CH

    2O(U

    RI),

    ppb

    0 50 1000

    1

    2

    3

    4

    C3H6, ppt

    CH

    2O(U

    RI),

    ppb

    0 500-2

    0

    2

    4

    6

    8

    C2H2, ppb

    CH

    2O(N

    CA

    R),

    ppb

    0 200 400-2

    0

    2

    4

    6

    8

    C2H4, ppt

    CH

    2O(N

    CA

    R),

    ppb

    0 2000 4000-2

    0

    2

    4

    6

    8

    isoprene, ppt

    CH

    2O(N

    CA

    R),

    ppb

    0 50 100-2

    0

    2

    4

    6

    8

    C3H6, pptC

    H2O

    (NC

    AR

    ), pp

    b

    Formaldehyde Relationships Continued Ethyne, Ethene, Isoprene, & Propene

  • 0 1000 20000

    1

    2

    3

    4

    CH3CHO, ppb

    CH

    2O(U

    RI),

    ppb

    DC-8 Flt6 07/10/04

    0 5000 100000

    1

    2

    3

    4

    CH3COCH3, ppt

    CH

    2O(U

    RI),

    ppb

    0 5000 100000

    1

    2

    3

    4

    CH3OH, ppt

    CH

    2O(U

    RI),

    ppb

    0 1000 20000

    1

    2

    3

    4

    CH3OOH, ppt

    CH

    2O(U

    RI),

    ppb

    0 1000 2000-2

    0

    2

    4

    6

    8

    CH3CHO, ppb

    CH

    2O(N

    CA

    R),

    ppb

    0 5000 10000-2

    0

    2

    4

    6

    8

    CH3COCH3, ppt

    CH

    2O(N

    CA

    R),

    ppb

    0 5000 10000-2

    0

    2

    4

    6

    8

    CH3OH, ppt

    CH

    2O(N

    CA

    R),

    ppb

    0 1000 2000-2

    0

    2

    4

    6

    8

    CH3OOH, pptC

    H2O

    (NC

    AR

    ), pp

    b

    Formaldehyde Acetaldehyde, Acetone, Methanol, Methylhydroperoxide

  • 0 50 1000

    1

    2

    3

    4

    HO2, ppt

    CH

    2O(U

    RI),

    ppb

    DC-8 Flt6 07/10/04

    0 50 1000

    1

    2

    3

    4

    O3, ppb

    CH

    2O(U

    RI),

    ppb

    102

    104

    106

    0

    1

    2

    3

    4

    H2O(proj), ppm

    CH

    2O(U

    RI),

    ppb

    10-2

    10-1

    100

    0

    1

    2

    3

    4

    HO, ppt

    CH

    2O(U

    RI),

    ppb

    0 50 100-2

    0

    2

    4

    6

    8

    HO2, ppt

    CH

    2O(N

    CA

    R),

    ppb

    0 50 100-2

    0

    2

    4

    6

    8

    O3, ppb

    CH

    2O(N

    CA

    R),

    ppb

    102 104 106-2

    0

    2

    4

    6

    8

    H2O(proj), ppm

    CH

    2O(N

    CA

    R),

    ppb

    10-2 10-1 100-2

    0

    2

    4

    6

    8

    HO, pptC

    H2O

    (NC

    AR

    ), pp

    b

    Formaldehyde Perhydroxyl, Ozone, Water, & Hydroxyl

  • 0 2 4

    200

    400

    600

    800

    1000

    P, h

    Pa

    CH2O(URI), ppb

    DC-8 Flt6 07/10/04

    0 50 1000

    1

    2

    3

    4

    RH(water), %

    CH

    2O(U

    RI),

    ppb

    100

    102

    104

    0

    1

    2

    3

    4

    NO2, ppt

    CH

    2O(U

    RI),

    ppb

    0 1 2x 10

    4

    0

    1

    2

    3

    4

    SO2, ppt

    CH

    2O(U

    RI),

    ppb

    0 5

    200

    400

    600

    800

    1000

    P, h

    Pa

    CH2O(NCAR), ppb0 50 100

    -2

    0

    2

    4

    6

    8

    RH(water), %

    CH

    2O(N

    CA

    R),

    ppb

    100

    102

    104

    -2

    0

    2

    4

    6

    8

    NO2, ppt

    CH

    2O(N

    CA

    R),

    ppb

    0 1 2x 10

    4

    -2

    0

    2

    4

    6

    8

    SO2, pptC

    H2O

    (NC

    AR

    ), pp

    b

    Formaldehyde vsPressure, RH, Nitrogen Dioxide, Sulfur Dioxide

  • Instrument Changes & Comparison

    H2O2 / CH3OOH / CH3C(O)OOH Initial setup for H2O2 / CH3OOH alone StL Samples Indicated 3rd ROOH;

    PAA on CIT New HPLC Column online in Portsmouth

    Tests for hydroxymethylhydroperoxide negative Tests for peroxyacetic acid positive

    Modify mode and run times to resolve PAA, PAA is a work in progress (~3 months more)

    Hence, less frequent sampling from NH on.

  • 0 2 4 6 8 10-1

    0

    1

    2

    3

    4

    5

    6

    7

    8

    9

    10

    H2O2, ppb (URI)

    H2O

    2, p

    pb (C

    alTe

    ch)

    DC-8 Flt06 07/10/04

    M-A Regression

    M-A Regression,

  • Hydrogen Peroxide Robust Fit: CIT = URI * slope + intercept

    0

    0.2

    0.4

    0.6

    0.8

    1

    1.2

    1.4

    7/7 7/12 7/17 7/22 7/27 8/1 8/6 8/11 8/16

    Flight Date

    Slop

    e

    0

    50

    100

    150

    200

    250

    Inte

    rcep

    t

    m-robustb-robust

  • 0 20 400

    1

    2

    3

    4

    HO2, ppt

    H2O

    2(U

    RI),

    ppb

    DC-8 Flt8 07/15/04

    0 100 2000

    1

    2

    3

    4

    O3, ppb

    H2O

    2(U

    RI),

    ppb

    100

    105

    0

    1

    2

    3

    4

    H2O(proj), ppm

    H2O

    2(U

    RI),

    ppb

    10-2

    10-1

    100

    0

    1

    2

    3

    4

    HO, ppt

    H2O

    2(U

    RI),

    ppb

    0 20 400

    1

    2

    3

    4

    HO2, ppt

    H2O

    2(C

    IT),

    ppb

    0 100 2000

    1

    2

    3

    4

    O3, ppb

    H2O

    2(C

    IT),

    ppb

    100

    105

    0

    1

    2

    3

    4

    H2O(proj), ppm

    H2O

    2(C

    IT),

    ppb

    10-2

    10-1

    100

    0

    1

    2

    3

    4

    HO, pptH

    2O2(

    CIT

    ), pp

    b

    Hydrogen Peroxide RelationshipsPerhydroxyl, Ozone, Water, & Hydroxyl

  • Hydrogen Peroxide Pressure, RH, Nitrogen Dioxide, Sulfur Dioxide

    0 2 4

    200

    400

    600

    800

    1000

    P, h

    Pa

    H2O2(URI), ppb

    DC-8 Flt8 07/15/04

    0 50 1000

    1

    2

    3

    4

    RH(water), %

    H2O

    2(U

    RI),

    ppb

    10-5 100 1050

    1

    2

    3

    4

    NO2, ppt

    H2O

    2(U

    RI),

    ppb

    0 1000 20000

    1

    2

    3

    4

    SO2, ppt

    H2O

    2(U

    RI),

    ppb

    0 2 4

    200

    400

    600

    800

    1000

    P, h

    Pa

    H2O2(CIT), ppb0 50 100

    0

    1

    2

    3

    4

    RH(water), %

    H2O

    2(C

    IT),

    ppb

    10-5 100 1050

    1

    2

    3

    4

    NO2, ppt

    H2O

    2(C

    IT),

    ppb

    0 1000 20000

    1

    2

    3

    4

    SO2, pptH

    2O2(

    CIT

    ), pp

    b

  • 0 500 10000

    1

    2

    3

    4

    CH3CHO, ppb

    H2O

    2(U

    RI),

    ppb

    DC-8 Flt8 07/15/04

    0 5000 100000

    1

    2

    3

    4

    CH3COCH3, ppt

    H2O

    2(U

    RI),

    ppb

    0 5000 100000

    1

    2

    3

    4

    CH3OH, ppt

    H2O

    2(U

    RI),

    ppb

    0 1000 20000

    1

    2

    3

    4

    CH3OOH, ppt

    H2O

    2(U

    RI),

    ppb

    0 500 10000

    1

    2

    3

    4

    CH3CHO, ppb

    H2O

    2(C

    IT),

    ppb

    0 5000 100000

    1

    2

    3

    4

    CH3COCH3, ppt

    H2O

    2(C

    IT),

    ppb

    0 5000 100000

    1

    2

    3

    4

    CH3OH, ppt

    H2O

    2(C

    IT),

    ppb

    0 1000 20000

    1

    2

    3

    4

    CH3OOH, pptH

    2O2(

    CIT

    ), pp

    b

    Hydrogen Peroxide Acetaldehyde, Acetone, Methanol, Methylhydroperoxide

  • Case Study: August 11, 2004; DC-8 Flight 18

    1

    2

    34

    56

    78

    910

  • New Brunswick Far Off N. Carolina

    St Louis Far Off N. Carolina

    2040 60 801001200

    5

    10

    Alti

    tude

    (GPS

    ), km

    O3, ppb

    DC-8 Flt18 08/11/04

    22040 60 801001200

    5

    10

    O3, ppb

    32040 60 801001200

    5

    10

    4

    O3, ppb2040 60 801001200

    5

    10

    5

    O3, ppb20 40 60 801001200

    5

    10

    6

    O3, ppb

    2040 60 801001200

    2

    4

    6

    8

    10

    12

    Alti

    tude

    (GPS

    ), km

    10

    O3, ppb2040 60 801001200

    2

    4

    6

    8

    10

    12

    9

    O3, ppb2040 60 801001200

    2

    4

    6

    8

    10

    12

    8

    O3, ppb2040 60 801001200

    2

    4

    6

    8

    10

    12

    7

    O3, ppb20 40 60 801001200

    2

    4

    6

    8

    10

    12

    6

    O3, ppb

  • New Brunswick Far Off N. Carolina

    St Louis Far Off N. Carolina

    50 100 1500

    5

    10

    Alti

    tude

    (GPS

    ), km

    CO, ppb

    DC-8 Flt18 08/11/04

    250 100 150

    0

    5

    10

    CO, ppb

    350 100 150

    0

    5

    10

    4

    CO, ppb50 100 150

    0

    5

    10

    5

    CO, ppb50 100 150

    0

    5

    10

    6

    CO, ppb

    50 100 1500

    5

    10

    Alti

    tude

    (GPS

    ), km

    10

    CO, ppb50 100 150

    0

    5

    10

    9

    CO, ppb50 100 150

    0

    5

    10

    8

    CO, ppb50 100 150

    0

    5

    10

    7

    CO, ppb50 100 150

    0

    5

    10

    6

    CO, ppb

  • 0 5000 100000

    5

    10

    Alti

    tude

    (GPS

    ), km

    CH3OOH (CH2O or H2O2), ppt

    DC-8 Flt18 08/11/04

    20 5000

    0

    5

    10

    CH3OOH (CH2O or H2O2), ppt

    30 5000

    0

    5

    10

    4

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    5

    10

    5

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    5

    10

    6

    CH3OOH (CH2O or H2O2), ppt

    0 50000

    246

    81012

    Alti

    tude

    (GPS

    ), km

    10

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    246

    81012

    9

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    246

    81012

    8

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    246

    81012

    7

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    246

    81012

    6

    CH3OOH (CH2O or H2O2), ppt

    New Brunswick Far Off N. Carolina

    St Louis Far Off N. Carolina

    grn H2O2 blk CH3OOH red CH2O(URI) mag CH2O(NCAR)

  • New Brunswick Far Off N. Carolina

    St Louis Far Off N. Carolina

    grn H2O2 blk CH3OOH red CH2O(URI) mag CH2O(NCAR)

    0 500 10000

    5

    10

    Alti

    tude

    (GPS

    ), km

    CH3OOH (CH2O or H2O2), ppt

    DC-8 Flt18 08/11/04

    20 500 1000

    0

    5

    10

    CH3OOH (CH2O or H2O2), ppt

    30 500 1000

    0

    5

    10

    4

    CH3OOH (CH2O or H2O2), ppt0 500 1000

    0

    5

    10

    5

    CH3OOH (CH2O or H2O2), ppt0 500 1000

    0

    5

    10

    CH3OOH (CH2O or H2O2), ppt

    0 500 10000

    5

    10

    Alti

    tude

    (GPS

    ), km

    10

    CH3OOH (CH2O or H2O2), ppt0 500 1000

    0

    5

    10

    9

    CH3OOH (CH2O or H2O2), ppt0 500 1000

    0

    5

    10

    8

    CH3OOH (CH2O or H2O2), ppt0 500 1000

    0

    5

    10

    7

    CH3OOH (CH2O or H2O2), ppt0 500 1000

    0

    5

    10

    CH3OOH (CH2O or H2O2), ppt

  • SummaryCH2O MeasurementsURI to NCAR comparison factor of 1.1 to 1.6Highly correlatedIndicate same functional relationships to other

    compounds

    H2O2 MeasurementsURI to CIT comparison factor of 0.7 to 1.2Well correlated with outliers, better when Xv

  • Case Study: August 2, 2004; DC-8 Flight 15

    1

    2

    34

    56

    7 8

    910

    11

    1213

    14

  • 0 100 2000

    2

    4

    6

    8

    10

    12

    Alti

    tude

    (GPS

    ), km

    O3, ppb

    DC-8 Flt15 08/02/04

    30 100 200

    0

    2

    4

    6

    8

    10

    12

    O3, ppb

    40 100 200

    0

    2

    4

    6

    8

    10

    12

    5

    O3, ppb0 100 200

    0

    2

    4

    6

    8

    10

    12

    6

    O3, ppb0 100 200

    0

    2

    4

    6

    8

    10

    12

    7

    O3, ppb0 100 200

    0

    2

    4

    6

    8

    10

    12

    Alti

    tude

    (GPS

    ), km

    8

    O3, ppb

    0 100 2000

    2

    4

    6

    8

    10

    12

    14

    O3, ppb0 100 200

    0

    2

    4

    6

    8

    10

    12

    13

    O3, ppb0 100 200

    0

    2

    4

    6

    8

    10

    12

    12

    O3, ppb0 100 200

    0

    2

    4

    6

    8

    10

    12

    11

    O3, ppb0 100 200

    0

    2

    4

    6

    8

    10

    12

    10

    O3, ppb0 100 200

    0

    2

    4

    6

    8

    10

    12

    9

    O3, ppb

    S. Quebec N. New Foundland

    S. Maine S. New Foundland

  • S. Quebec N. New Foundland

    S. Maine S. New Foundland

    50 1001500

    2

    4

    6

    8

    10

    12

    Alti

    tude

    (GPS

    ), km

    C O , ppb

    D C -8 F lt15 08/02/04

    350 100150

    0

    2

    4

    6

    8

    10

    12

    C O , ppb

    450 100150

    0

    2

    4

    6

    8

    10

    12

    5

    C O , ppb50 100150

    0

    2

    4

    6

    8

    10

    12

    6

    C O , ppb50 100 150

    0

    2

    4

    6

    8

    10

    12

    7

    C O , ppb50100150

    0

    2

    4

    6

    8

    10

    12

    Alti

    tude

    (GPS

    ), km

    8

    C O , ppb

    50 1001500

    2

    4

    6

    8

    10

    12

    14

    C O , ppb50 100150

    0

    2

    4

    6

    8

    10

    12

    13

    C O , ppb50 100150

    0

    2

    4

    6

    8

    10

    12

    12

    C O , ppb50 100150

    0

    2

    4

    6

    8

    10

    12

    11

    C O , ppb50 100 150

    0

    2

    4

    6

    8

    10

    12

    10

    C O , ppb50100150

    0

    2

    4

    6

    8

    10

    12

    9

    C O , ppb

  • S. Quebec N. New Foundland

    S. Maine S. New Foundland

    0 50000

    2

    4

    6

    8

    10

    12

    Alti

    tude

    (GP

    S),

    km

    CH3OOH (CH2O or H2O2), ppt

    DC-8 Flt15 08/02/04

    30 5000

    0

    2

    4

    6

    8

    10

    12

    CH3OOH (CH2O or H2O2), ppt

    40 5000

    0

    2

    4

    6

    8

    10

    12

    5

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    2

    4

    6

    8

    10

    12

    6

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    2

    4

    6

    8

    10

    12

    7

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    2

    4

    6

    8

    10

    12

    Alti

    tude

    (GP

    S),

    km

    8

    CH3OOH (CH2O or H2O2), ppt

    0 50000

    2

    4

    6

    8

    10

    12

    14

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    2

    4

    6

    8

    10

    12

    13

    CH3OOH (CH2O or H2O2), ppt0 5000

    0

    2

    4

    6

    8

    10

    12

    12

    CH3OOH

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