Hydrogen Peroxide Methylhydroperoxide Formaldehyde & (Peroxyacetic Acid)

Brian G. Heikes & Haiwei Shen, URI Daniel W. O’Sullivan, USNA Julie A. Snow, Slippery Rock U. Our INTEX Objectives In Measuring Title Compounds

• Tropospheric Ozone • Radical Oxidants: HO, HO2, CH3OO, CH3C(O)OO ? • Carbon Processing: – HC’s -> 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 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 DC-8 Flt06 07/10/04 DC-8 Flt19 08/13/04 7 7 Major Axis Reg.(All); Dotted Major Axis Reg.(All); Dotted Intercept = -7.7781 ± 16.4423 Intercept = -97.5188 ± 9.0237 6 6 Slope = 1.4846 ± 0.016654 Slope = 1.1835 ± 0.01175 corr-coef = 0.95706 corr-coef = 0.95563 5 5

4 4

3 3 O, ppb (NCAR) O, ppb (NCAR) O, 2 ~1.5 2 ~1.1 CH 2 CH 2

1 1 MatLab Robust Fit; Solid MatLab Robust Fit; Solid b(robfit) = 58.048 b(robfit) = -54.7793 0 m(robfit) = 1.4183 0 m(robfit) = 1.0647

0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 CH O, ppb (URI) CH O, ppb (URI) 2 2

Direct comparison, URI & NCAR, 10-s Merge Product red – ascent/descent green – level blue – Xw > 1% Formaldehyde Robust Fit Regression: NCAR = URI*slope + intercept

1.80 120

1.60 100

1.40 80 60 1.20 40 1.00 20

Slope 0.80

0 Intercept 0.60 -20

0.40 m-robust -40 b-robust 0.20 -60 Linear (m-robust) 0.00 -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 Formaldehyde Relationships with Parents & Daughter Carbon Monoxide, Ethane, Propane, & Benzene

DC-8 Flt6 07/10/04 4 4 4 4

3 3 3 3

2 2 2 2 O(URI), ppb O(URI), ppb O(URI), ppb O(URI), ppb 2 2 1 2 1 2 1 1 CH CH CH CH

0 0 0 0 0 200 400 0 5000 10000 0 2000 4000 0 100 200 CO, ppb C H , ppt C H , ppt benzene, ppt 2 6 3 8 8 8 8 8

6 6 6 6

4 4 4 4

2 2 2 2 O(NCAR), ppb O(NCAR), ppb O(NCAR), ppb O(NCAR), ppb 2 2 0 2 0 2 0 0 CH CH CH CH -2 -2 -2 -2 0 200 400 0 5000 10000 0 2000 4000 0 100 200 CO, ppb C H C H , ppt benzene, ppt 2 6 3 8 Formaldehyde Relationships Continued Ethyne, Ethene, Isoprene, & Propene

DC-8 Flt6 07/10/04 4 4 4 4

3 3 3 3

2 2 2 2 O(URI), ppb O(URI), ppb O(URI), ppb O(URI), ppb 2 2 1 2 1 2 1 1 CH CH CH CH

0 0 0 0 0 500 0 200 400 0 2000 4000 0 50 100 C H , ppb C H , ppt isoprene, ppt C H , ppt 2 2 2 4 3 6 8 8 8 8

6 6 6 6

4 4 4 4

2 2 2 2 O(NCAR), ppb O(NCAR), ppb O(NCAR), ppb O(NCAR), ppb 2 2 0 2 0 2 0 0 CH CH CH CH -2 -2 -2 -2 0 500 0 200 400 0 2000 4000 0 50 100 C H , ppb C H , ppt isoprene, ppt C H , ppt 2 2 2 4 3 6 Formaldehyde … Acetaldehyde, Acetone, Methanol, Methylhydroperoxide

DC-8 Flt6 07/10/04 4 4 4 4

3 3 3 3

2 2 2 2 O(URI), ppb O(URI), ppb O(URI), ppb O(URI), ppb 2 2 2 2 1 1 1 1 CH CH CH CH

0 0 0 0 0 1000 2000 0 5000 10000 0 5000 10000 0 1000 2000 CH CHO, ppb CH COCH , ppt CH OH, ppt CH OOH, ppt 3 3 3 3 3

8 8 8 8

6 6 6 6

4 4 4 4

2 2 2 2 O(NCAR), ppb O(NCAR), ppb O(NCAR), ppb O(NCAR), ppb 2 2 2 2 0 0 0 0 CH CH CH CH

-2 -2 -2 -2 0 1000 2000 0 5000 10000 0 5000 10000 0 1000 2000 CH CHO, ppb CH COCH , ppt CH OH, ppt CH OOH, ppt 3 3 3 3 3 Formaldehyde … Perhydroxyl, Ozone, Water, & Hydroxyl

DC-8 Flt6 07/10/04 4 4 4 4

3 3 3 3

2 2 2 2 O(URI), ppb O(URI), ppb O(URI), ppb O(URI), ppb 2 2 2 2 1 1 1 1 CH CH CH CH

0 0 0 0 2 4 6 -2 -1 0 0 50 100 0 50 100 10 10 10 10 10 10 HO , ppt O , ppb H O(proj), ppm HO, ppt 2 3 2 8 8 8 8

6 6 6 6

4 4 4 4

2 2 2 2 O(NCAR), ppb O(NCAR), ppb O(NCAR), ppb O(NCAR), ppb 2 2 2 2 0 0 0 0 CH CH CH CH

-2 -2 -2 -2 2 4 6 -2 -1 0 0 50 100 0 50 100 10 10 10 10 10 10 HO , ppt O , ppb H O(proj), ppm HO, ppt 2 3 2 Formaldehyde vs Pressure, RH, Nitrogen Dioxide, Sulfur Dioxide

DC-8 Flt6 07/10/04 200 4 4 4

400 3 3 3

600 2 2 2 P, hPa O(URI), ppb O(URI), O(URI), ppb O(URI), ppb O(URI), 2 2 2 800 1 1 1 CH CH CH

1000 0 0 0 0 2 4 0 2 4 0 50 100 10 10 10 0 1 2 CH O(URI), ppb RH(water), % NO , ppt SO , ppt 4 2 2 2 x 10 200 8 8 8

6 6 6 400 4 4 4 600

P, hPa 2 2 2 O(NCAR), ppb O(NCAR), ppb O(NCAR), ppb 2 800 2 2 0 0 0 CH CH CH 1000 -2 -2 -2 0 2 4 0 5 0 50 100 10 10 10 0 1 2 CH O(NCAR), ppb RH(water), % NO , ppt SO , ppt 4 2 2 2 x 10 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. DC-8 Flt06 07/10/04 DC-8 Flt19 08/13/04 10 10 M-A Regression 9 9

8 8

7 7

6 6 M-A Regression, <1 5 5 M-A Regression M-A Regression, <1 4 4 , ppb (CalTech) , ppb , ppb (CalTech) 2 2 Robust Fit O O 2 2 3 3 b(robfit) = 0.1 H H m(robfit) = 0.64912 2 2 ~1.2 1 1 Robust Fit ~0.65 0 b(robfit) = 0.0 0 m(robfit) = 1.214 -1 -1 0 2 4 6 8 10 0 2 4 6 8 10 H O , ppb (URI) H O , ppb (URI) 2 2 2 2

URI-CIT Direct Comparison – OUTLIERS – Robust Fit Algorithm (MatLab) red – ascent/descent green – level blue – Xv < 1% Hydrogen Peroxide Robust Fit: CIT = URI * slope + intercept

1.4 250

1.2 200 1

150 0.8

Slope 0.6 m-robust Intercept b-robust 100

0.4 50 0.2

0 0 7/7 7/12 7/17 7/22 7/27 8/1 8/6 8/11 8/16 Flight Date Hydrogen Peroxide Relationships Perhydroxyl, Ozone, Water, & Hydroxyl

DC-8 Flt8 07/15/04 4 4 4 4

3 3 3 3

2 2 2 2 (URI), ppb (URI), ppb (URI), ppb (URI), ppb 2 2 2 2 O O O O 2 2 1 2 1 2 1 1 H H H H

0 0 0 0 0 5 -2 -1 0 0 20 40 0 100 200 10 10 10 10 10 HO , ppt O , ppb H O(proj), ppm HO, ppt 2 3 2 4 4 4 4

3 3 3 3

2 2 2 2 (CIT), ppb (CIT), ppb (CIT), ppb (CIT), ppb 2 2 2 2 O O O O 2 2 1 2 1 2 1 1 H H H H

0 0 0 0 0 5 -2 -1 0 0 20 40 0 100 200 10 10 10 10 10 HO , ppt O , ppb H O(proj), ppm HO, ppt 2 3 2 Hydrogen Peroxide … Pressure, RH, Nitrogen Dioxide, Sulfur Dioxide

DC-8 Flt8 07/15/04 200 4 4 4

400 3 3 3

600 2 2 2 (URI), ppb (URI), ppb (URI), ppb P, hPa 2 2 2 O O O 2 800 2 1 2 1 1 H H H

1000 0 0 0 -5 0 5 0 2 4 0 50 100 10 10 10 0 1000 2000 H O (URI), ppb RH(water), % NO , ppt SO , ppt 2 2 2 2 200 4 4 4

400 3 3 3

600 2 2 2 (CIT), ppb (CIT), ppb (CIT), ppb P, hPa 2 2 2 O O O 2 800 2 1 2 1 1 H H H

1000 0 0 0 -5 0 5 0 2 4 0 50 100 10 10 10 0 1000 2000 H O (CIT), ppb RH(water), % NO , ppt SO , ppt 2 2 2 2 Hydrogen Peroxide … Acetaldehyde, Acetone, Methanol, Methylhydroperoxide

DC-8 Flt8 07/15/04 4 4 4 4

3 3 3 3

2 2 2 2 (URI), ppb (URI), ppb (URI), ppb (URI), ppb 2 2 2 2 O O O O 2 2 1 2 1 2 1 1 H H H H

0 0 0 0 0 500 1000 0 5000 10000 0 5000 10000 0 1000 2000 CH CHO, ppb CH COCH , ppt CH OH, ppt CH OOH, ppt 3 3 3 3 3 4 4 4 4

3 3 3 3

2 2 2 2 (CIT), ppb (CIT), ppb (CIT), ppb (CIT), ppb 2 2 2 2 O O O O 2 2 1 2 1 2 1 1 H H H H

0 0 0 0 0 500 1000 0 5000 10000 0 5000 10000 0 1000 2000 CH CHO, ppb CH COCH , ppt CH OH, ppt CH OOH, ppt 3 3 3 3 3 Case Study: August 11, 2004; DC-8 Flight 18

2

1 3 4 5 10 9 6 8 7 New Brunswick Far Off N. Carolina

DC-8 Flt18 08/11/04

10 10 10 10 10

5 5 5 5 5 Altitude(GPS), km Altitude(GPS), 0 2 0 3 0 4 0 5 0 6 2040 60 80100120 2040 60 80100120 2040 60 80100120 2040 60 80100120 20 40 60 80100120 O , ppb O , ppb O , ppb O , ppb O , ppb 3 3 3 3 3

12 12 12 12 12 10 10 10 10 10 8 8 8 8 8 6 6 6 6 6 4 4 4 4 4 2 2 2 2 2 Altitude(GPS), km Altitude(GPS), 0 10 0 9 0 8 0 7 0 6 2040 60 80100120 2040 60 80100120 2040 60 80100120 2040 60 80100120 20 40 60 80100120 O , ppb O , ppb O , ppb O , ppb O , ppb 3 3 3 3 3

St Louis Far Off N. Carolina New Brunswick Far Off N. Carolina

DC-8 Flt18 08/11/04

10 10 10 10 10

5 5 5 5 5

Altitude(GPS), km 0 2 0 3 0 4 0 5 0 6 50 100 150 50 100 150 50 100 150 50 100 150 50 100 150 CO, ppb CO, ppb CO, ppb CO, ppb CO, ppb

10 10 10 10 10

5 5 5 5 5

Altitude(GPS), km 0 10 0 9 0 8 0 7 0 6 50 100 150 50 100 150 50 100 150 50 100 150 50 100 150 CO, ppb CO, ppb CO, ppb CO, ppb CO, ppb

St Louis Far Off N. Carolina New Brunswick Far Off N. Carolina

DC-8 Flt18 08/11/04

10 10 10 10 10

5 5 5 5 5 Altitude(GPS), km 0 2 0 3 0 4 0 5 0 6 0 5000 10000 0 5000 0 5000 0 5000 0 5000 CH OOH (CH O or HCHOOOH), ppt (CH O orCH H OOOH), ppt (CH O orCH H OOOH), ppt (CH O orCH H OOOH), ppt (CH O or H O ), ppt 3 2 2 32 2 23 2 2 23 2 2 23 2 2 2 2

12 12 12 12 12 10 10 10 10 10 8 8 8 8 8 6 6 6 6 6 4 4 4 4 4 2 2 2 2 2 Altitude(GPS), km 0 10 0 9 0 8 0 7 0 6 0 5000 0 5000 0 5000 0 5000 0 5000 CH OOH (CH O or HCHOOOH), ppt (CH O orCH H OOOH), ppt (CH O orCH H OOOH), ppt (CH O orCH H OOOH), ppt (CH O or H O ), ppt St3 Louis2 2 32 2 23 2 2 23 2 2 2 Far3 2 Off N.2 Carolina2 2

grn – H2O2 blk – CH3OOH red – CH2O(URI) mag – CH2O(NCAR) New Brunswick Far Off N. Carolina

DC-8 Flt18 08/11/04

10 10 10 10 10

5 5 5 5 5

2 3 4 5

Altitude(GPS), km Altitude(GPS), 0 0 0 0 0 0 500 1000 0 500 1000 0 500 1000 0 500 1000 0 500 1000 CH OOH (CH O or HCHO ),OOH ppt (CH O or HCHO ),OOH ppt (CH O or HCHO ),OOH ppt (CH O or H CHO ),OOH ppt (CH O or H O ), ppt 3 2 2 23 2 2 23 2 2 23 2 2 23 2 2 2

10 10 10 10 10

5 5 5 5 5

Altitude(GPS), km Altitude(GPS), 0 0 10 0 9 0 8 0 7 0 500 1000 0 500 1000 0 500 1000 0 500 1000 0 500 1000 CH OOH (CH O or HCHO ),OOH ppt (CH O or HCHO ),OOH ppt (CH O or HCHO ),OOH ppt (CH O or H CHO ),OOH ppt (CH O or H O ), ppt 3 2 2 23 2 2 23 2 2 23 2 2 23 2 2 2 St Louis Far Off N. Carolina

grn – H2O2 blk – CH3OOH red – CH2O(URI) mag – CH2O(NCAR) Summary CH2O Measurements URI to NCAR comparison factor of 1.1 to 1.6 Highly correlated Indicate same functional relationships to other compounds

H2O2 Measurements URI to CIT comparison factor of 0.7 to 1.2 Well correlated with outliers, better when Xv<1% Indicate same functional relationships to other compounds Case Study: August 2, 2004; DC-8 Flight 15

7 8 6 5 4 3 9 10 2 11 14 1 12 13 S. Quebec N. New Foundland

DC-8 Flt15 08/02/04 12 12 12 12 12 12 10 10 10 10 10 10 8 8 8 8 8 8 6 6 6 6 6 6 4 4 4 4 4 4

Altitude(GPS), km Altitude(GPS), 2 2 2 2 2 km Altitude(GPS), 2 0 3 0 4 0 5 0 6 0 7 0 8 0 100 200 0 100 200 0 100 200 0 100 200 0 100 200 0 100 200 O , ppb O , ppb O , ppb O , ppb O , ppb O , ppb 3 3 3 3 3 3

12 12 12 12 12 12 10 10 10 10 10 10

8 8 8 8 8 8 6 6 6 6 6 6

4 4 4 4 4 4 2 2 2 2 2 2

0 14 0 13 0 12 0 11 0 10 0 9 0 100 200 0 100 200 0 100 200 0 100 200 0 100 200 0 100 200 O , ppb O , ppb O , ppb O , ppb O , ppb O , ppb 3 3 3 3 3 3 S. Maine S. New Foundland S. Quebec N. New Foundland DC-8 Flt15 08/02/04 12 12 12 12 12 12

10 10 10 10 10 10

8 8 8 8 8 8

6 6 6 6 6 6

4 4 4 4 4 4 Altitude(GPS), km Altitude(GPS), Altitude(GPS), km Altitude(GPS), 2 2 2 2 2 2

0 3 0 4 0 5 0 6 0 7 0 8 50 100150 50 100150 50 100150 50 100150 50 100150 50100150 CO, ppb CO, ppb CO, ppb CO, ppb CO, ppb CO, ppb

12 12 12 12 12 12

10 10 10 10 10 10

8 8 8 8 8 8

6 6 6 6 6 6

4 4 4 4 4 4

2 2 2 2 2 2

0 14 0 13 0 12 0 11 0 10 0 9 50 100150 50 100150 50 100150 50 100150 50 100150 50100150 CO, ppb CO, ppb CO, ppb CO, ppb CO, ppb CO, ppb

S. Maine S. New Foundland S. Quebec N. New Foundland

DC-8 Flt15 08/02/04 12 12 12 12 12 12

10 10 10 10 10 10

8 8 8 8 8 8

6 6 6 6 6 6

4 4 4 4 4 4 Altitude(GPS), km Altitude(GPS), km Altitude(GPS),

2 2 2 2 2 2

3 4 5 6 7 8 0 0 0 0 0 0 0 5000 0 5000 0 5000 0 5000 0 5000 0 5000 CH OOH (CH O or H OCH), pptOOH (CH O or H CHO ),OOH ppt (CH O or H CHO ),OOH ppt (CH O or H CHO ),OOH ppt (CH O or H OCH), pptOOH (CH O or H O ), ppt 3 2 2 2 3 2 2 2 3 2 2 2 3 2 2 2 3 2 2 2 3 2 2 2

12 12 12 12 12 12

10 10 10 10 10 10

8 8 8 8 8 8

6 6 6 6 6 6

4 4 4 4 4 4

2 2 2 2 2 2

14 13 12 11 10 9 0 0 0 0 0 0 0 5000 0 5000 0 5000 0 5000 0 5000 0 5000 CH OOH (CH O or H OCH), pptOOH (CH O or H CHO ),OOH ppt (CH O or H CHO ),OOH ppt (CH O or H CHO ),OOH ppt (CH O or H OCH), pptOOH (CH O or H O ), ppt 3 2 2 2 3 2 2 2 3 2 2 2 3 2 2 2 3 2 2 2 3 2 2 2 S. Maine S. New Foundland grn – H2O2 blk – CH3OOH red – CH2O(URI) mag – CH2O(NCAR) S. Quebec N. New Foundland DC-8 Flt15 08/02/04

10 10 10 10 10 10

5 5 5 5 5 5

0 0 3 0 4 0 5 0 6 70 8 Altitude(GPS), km Altitude(GPS), km Altitude(GPS), 0 5001000 0 5001000 0 5001000 0 5001000 0 5001000 0 5001000 CH OOH (CH CHO orOOH H O (CH), pptCHO orOOH H O (CH), pptCHO orOOH H O (CH), pptCHO orOOH H O (CH), pptO CHor HOOHO ), (CHppt O or H O 3 2 3 2 2 2 3 2 2 2 3 2 2 2 3 2 2 2 32 2 2 2 2

10 10 10 10 10 10

5 5 5 5 5 5

0 0 14 0 13 0 12 0 11 100 9 0 5001000 0 5001000 0 5001000 0 5001000 0 5001000 0 5001000 CH OOH (CH CHO orOOH H O (CH), pptCHO orOOH H O (CH), pptCHO orOOH H O (CH), pptCHO orOOH H O (CH), pptO CHor HOOHO ), (CHppt O or H O 3 2 3 2 2 2 3 2 2 2 3 2 2 2 3 2 2 2 32 2 2 2 2 S. Maine S. New Foundland grn – H2O2 blk – CH3OOH red – CH2O(URI) mag – CH2O(NCAR)