hydrogen peroxide methylhydroperoxide formaldehyde & (peroxyacetic acid) brian g. heikes &...

Hydrogen PeroxideMethylhydroperoxide

Formaldehyde & (Peroxyacetic Acid)

Brian G. Heikes & Haiwei Shen, URI

Daniel W. O’Sullivan, USNA

Julie A. Snow, Slippery Rock U.

• 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

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,

pp

b (

NC

AR

) 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,

pp

b (

NC

AR

)

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

Slo

pe

-80

-60

-40

-20

0

20

40

60

80

100

120

Inte

rce

pt

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)

, pp

b

DC-8 Flt6 07/10/04

0 5000 100000

1

2

3

4

C2H

6, ppt

CH

2O(U

RI)

, pp

b

0 2000 40000

1

2

3

4

C3H

8, ppt

CH

2O(U

RI)

, pp

b

0 100 2000

1

2

3

4

benzene, ppt

CH

2O(U

RI)

, pp

b0 200 400

-2

0

2

4

6

8

CO, ppb

CH

2O(N

CA

R),

pp

b

0 5000 10000-2

0

2

4

6

8

C2H

6

CH

2O(N

CA

R),

pp

b

0 2000 4000-2

0

2

4

6

8

C3H

8, ppt

CH

2O(N

CA

R),

pp

b

0 100 200-2

0

2

4

6

8

benzene, pptC

H2O

(NC

AR

), p

pb

0 5000

1

2

3

4

C2H

2, ppb

CH

2O(U

RI)

, pp

b

DC-8 Flt6 07/10/04

0 200 4000

1

2

3

4

C2H

4, ppt

CH

2O(U

RI)

, pp

b

0 2000 40000

1

2

3

4

isoprene, ppt

CH

2O(U

RI)

, pp

b

0 50 1000

1

2

3

4

C3H

6, ppt

CH

2O(U

RI)

, pp

b0 500

-2

0

2

4

6

8

C2H

2, ppb

CH

2O(N

CA

R),

pp

b

0 200 400-2

0

2

4

6

8

C2H

4, ppt

CH

2O(N

CA

R),

pp

b

0 2000 4000-2

0

2

4

6

8

isoprene, ppt

CH

2O(N

CA

R),

pp

b

0 50 100-2

0

2

4

6

8

C3H

6, ppt

CH

2O(N

CA

R),

pp

b

Formaldehyde Relationships Continued Ethyne, Ethene, Isoprene, & Propene

0 1000 20000

1

2

3

4

CH3CHO, ppb

CH

2O(U

RI)

, p

pb

DC-8 Flt6 07/10/04

0 5000 100000

1

2

3

4

CH3COCH

3, ppt

CH

2O(U

RI)

, p

pb

0 5000 100000

1

2

3

4

CH3OH, ppt

CH

2O(U

RI)

, p

pb

0 1000 20000

1

2

3

4

CH3OOH, ppt

CH

2O(U

RI)

, p

pb

0 1000 2000-2

0

2

4

6

8

CH3CHO, ppb

CH

2O(N

CA

R),

pp

b

0 5000 10000-2

0

2

4

6

8

CH3COCH

3, ppt

CH

2O(N

CA

R),

pp

b

0 5000 10000-2

0

2

4

6

8

CH3OH, ppt

CH

2O(N

CA

R),

pp

b

0 1000 2000-2

0

2

4

6

8

CH3OOH, ppt

CH

2O(N

CA

R),

pp

b

Formaldehyde … Acetaldehyde, Acetone, Methanol, Methylhydroperoxide

0 50 1000

1

2

3

4

HO2, ppt

CH

2O(U

RI)

, pp

b DC-8 Flt6 07/10/04

0 50 1000

1

2

3

4

O3, ppb

CH

2O(U

RI)

, pp

b

102

104

106

0

1

2

3

4

H2O(proj), ppm

CH

2O(U

RI)

, pp

b

10-2

10-1

100

0

1

2

3

4

HO, ppt

CH

2O(U

RI)

, pp

b0 50 100

-2

0

2

4

6

8

HO2, ppt

CH

2O(N

CA

R),

pp

b

0 50 100-2

0

2

4

6

8

O3, ppb

CH

2O(N

CA

R),

pp

b

102

104

106

-2

0

2

4

6

8

H2O(proj), ppm

CH

2O(N

CA

R),

pp

b

10-2

10-1

100

-2

0

2

4

6

8

HO, pptC

H2O

(NC

AR

), p

pb

Formaldehyde … Perhydroxyl, Ozone, Water, & Hydroxyl

0 2 4

200

400

600

800

1000

P,

hP

a

CH2O(URI), ppb

DC-8 Flt6 07/10/04

0 50 1000

1

2

3

4

RH(water), %

CH

2O(U

RI)

, p

pb

100

102

104

0

1

2

3

4

NO2, ppt

CH

2O(U

RI)

, p

pb

0 1 2

x 104

0

1

2

3

4

SO2, ppt

CH

2O(U

RI)

, p

pb

0 5

200

400

600

800

1000

P,

hP

a

CH2O(NCAR), ppb

0 50 100-2

0

2

4

6

8

RH(water), %

CH

2O(N

CA

R),

pp

b

100

102

104

-2

0

2

4

6

8

NO2, ppt

CH

2O(N

CA

R),

pp

b

0 1 2

x 104

-2

0

2

4

6

8

SO2, ppt

CH

2O(N

CA

R),

pp

b

Formaldehyde vs Pressure, 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

H2O

2, ppb (URI)

H2O

2, p

pb

(C

alT

ec

h)

DC-8 Flt06 07/10/04

M-A Regression

M-A Regression, <1

Robust Fit

b(robfit) = 0.0m(robfit) = 1.214

0 2 4 6 8 10-1

0

1

2

3

4

5

6

7

8

9

10

H2O

2, ppb (URI)

H2O

2, p

pb

(C

alT

ec

h)

DC-8 Flt19 08/13/04

M-A Regression

M-A Regression, <1

Robust Fitb(robfit) = 0.1

m(robfit) = 0.64912

~1.2

~0.65

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

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

Slo

pe

0

50

100

150

200

250

Inte

rcep

t

m-robust

b-robust

0 20 400

1

2

3

4

HO2, ppt

H2O

2(UR

I),

pp

b

DC-8 Flt8 07/15/04

0 100 2000

1

2

3

4

O3, ppb

H2O

2(UR

I),

pp

b

100

105

0

1

2

3

4

H2O(proj), ppm

H2O

2(UR

I),

pp

b

10-2

10-1

100

0

1

2

3

4

HO, ppt

H2O

2(UR

I),

pp

b0 20 40

0

1

2

3

4

HO2, ppt

H2O

2(CIT

), p

pb

0 100 2000

1

2

3

4

O3, ppb

H2O

2(CIT

), p

pb

100

105

0

1

2

3

4

H2O(proj), ppm

H2O

2(CIT

), p

pb

10-2

10-1

100

0

1

2

3

4

HO, pptH

2O2(C

IT),

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

H2O

2(URI), ppb

DC-8 Flt8 07/15/04

0 50 1000

1

2

3

4

RH(water), %

H2O

2(UR

I), p

pb

10-5

100

105

0

1

2

3

4

NO2, ppt

H2O

2(UR

I), p

pb

0 1000 20000

1

2

3

4

SO2, ppt

H2O

2(UR

I), p

pb

0 2 4

200

400

600

800

1000

P, h

Pa

H2O

2(CIT), ppb

0 50 1000

1

2

3

4

RH(water), %

H2O

2(CIT

), p

pb

10-5

100

105

0

1

2

3

4

NO2, ppt

H2O

2(CIT

), p

pb

0 1000 20000

1

2

3

4

SO2, ppt

H2O

2(CIT

), p

pb

0 500 10000

1

2

3

4

CH3CHO, ppb

H2O

2(UR

I),

pp

b

DC-8 Flt8 07/15/04

0 5000 100000

1

2

3

4

CH3COCH

3, ppt

H2O

2(UR

I),

pp

b

0 5000 100000

1

2

3

4

CH3OH, ppt

H2O

2(UR

I),

pp

b

0 1000 20000

1

2

3

4

CH3OOH, ppt

H2O

2(UR

I),

pp

b0 500 1000

0

1

2

3

4

CH3CHO, ppb

H2O

2(CIT

), p

pb

0 5000 100000

1

2

3

4

CH3COCH

3, ppt

H2O

2(CIT

), p

pb

0 5000 100000

1

2

3

4

CH3OH, ppt

H2O

2(CIT

), p

pb

0 1000 20000

1

2

3

4

CH3OOH, ppt

H2O

2(CIT

), p

pb

Hydrogen Peroxide … Acetaldehyde, Acetone, Methanol, Methylhydroperoxide

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

1

2

3

4

56

78

910

New Brunswick Far Off N. Carolina

St Louis Far Off N. Carolina

2040 60 801001200

5

10

Alt

itu

de(

GP

S),

km

O3, ppb

DC-8 Flt18 08/11/04

22040 60 801001200

5

10

O3, ppb

32040 60 801001200

5

10

4

O3, ppb

2040 60 801001200

5

10

5

O3, ppb

20 40 60 801001200

5

10

6

O3, ppb

2040 60 801001200

2

4

6

8

10

12

Alt

itu

de(

GP

S),

km

10

O3, ppb

2040 60 801001200

2

4

6

8

10

12

9

O3, ppb

2040 60 801001200

2

4

6

8

10

12

8

O3, ppb

2040 60 801001200

2

4

6

8

10

12

7

O3, ppb

20 40 60 801001200

2

4

6

8

10

12

6

O3, ppb



50 100 1500

5

10

Alt

itu

de(

GP

S),

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

Alt

itu

de(

GP

S),

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

Alt

itu

de(

GP

S),

km

CH3OOH (CH

2O or H

2O

2), ppt

DC-8 Flt18 08/11/04

20 5000

0

5

10

CH3OOH (CH

2O or H

2O

2), ppt

30 5000

0

5

10

4

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

5

10

5

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

5

10

6

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

Alt

itu

de(

GP

S),

km

10

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

9

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

8

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

7

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

6

CH3OOH (CH

2O or H

2O

2), ppt



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




0 500 10000

5

10

Alti

tude

(GP

S),

km

CH3OOH (CH

2O or H

2O

2), ppt

DC-8 Flt18 08/11/04

20 500 1000

0

5

10

CH3OOH (CH

2O or H

2O

2), ppt

30 500 1000

0

5

10

4

CH3OOH (CH

2O or H

2O

2), ppt

0 500 10000

5

10

5

CH3OOH (CH

2O or H

2O

2), ppt

0 500 10000

5

10

6

CH3OOH (CH

2O or H

2O

2), ppt

0 500 10000

5

10

Alti

tude

(GP

S),

km

10

CH3OOH (CH

2O or H

2O

2), ppt

0 500 10000

5

10

9

CH3OOH (CH

2O or H

2O

2), ppt

0 500 10000

5

10

8

CH3OOH (CH

2O or H

2O

2), ppt

0 500 10000

5

10

7

CH3OOH (CH

2O or H

2O

2), ppt

0 500 10000

5

10

6

CH3OOH (CH

2O or H

2O

2), ppt

SummaryCH2O 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

1

2

34

56

7 8

910

11

1213

14

0 100 2000

2

4

6

8

10

12

Alt

itu

de

(GP

S),

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, ppb

0 100 2000

2

4

6

8

10

12

6

O3, ppb

0 100 2000

2

4

6

8

10

12

7

O3, ppb

0 100 2000

2

4

6

8

10

12

Alt

itu

de

(GP

S),

km

8

O3, ppb

0 100 2000

2

4

6

8

10

12

14

O3, ppb

0 100 2000

2

4

6

8

10

12

13

O3, ppb

0 100 2000

2

4

6

8

10

12

12

O3, ppb

0 100 2000

2

4

6

8

10

12

11

O3, ppb

0 100 2000

2

4

6

8

10

12

10

O3, ppb

0 100 2000

2

4

6

8

10

12

9

O3, ppb

S. Quebec N. New Foundland

S. Maine S. New Foundland



50 1001500

2

4

6

8

10

12

Alt

itu

de

(GP

S),

km

CO, ppb

DC-8 Flt15 08/02/04

350 100150

0

2

4

6

8

10

12

CO, ppb

450 100150

0

2

4

6

8

10

12

5

CO, ppb50 100150

0

2

4

6

8

10

12

6

CO, ppb50 100150

0

2

4

6

8

10

12

7

CO, ppb50100150

0

2

4

6

8

10

12

Alt

itu

de

(GP

S),

km

8

CO, ppb

50 1001500

2

4

6

8

10

12

14

CO, ppb50 100150

0

2

4

6

8

10

12

13

CO, ppb50 100150

0

2

4

6

8

10

12

12

CO, ppb50 100150

0

2

4

6

8

10

12

11

CO, ppb50 100150

0

2

4

6

8

10

12

10

CO, ppb50100150

0

2

4

6

8

10

12

9

CO, ppb



0 50000

2

4

6

8

10

12

Altitude(G

PS

), k

m

CH3OOH (CH

2O or H

2O

2), ppt

DC-8 Flt15 08/02/04

3

0 50000

2

4

6

8

10

12

CH3OOH (CH

2O or H

2O

2), ppt

4

0 50000

2

4

6

8

10

12

5

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

6

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

7

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

Altitude(G

PS

), k

m

8

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

14

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

13

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

12

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

11

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

10

CH3OOH (CH

2O or H

2O

2), ppt

0 50000

2

4

6

8

10

12

9

CH3OOH (CH

2O or H

2O

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DC-8 Flt15 08/02/04

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CH3OOH (CH

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CH3OOH (CH

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hydrogen peroxide methylhydroperoxide formaldehyde & (peroxyacetic acid) brian g. heikes &...

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