Acetaldehyde in the Central Valley

of California

Steven Walsh
SARP 2009
WAS Group
 Outline
- Overview
- Photochemistry
- Relationships
- Implications/conclusions
- Future work
- References
- Acknowledgments
 Overview

Acetaldehyde is an important resultant photochemical
species that is not believed to have a ground based
emission source.

Acetaldehyde and ethanol correlate well with each
other when examining all collected flight data.

Acetaldehyde to ethanol ratios do not correlate with
distinct observed acetaldehyde concentrations.

Does biomass burning affect acetaldehyde
occurence?
 Conceptual model

Central
Acetaldehyde
Valley
Photolysis
? HOx most

Winery/vineyard Dairy Farm

Ethanol
 Acetaldehyde photochemistry

ETHANOL - OH REACTION
.
5% CH2CH2OH(g)
.
+OH(g) . +O2(g)
C2H5OH(g) 90% CH3CHOH(g) CH3CHO(g)
H2O(g)
. Acetaldehyde
Ethanol
. HO2(g)
5% CH3CH2O(g)

Jacobson, 2002
 Ethanol vs. Acetaldehyde

1600

1400
y = 0.1185x + 161.47
2
R = 0.6864
1200

1000 y = 0.1047x + 215.76

2
R = 0.6995

800

Ethanol-
600 Acetaldehyde
Flight 1
Ethanol-
Acetaldehyde
400
Flight 2
Acetaldehyde (pptv) Flight 1

200
Flight 2

0
0 2000 4000 6000 8000 10000 12000

Ethanol (pptv)
 Acetaldehyde vs. A/E

1.6000

1.4000

1.2000

1.0000 Acetaldehyde
vs. A/E Flt1
0.8000
A/E
0.6000

0.4000 Acetaldehyde
vs. A/E Flt2
0.2000

0.0000
0 200 400 600 800 1000 1200

Acetaldehyde (pptv)
Ethanol correlates to acetaldehyde but why is
there variability?
Ethanol distribution-both flights
Flight 1 Acetaldehyde distribution
Flight 2 Acetaldehyde distribution
Can biomass burning affect the
observation of Acetaldehyde?
Automated Biomass Burning
Algorithm
(ABBA GOES-8) on day July 22
2009-Flight 1.

Automated Biomass Burning

Algorithm
(ABBA GOES-8) on day July 24
2009-Flight 2.
Flight 1 CH3Cl
Flight 2 CH3Cl
 CH3Cl vs. Acetaldehyde

1200

1000

800

600

400 Flight 1

Acetaldehyde (pptv)
200
Flight 2

0
550 560 570 580 590 600 610 620 630 640

CH3Cl (pptv)
 CH3Cl vs. Acetaldhyde

1200

y = 8.0122x - 3940.5
2
1000 R = 0.9345

Flight1
800

600 y = 6.1925x - 3102.8 Flight 2

2
R = 0.8496

400
Linear (Flight 2)

Acetaldehyde (pptv)
200
Linear (Flight1)

0
560 570 580 590 600 610 620 630 640

CH3Cl (pptv)
 CH3Cl vs. Methane

2.04

2.02

2
Flight 1
R2 = 0.9094
1.98

1.96
Flight 2
1.94

Methane
1.92 (ppmv)
Linear (Flight 2)
1.9

1.88
560 570 580 590 600 610 620 630 640

CH3Cl (pptv)
 Methane vs. Acetaldehyde
1200

1000
R2 = 0.9589

800

Flight 1
600

Flight 2
400

Acetaldehyde (pptv)
200
Linear (Flight 2)

0
1.88 1.9 1.92 1.94 1.96 1.98 2 2.02 2.04

Methane (ppmv)
 Ethanol vs. Acetaldehyde

1100

1000

900
Flight 1+2
suspect points
800
2
R = 0.3053

700

600

Linear (Flight
500
Acetaldehyde (pptv) 1+2 suspect
points)
400

300
2000 3000 4000 5000 6000 7000 8000

Ethanol (pptv)
 Interpretation of suspect biomass
burning samples

High ethanol source-

Dairy?
Distal evidence of Biomass
Burning event

High ethanol
influence
Proximal to
biomass burning
event
Sample Methane (ppmv) Acetaldehyde (pptv) CH3Cl (pptv) A/C
Distal samples
711 1.894 426 572 0.745
722 1.931 446 577 0.773
1104 1.894 575 570 1.009
Proximal samples
1116 2.019 1015 615 1.650
1103 1.999 1008 621 1.623
1118 1.951 851 600 1.418
1115 1.93 765 579 1.321
710 1.909 769 609 1.263
707 1.918 729 629 1.159
 Conclusions
- It is plausible that there is a coupling between biomass
burning and acetaldehyde. This observation is more
strongly supported by data collected on flight 2. This
coupling seems disconnected to ethanol when
compared to the entire data set ‘Acetaldehyde-Ethanol’
relationship.
- The ratio between these tracers and acetaldehyde
coupled with satellite data will be valuable in identifying
biomass burning events as well as understanding
important photochemical and source interactions.
- It is sometimes very difficult to understand the impact
that different sources contribute to a particular species
in an area.
 Future work
- More projects on the interaction between
biomass burning and secondary photochemical
products.
- Continue to assess the impact of biomass
burning against other sources of pollution.
- Continue conducting airborne missions because
of their ability to detect secondary
photochemical products.
 References
Carter, W.P.L (1994) Development of ozone reactivity scales for volatile
organic compounds, J. Air Waste Manag. Assoc., 44, 881-899.

Holzinger, R., C. Warneke, A. Hansel, A. Jordan, W. Lindinger, D. H. Scharffe, G. Schade,

and P. J. Crutzen (1999), Biomass burning as a source of formaldehyde, acetaldehyde,
methanol, acetone, acetonitrile, and hydrogen cyanide,
Geophys. Res. Lett., 26(8), 1161–1164.
Jacobson, M., Z. (2002). Atmospheric pollution: history, science, and regulation.
Cambridge: Cambridge University Press. 109-111.

Seinfeld, J., H. and Pandis, S., N. (1998), Atmospheric chemistry and physics:
From air pollution to climate change. Canada: John Wiley & Sons, Inc. 286-288.
Steiner, A. L., Cohen, R. C., Harley, R. A., Tonse, S., Millet, D. B., Schade, G. W.,
and Goldstein, A. H. (2008), VOC reactivity in central California:
comparing an air quality model to ground-based measurements,
Atmos. Chem. Phys., 8, 351-368.
 Acknowledgments
NASA
DC8 Crew
NSERC
UCI
Dr. Sherwood Rowland
Dr. Donald Blake
Dr. Melissa Yang
SARP WAS Group