VALIDATING METEOROLOGICAL

MODELS USING CHEMICAL

TRACERS IN THE TCCON SPIRAL
1

Dakota Crane ; Stacey Hughes ; Don Blake ; Rafe Day

1

Department
2 of Atmospheric Science and Mathematics, Lyndon State College
Department of Chemistry, University of California Irvine

Example Chromatogram

Every peak was examined for all SIX columns.

Up to 77 compounds per column.
Based on a gases retention time, its baseline was corrected if
necessary.
A peak ! certain gas ! area of the peak = analyze concentration!!

Alkanes

Alkenes

Aromatics

1. Methane
2. Ethane
3. Propane
4. i-Butane
5. n-Butane
6. i-Pentane
7. n-Pentane
8. n-Hexane
9. n-Heptane
10. n-Octane
11. n-Nonane
12. n-Decane
13. 2,2-Dimethylbutane
14. 2,3-Dimethylbutane
15. 2-Methylpentane
16. 3-Methylpentane
17. 2-Methylhexane
18. 3-Methylhexane
19. 2,3-Dimethylpentane
20. 2,2,4-Trimethylpentane
21. 2,3,4-Trimethylpentane
22. 2-Methylheptane
23. 3-Methylheptane

25. Ethene
26. Propene
27. 1-Butene
28. i-Butene
29. cis-2-Butene
30. trans-2-Butene
31. 1,3-Butadiene
32. 1-Pentene
33. cis-2-Pentene
34. trans-2-Pentene
35. 2-Methyl-1-Butene
36. 2-Methyl-2-Butene
37. 3-Methyl-1-Butene
38. 2-Methyl-1-Pentene
39. 4-Methyl-1-Pentene
40. Isoprene
41. -Pinene
42. -Pinene

51. Benzene
52. Toluene
53. Ethylbenzene
54. m-Xylene
55. o-Xylene
56. p-Xylene
57. Styrene
58. i-Propylbenzene
59. n-Propylbenzene
60. 2-Ethyltoluene
61. 3-Ethyltoluene
62. 4-Ethyltoluene
63. 1,2,3-Trimethylbenzene
64. 1,2,4-Trimethylbenzene
65. 1,3,5-Trimethylbenzene

Alkynes
24. Ethyne

Alkyl Nitrates
43. MeONO2
44. EtONO2
45. i-PrONO2
46. n-PrONO2
47. 2-BuONO2
48. 2-PeONO2
49. 3-PeONO2
50. 3-Methyl-2-BuONO2

Cycloalkanes/-enes
66. Cyclopentane
67. Methylcyclopentane
68. Cyclohexane
69. Methylcyclohexane
70. Cyclopentene

Sulfur Species
71. OCS
72. DMS
73. CS2

Halocarbons
74. CFC-11
75. CFC-12
76. CFC-113
77. CFC-114
78. CCl4
79. CH3CCl3
80. HCFC-22
81. HCFC-124
82. HCFC-141b
83. HCFC-142b
84. HFC-134a
85. HFC-152a
86. H-1211
87. H-1301
88. H-2402
89. CH3Cl
90. CH3Br
91. CH3I
92. CH2Cl2
93. CHCl3
94. CHBr3
95. C2Cl4
96. CHBrCl2
97. CHBr2Cl
98. Ethylchloride
99. 1,2-DCE

TCCON SITE
Total Carbon Column Observing
Network
Measures carbon dioxide, methane,
carbon monoxide, nitrous oxide, etc
Developed due to modeling
errors between mixing efficiency
between the PBL and the
free troposphere
Believes free troposphere is
homogeneous
Flight 2: June 18, 2016

https://tccon-wiki.caltech.edu/

Previous Research with TCCON

SARP 2014, Jean Guo.

Used chemical tracers to locate source of

plume at 7,620 meters.

Originated in China around 4-5 days prior

Source from coal plants and biomass

burning.

Motivation

Validate the column of air above TCCON

site.
Locate the sources of higher
concentration gases above boundary
layer.
Observe transport of air masses at different

altitudes.
Important to understand the source of
pollutants

Research Outline
1.
2.
3.
4.
5.

Air mass age

Homogeneous gas profile
Observe heterogeneous gas profiles
Results/HYSPLIT
Conclusions

Calculating Age of Air Mass

Ethyne/Carbon monoxide(CO) Ratio

Both produced by combustion.

Ethyne has a lifetime of about 2-4 weeks.
Carbon monoxide has a lifetime of about 2
months.

Ethyne/CO Ratio

Homogeneous Profile in TCCON

 Halocarbon
Lifetime 1.4 year
Replacement for CFCs
and HCFCs
Used as a foam-blowing
agent and in aerosol spray
applications
B. Barletta et. al. 2011

Gases exhibiting
heterogeneous
behavior

Biomass Burning

 Alkane
Lifetime two months
Emissions from biomass
burning and natural gas

 Alkyne
Lifetime 2-4 weeks
Emissions from biomass
burning and natural gas

i/n Pentane Ratio

Industrial

 Halocarbon
Lifetime 2 months
Emitted from byproduct of
vinyl chloride
Used to produce
plastic piping.

Results

10.9km

13 12 11 10 9 8

7 6

5 4

3 2

Mexico Ethane/CO ratio = 7.40

Air mass at 10.9km = 7.50
U.S. cities ratio: 2.40

9.4km

13 12 11 10 9 8

6 5 4

Mexico Ethane/CO ratio = 7.40

Air mass at 9.1km = 7.40
U.S. cities ratio: 2.40

7.3km

13 12 11 10 9 8

6 5 4

Ethyne/CO ratio = 0.35 (oldest air mass)

Ethane, Propane, Benzene are also low

5.6km

13 12 11 10 9 8

6 5 4

1,2-Dichloroethene is emitted
by vinyl chloride production

The Pemex Vinyl Chloride Plant Explosion

Petroquimica Mexicana de Vinilo SA de CV plant

Occurred on April 20, 2016
13 killed, 88 injured, and 2000 evacuated!

Conclusions

TCCON site is not one column of air but

multiple air masses with different
sources.
Not always homogeneous

HYSPLIT back trajectories are accurate

in free troposphere.
Chemical tracers provide supporting

evidence.

Acknowledgements

Dr. Blake
Stacey Hughes
WAS Group
Rowland-Blake Lab
Rafe Day
Emily Schaller
Dr. Heath
Dr. Fuelberg
Jim Crawford
KORUS-AQ
DC-8 Flight Crew
NASA
Everyone in SARP 2016

Questions?

References
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Xiao, Y & Fu, TM 2011, 'Ethane, ethyne and carbon monoxide concentrations in the upper troposphere and lower stratosphere from
ACE and GEOS-Chem: a comparison study' Atmospheric chemistry and physics, vol 11, no. 18, pp. 9927-9941., 10.5194/
acp-11-9927-2011
Apel, E. C., Emmons, L. K., Karl, T., Flocke, F., Hills, A. J., Madronich, S., Lee-Taylor, J., Fried, A., Weibring, P., Walega, J., Richter, D., Tie,
X., Mauldin, L., Campos, T., Weinheimer, A., Knapp, D., Sive, B., Kleinman, L., Springston, S., Zaveri, R., Ortega, J., Voss, P., Blake,
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Chemical evolution of volatile organic compounds in the outflow of the Mexico City Metropolitan area, Atmos. Chem. Phys., 10,
2353-2375, doi:10.5194/acp-10-2353-2010, 2010.
Barletta, B., Nissenson, P., Meinardi, S., Dabdub, D., Sherwood Rowland, F., VanCuren, R. A., Pederson, J., Diskin, G. S., and Blake, D. R.: HFC-152a and
HFC-134a emission estimates and characterization of CFCs, CFC replacements, and other halogenated solvents measured during the 2008
ARCTAS campaign (CARB phase) over the South Coast Air Basin of California, Atmos. Chem. Phys., 11, 2655-2669, doi:10.5194/
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Atmospheric budget and use as a tracer of marine convection in global models, J. Geophys. Res.,107(D17), 4340, doi:
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Res., 107(D10), doi:10.1029/2001JD000694, 2002.
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Weinheimer, A. J., Yang, M., and Blake, D. R.: Characterization of trace gases measured over Alberta oil sands mining operations: 76
speciated C2C10 volatile organic compounds (VOCs), CO2, CH4, CO, NO, NO2, NOy, O3 and SO2, Atmos. Chem. Phys., 10,
11931-11954, doi:10.5194/acp-10-11931-2010, 2010.
Xiao, Y., D. J. Jacob, and S. Turquety (2007), Atmospheric acetylene and its relationship with CO as an indicator of air mass age, J.
Geophys. Res., 112, D12305, doi:10.1029/2006JD008268.
file:///C:/Users/SARP/Downloads/Nicola_Poster_FRAPPE_Sci%20team%20May%202015%202%20(2).pdf
http://www.plasticsnews.com/article/20160420/NEWS/160429969/explosion-kills-13-injures-88-at-mexichem-vinyl-chloride-plant