Using Chemical Tracers and Trajectory Analysis to Determine Air Mass Composition

Tamara Sparks
Westmont College

Student Airborne Research Program 2012

Advisor: Donald R. Blake Mentor: Gregory Hartt

Research Flight 2

Goal
Two-fold

approach to examining the air mass in the marine boundary layer

1) Urban and marine tracer gases n Marine Tracers n Urban Tracers
DMS n MeONO2 n CH3I n CHBr3
n

C2Cl4 n HFC-134a n Ethyne n i-Pentane

n

2) NOAA HYSPLIT trajectories

Marine Tracers
Dimethyl Sulfide (DMS) Primarily produced by algae Minor source Industrial catalyst Methyl Nitrate (MeONO2) Photochemical production from aqueous CH3OO + NO in the ocean and atmosphere Methyl Iodide (CH3I) Bulk is produced by algae Minor sources Biomass burning Pesticide Bromoform (CHBr3) Primarily produced by algae Former industry and medicinal use

Carpenter, L.J., Liss P.S. J. Geophys. Res. 2000, 105, 20,539-20,547. Charlson, R.J., et al. Nature. 1987, 326,655-661. Dahl, E.E., Saltzman, E.S. Geophys. Res. Lett. 2003, 30, 1271-1274. www.gaylordchemical.com; http://toxnet.nlm.nih.gov Wollan, Malia. Marker Pulls Pesticide Amid Fear of Toxicity The New York Times, 2012. Toxicological Profile for Bromoform and Dibromochloromethane; U.S. Department of Health and Human Services: 2005.

Methyl Iodide

Marine tracers and altitude

1600 1400

Pressure Altitude (ft)

1200 1000 800 600

y = -1608.1x + 1975.9 R = 0.85

2

0.2

0.4

0.6

0.8

1.0

CH3I (ppt)

Correlation between marine tracers

6

MeONO2 (ppt)

y = 0.75x + 2.69 R = 0.76

2

2 1 2 3 4

CHBr3 (ppt)

Correlation between marine tracers

6

MeONO2 (ppt)

y = 0.92x + 2.24 R = 0.87 Flight 2 Flight 1

2

2 1 2 3 4

CHBr3 (ppt)

Urban Tracers
Perchloroethylene (C2Cl4) Chemical solvent tracer Drycleaning Dominantly anthropogenic production HFC-134a 1,1,1,2-Tetrafluoroethane Chemical solvent tracer Replacement for CFC uses such as refrigeration Ethyne Combustion tracer Product of internal combustion engines i-Pentane Gasoline tracer Gasoline evaporation and leakage

Barletta, B., et al. Atmos. Environ. 2005, 39, 5979-5990. Franklin, J. Chemosphere. 1993,27,1565-1601. Simpson, I.J., et al. Geophys. Res. Lett. 2004, 31, L08108.

Ethyne

Correlation between urban tracers

400

Ethyne (ppt)

300 y = 40.09x - 19.25 200 R = 0.88

2

100

10

C2Cl4 (ppt)

Correlation between urban tracers

110

100

HFC-134a (ppt)

90

y = 0.09x + 70.14 R = 0.86

2

80

70 100 200 300 400

i-Pentane (ppt)

Urban tracers and altitude

1600 1400

Pressute Altitude (ft)

1200 1000 800 600

10

C2Cl4 (ppt)

Urban and marine tracers

110

100

HFC-134a (ppt)

90

80

70

0.2

0.4

0.6

0.8

1.0

CH3I (ppt)

Backward Trajectories

Forward Trajectory
Elevated baselines Implications for air aging studies Marine air inflow

Riverside

Bromoform

Back Trajectory from Riverside

Conclusions
Confirmed the gases used as good urban or marine tracers Identified a possible path for the air mass Shows that Riverside is getting air that had an elevated baseline for urban pollution before entering the LA basin as well as marine inflow

Future Studies

Long-term study
Regular

occurrence or fluke?

More samples in Riverside

Can

correlations between tracers connect air in Riverside to air in marine boundary layer?

References

Barletta, B., et al. Volatile organic compounds in 43 Chinese cities. Atmos. Environ. 2005, 39, 5979-5990. Carpenter, L.J., Liss P.S. On temperate sources of bromoform and other reactive organic bromine gases. J. Geophys. Res. 2000, 105, 20,539-20,547. Charlson, R.J., et al. Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate. Nature. 1987, 326,655-661. Cohan, D.S., et al. Convective injection and photochemical decay of peroxides in the tropical upper troposphere: Methyl iodide as a tracer of marine convection. J. Geophys. Res. 1999, 104, 5717-5724. Dahl, E.E., Saltzman, E.S. The aqueous phase yield of alkyl nitrates from ROO + NO: Implications for photochemical production in seawater. Geophys. Res. Lett. 2003, 30, 1271-1274. Franklin, J. The Atmospheric Degradation and Impact of 1,1,1,2-Tetrafluoroethane (Hydrofluorocarbon 134a). Chemosphere. 1993,27,1565-1601. www.gaylordchemical.com Jordan, C., et al. Long-term study of VOCs measured with PTR-MS at a rural site in New Hampshire with urban influences. Atmos. Chem. Phys. 2009, 9, 4677-4697. Moore, R.M., Blough, N.V. A marine source of methyl nitrate. Geophys. Res. Lett. 2002, 29, 1737-1740. Simpson, I.J., et al. Long-term decrease in the global atmospheric burden of tetrachloroethene (C2Cl4). Geophys. Res. Lett. 2004, 31, L08108. Toxicological Profile for Bromoform and Dibromochloromethane; U.S. Department of Health and Human Services: 2005. http://toxnet.nlm.nih.gov Wollan, Malia. Marker Pulls Pesticide Amid Fear of Toxicity The New York Times, 2012. Zhou, Y., et al. Bromoform and dibromomethane measurements in the seacoast region of New Hampshire, 2002-2004. J. Geophys. Res. 2008, 113, D08305.

Acknowledgments
WAS Group Greg Hartt Don Blake Blake/Rowland Lab Group Emily Schaller, Rick Shetter, rest of NSERC NASA Airborne Science Program

Questions?