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The Utility of Combinations of

Tracers in Determining Emission


Nicole Grossberg
University of Houston
SARP 2010
  Overview of alkyl nitrates
  Description of experiment
  Investigation of source of methyl nitrate
  Conclusions
  References
  Acknowledgements
Alkyl Nitrates (RONO2)
  Component of NOy (Sum of NO and its atmospheric oxidation
products), comprise up to 80% in equatorial marine boundary layer
over the Pacific. Less than 10% in continental air masses.
  Low reactivity compared with other NOy components
  Serve as reservoir for the long-range transport of nitrogen oxides
  Important in regulating ozone levels
  Originally thought only to be of anthropogenic origin
  There are two major pathways for alkyl nitrate production
  Marine emissions
  Methyl and Ethyl nitrates
  Photochemical oxidation of parent hydrocarbons
Photochemical Mechanism of Alkyl
Nitrate Production

• RH is a parent
• R is the alkyl
• RO2 is an alkyl
peroxy radical
• RO is an alkoxyl

  Whole air samples were taken during two science flights on

the NASA DC-8 aircraft on June 29, 2010 and July 1, 2010
  Collected samples in evacuated 2L stainless steel sampling
  Cans were analyzed at the University of California, Irvine
  Alkyl nitrates were measured using gas chromatography
(GC) with electron capture detection (ECD)
  Methane analysis was done using GC with a flame ionization
detector (FID)
Methyl Nitrate along Flight tracks

12 pptv decrease
Methyl Nitrate mixing ratios
How can it be determined if the origin
of the MeONO2 is marine or
  Look at the parent hydrocarbon, methane
  If methane is present, the MeONO2 is made photochemically
  Ratio Methyl Nitrate to Ethyl Nitrate
  Marine values are 4:1
  DMS levels are an indication of marine air
  Back trajectories show where the air mass came from
Methane Concentrations
Methane is most likely coming from the
Methyl and Ethyl Nitrate Mixing Ratios
In studies investigating the hypothesis that the ocean is a source of light alkyl nitrates, the surface
distribution of EtONO2 mirrored that of MeONO2. In the remote marine atmosphere, reported
concentrations of MeONO2 range from 0.2 to 50 pptv, and EtONO2 ranges from 0.3 to 12.2 pptv.
While surface water shows strong correlation, depth profiles reveal differences that suggest distinct
mechanisms of the production of methyl and ethyl nitrate.
Methyl Nitrate / Ethyl Nitrate

The ratio value at the first peak is 2.28, the

second peak 2.80, and at the third peak, 3.88.
The third peak value is closet to the typical 4:1
marine air methyl/ethyl nitrate ratio
Dimethylsulfide (DMS)
  Component of an active
seawater sulfur cycle
  Secondarily produced by
  Atmospheric mixing ratios
depend on concentration in
water, chemical removal
rates, boundary layer height,
exchange with the free
troposphere, and wind speed
  The lifetime of DMS is short
Because it is produced by phytoplankton, DMS is a
good indicator of marine air

Giant spike in DMS,

Smaller peak in DMS confirming that this methyl
nitrate is from a marine source
Back Trajectories
Inputs: time, GPS coordinates, and altitude
Uses historical meteorological data to create back
  In order to correctly identify the source of a compound with
multiple emission pathways, a number of factors should be
  By looking at a combination of tracers, along with historical
meteorological data, the origin of the MeONO2 measured in
this experiment could be determined.
  The highest mixing ratios of methyl nitrate found were
produced both photochemically and by the ocean.
  Blake, N. J., D. R. Blake, B. C. Sive, A. S. Katzenstein, S. Meinardi, O. W. Wingenter, E. L. Atlas, F. Flocke, B. A.
Ridley, and F. S. Rowland, The seasonal evolution of NMHCs and light alkyl nitrates at middle to high northern
latitudes during TOPSE, J. Geophys. Res., 108(D4), 8359, doi:10.1029/2001JD001467, 2003.
  Blake, N. J., et al. (1999), Aircraft measurements of the latitudinal, vertical, and seasonal variations of NMHCs,
methyl nitrate, methyl halides, and DMS during the First Aerosol Characterization Experiment (ACE 1), J.
Geophys. Res., 104(D17), 21,803–21,817, doi:10.1029/1999JD900238.
  Chuck, A.L., Turner, S.M, and Liss, P.S., Source of C1 and C2 Alkyl Nitrates, Science., 297, 1151-1154 (2002).
  Muhle, J., A. Zahn, C. A. M. Brenninkmeijer, V. Gros, and P. J. Crutzen, Air mass classification during the
INDOEX R/V Ronald Brown cruise using measurements of nonmethane hydrocarbons, CH4, CO2, CO, 14CO,
and 18O(CO), J. Geophys. Res., 107(D19), 8021, doi: 10.1029/2001JD000730, 2002.
  Simpson, I. J., N. J. Blake, D. R. Blake, E. Atlas, F. Flocke, J. H. Crawford, H. E. Fuelberg, C. M. Kiley, S.
Meinardi, and F. S. Rowland, Photochemical production and evolution of selected C2 – C5 alkyl nitrates in
tropospheric air influenced by Asian outflow, J. Geophys. Res., 108(D20), 8808, doi:10.1029/2002JD002830,
  Simpson, I. J., S. Meinardi, D. R. Blake, N. J. Blake, F. S. Rowland, E. Atlas, and F. Flocke, A biomass burning
source of C1–C4 alkyl nitrates, Geophys. Res. Lett., 29(24), 2168, doi:10.1029/2002GL016290, 2002.
  Singh, H. B., W. Viezee, and L. J. Salas (1988), Measurements of selected C2–C5 hydrocarbons in the troposphere:
Latitudinal, vertical, and temporal variations, J. Geophys. Res., 93(D12), 15,861–15,878.
  Volz-Thomas, A., Berg, M., Heil, T., Houben, N., Lerner, A., Petrick, W., Raak, D., and Pätz, H.-W.:
Measurements of total odd nitrogen (NOy) aboard MOZAIC in-service aircraft: instrument design, operation and
performance, Atmos. Chem. Phys., 5, 583-595, doi:10.5194/acp-5-583-2005, 2005.
  Dr. Donald Blake
  Rick Shetter
  Matthew Gartner, UCI Graduate Student
  DC-8 Crew