What causes aerosol growth and ozone production in smoke plumes?

Conference Proceedings Paper
What causes aerosol growth and ozone production in smoke plumes?
Alvarado, M.J., and R.G. Prinn (2006)
Eos Transactions, 87(52), Abstract A31F-03

Abstract/Summary:

The growth of aerosol particles and production of ozone in smoke plumes is the result of a complex interaction between horizontal diffusion, gas-phase oxidation, coagulation, and mass transfer between phases. Models allow us to separate the effects of these processes and predict their impact on the global environment. We present the results of a new model of gas and aerosol chemistry applied to young biomass burning plumes. The model includes heterogeneous chemistry, kinetic mass transfer, coagulation and the formation of secondary organic and inorganic aerosol. Comparison with measurements from SAFARI 2000 (Hobbs et al., 2003, JGR, doi:10.1029/2002JD002352) suggests the baseline model underpredicts ozone formation and the growth of aerosol within the plume. We explore whether the model predictions can be improved by (1) including heterogeneous HONO production, and (2) adding in surrogates for the uncharacterized organic compounds emitted by the biomass burning. Including the heterogeneous reaction NO2 => HONO greatly improves the match for ozone, OH, and aerosol nitrate concentration, but only when the uptake coefficient approaches 10-3, which is over an order of magnitude higher than previously reported values (Stemmler et al., 2006, doi:10.1038/nature04603). Using the reaction NO2 => 0.5 HONO + 0.5 HNO3 with an uptake coefficient of 10-3 (the top of the range recommended by Jacob, 2000, Atm. Env.,34, 2131-2159) provides an even better match for aerosol nitrate, but produces less O3 and OH than the first reaction. Direct measurements of HONO and OH in young biomass plumes would help determine if this chemistry is taking place. We used two surrogates to model the uncharacterized compounds: long chain alkanes and monoterpenes, representing primary and secondary sources of condensable compounds respectively. Complete condensation of the long-chain alkanes can account for nearly all of the observed increase in organic carbon. However, the accommodation coefficient must be near 10-3 or the alkanes will condense too quickly or too slowly. This value is reasonable when compared to measured accommodation coefficients of organic vapors on organic films (Donaldson et al, 2005, Faraday Discuss, doi:10.1039/b418859d). Monoterpenes gradually increase condensed organic carbon even with accommodation coefficients of 0.1, but produced only 35% as much as the alkanes. Production of sulfate and total particulate matter is below observations in all simulations described above. Better characterization of the composition of the condensed organic matter as a function of downwind distance could help determine the source of the organic aerosol growth.

Citation:

Alvarado, M.J., and R.G. Prinn (2006): What causes aerosol growth and ozone production in smoke plumes?. Eos Transactions, 87(52), Abstract A31F-03 (http://www.agu.org/meetings/fm06/?content=program)
  • Conference Proceedings Paper
What causes aerosol growth and ozone production in smoke plumes?

Alvarado, M.J., and R.G. Prinn

87(52), Abstract A31F-03

Abstract/Summary: 

The growth of aerosol particles and production of ozone in smoke plumes is the result of a complex interaction between horizontal diffusion, gas-phase oxidation, coagulation, and mass transfer between phases. Models allow us to separate the effects of these processes and predict their impact on the global environment. We present the results of a new model of gas and aerosol chemistry applied to young biomass burning plumes. The model includes heterogeneous chemistry, kinetic mass transfer, coagulation and the formation of secondary organic and inorganic aerosol. Comparison with measurements from SAFARI 2000 (Hobbs et al., 2003, JGR, doi:10.1029/2002JD002352) suggests the baseline model underpredicts ozone formation and the growth of aerosol within the plume. We explore whether the model predictions can be improved by (1) including heterogeneous HONO production, and (2) adding in surrogates for the uncharacterized organic compounds emitted by the biomass burning. Including the heterogeneous reaction NO2 => HONO greatly improves the match for ozone, OH, and aerosol nitrate concentration, but only when the uptake coefficient approaches 10-3, which is over an order of magnitude higher than previously reported values (Stemmler et al., 2006, doi:10.1038/nature04603). Using the reaction NO2 => 0.5 HONO + 0.5 HNO3 with an uptake coefficient of 10-3 (the top of the range recommended by Jacob, 2000, Atm. Env.,34, 2131-2159) provides an even better match for aerosol nitrate, but produces less O3 and OH than the first reaction. Direct measurements of HONO and OH in young biomass plumes would help determine if this chemistry is taking place. We used two surrogates to model the uncharacterized compounds: long chain alkanes and monoterpenes, representing primary and secondary sources of condensable compounds respectively. Complete condensation of the long-chain alkanes can account for nearly all of the observed increase in organic carbon. However, the accommodation coefficient must be near 10-3 or the alkanes will condense too quickly or too slowly. This value is reasonable when compared to measured accommodation coefficients of organic vapors on organic films (Donaldson et al, 2005, Faraday Discuss, doi:10.1039/b418859d). Monoterpenes gradually increase condensed organic carbon even with accommodation coefficients of 0.1, but produced only 35% as much as the alkanes. Production of sulfate and total particulate matter is below observations in all simulations described above. Better characterization of the composition of the condensed organic matter as a function of downwind distance could help determine the source of the organic aerosol growth.