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The Impact of Secondary Organic Aerosol Derivatives of Isoprene on Cloud Formation and Albedo

The Impact of Secondary Organic Aerosol Derivatives of Isoprene on Cloud Formation and Albedo. Akua Asa-Awuku EAS6410 Term Paper Presentation. Summary. Motivation Biogenic Emissions Sources of Isoprene Sources of SOA from Isoprene The impact of SOA’s on Cloud Formation

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The Impact of Secondary Organic Aerosol Derivatives of Isoprene on Cloud Formation and Albedo

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  1. The Impact of Secondary Organic Aerosol Derivatives of Isoprene on Cloud Formation and Albedo Akua Asa-Awuku EAS6410 Term Paper Presentation

  2. Summary • Motivation • Biogenic Emissions • Sources of Isoprene • Sources of SOA from Isoprene • The impact of SOA’s on Cloud Formation • Cloud Formation and Albedo • Hydrological Implications

  3. The Importance of Biogenic Emissions • Amazon has low levels of anthropogenic emissions • Isoprene emissions in US larger than anthropogenic particulate matter • Eight Different Vegetation Types are major sources of Isoprene

  4. Major Sources of NMHC Tg C yr-1

  5. What is Isoprene • Olefinic • Highly reactive Double Bonds • Volatile Organic Compound (VOC) • Non-Methane Hydrogen Carbon (NHMC)

  6. Products of Isoprene Photooxidation

  7. Derivatives of Photoxidation • Assumed to be extremely volatile (e.g formaldehyde) • Assumed Most likely not to be SOA’s • Two newly identified species hypothesized to be SOA’s from photooxidation of isoprene • Formation of SOA via acidic catalysts

  8. Data Collection • Data Samples collected from LBA-CLAIRE campaign July 25 -27 [Claeys, 2004] • Assumptions • Very low Anthropogenic emissions • Tropics site of high photoxidation • Samples Subjected to GS-MS

  9. SOA from Isoprene • Gas Chromatography results that show presence of a product of isoprene photo-oxidation • Similar 5 carbon skeleton as that of isoprene

  10. SOA from Isoprene • Proposed formation of the 2-methyltetrols from isoprene by reaction with OH’O2 followed by self-and cross-reactions with radicals • Intermediate 1,2, diols have been previously reported under low NOx conditions [Ruppert, 2000]

  11. Significance of (1) and (2) • SOA’s have low yield from Isoprene photooxidation • However, large emissions of Isoprene, suggest significant annual formation of SOA’s • Estimated 2 Tg per year of (1) and (2) in Amazon Basin • IPCC estimates 8 to 40 Tg of biogenic SOA annually • Low Vapor Pressure and High Hygroscopicity

  12. SOA’s via Sulfuric Acid Catalysts • Urban and Rural Areas contain sufficient amounts of background acidic catalysts • Also significant emissions of Isoprene in these regions • Limbeck explained that proposed pathway contribute to the explanation of HULIS substances on continental Europe

  13. Reaction Yield increases with catalyst • Influence of ozone as competing oxidant • Effect of Relative air Humidity

  14. Short Recap • SOA’s from Isoprene Exist • Photooxidative products have low vapor pressures • Humic-like substances generated from acidic catalysts • All SOA’s from Isoprene can be considered to be highly hydroscopic

  15. Cloud Formation • Kohler Equation • Kelvin Effects • Strong functions of Surface Tension • Humic-like aerosols decrease σ

  16. Decreasing Surface Tension

  17. Kohler Curves

  18. Consequences of Surfactants • Great Cloud Droplet Number • 30% decrease in σ yields a 20% increase in droplet number • Smaller cloud droplet Radii • Average 6% decrease in droplet size • Significant Change in Cloud Properties (hence Albedo)

  19. Droplet Number and Albedo

  20. Albedo and Cloud Optical Thickness

  21. Susceptiblity • defined as the sensitivity of cloud albedo in comparison to cloud droplet number concentration • ten percent increase in droplet number concentration, leads to an increase of 0.75% in albedo

  22. Albedo and Cloud Optical Thickness

  23. Hydrological Cycle Cloud Albedo Cloud Formation SOA Formation Isoprene Emissions Precipitation/ Water Stress Surface Temperature

  24. Conclusions • SOA’s from Isoprene do exist • Humic-like SOA’s decrease surface tensions of pure water by 30% increase the droplet number concentration by 20% • 20% increase in droplet number, correlates to a change in top of atmospheric cloud albedo of nearly 1% • a global mean forcing of almost -1 Wm-2 due to SOA’s from Isoprene

  25. References • Barth, Mary et. al., Future Scientific Directions: Coupling between land ecosystems and the atmospheric hydrologic cycle through biogenic aerosol pathways., Bulletin of the American Meteorological Society, (submitted) • Brasseur, G., J. Orlando and G. Tyndall, Atmospheric Chemistry and Global Change, Oxford Univ. Press, New York, NY,1999 • Claeys M, Graham B, Vas G, Wang W Vermeylen R, Pashaynshka V, Cafmeyer J, Guyon P, Andrae MO, Artaxo P, Maehunt W., Formation of Secondary Organic Aerosols through photooxidation of Isoprene, Science, 202 (5661):1173-1176 Feb. 20. 2004 • Helmig, Detlev .,Ben Balsley, Kenneth Davis, Laura R. Kcuck. Mike Jensen, John Bognar, Tyrrel Smith Jr., Rosaura Vasquez Arrieta, Roldolfo Rodriguez, and John W. Berks., Vertical profiling and determination of landscape fluxes of biogenic non methange hydrocarbons with the planetary boundary layer in the Peruvian Amazon, J. Geophys. Res.¸103 (D19): 25519-25532, 1998 • Durieux, L., L.A.T. Machado, H. Laurent, The impact of deforestation on cloud cover over the Amazon arc of deforestation, Remote Sensing of Environ., 86, 132-140, 2003. • Facchini, M.., M. Mircea, S. Fuzzi, and R. J. Charlson, Cloud albedo enhancement by surface-active organic solutes in growing droplets, Nature, 401, 257-259. 1999 • Fall, R. and M.C. Wildermuth. Isoprene synthase: From biochemical mechanism to emission algorithm, J. Geophys. Res.¸103 (D19): 25599-25609, 1998. • Griffin, R.J., D.R. Cocker III, J.H. Seinfeld and D. Dabdub. Estimate of global atmospheric organic aerosol from oxidation of biogenic hydrocarbons, Geophys. Res. Lett., 26 (17), 2721-2724, 1999. • Guenther, A., C.N. Hewitt, D. Erickson, R. Fall, C. Geron, T. Graedel, P. Harley, L. Klinger, M. Lerdau, W.A. Mckay, T. Pierce, B. Scholes, R. Steinbrecher, R. Tallamraju, J. Taylor and P. Zimmerman, A global model of natural volatile organic compound emissions, J.Geophys. Res. 100, 8873-8892,1995. • Guenther, A., S. Archer, J. Greenberg, P. Harley, D. Helmig, L. Klinger, L. Vierling, M. Wildermuth, Biogenic hydrocarbon emissions and landcover/climate change in a subtropical savanna, Phys. Chem. Earth (B), 24, 659-667, 1999. • Jang, M., and R. Kamens, Atmospheric secondary aerosol formation by heterogeneous reaction of aldehydes in the presence of a sulfuric acid aerosol catalyst, Environ. Sci. Technol., 35, 4758-4766, 2001. • Klinger, L.F., J. Greenberg, A. Guenther, G. Tyndall, P. Zimmerman, M. M’Bangui, J.M. Moutsambot, and D. Kenfck, Patterns in volatile organic compound emissions along a savanna rainforesst gradient in central Africa, J. Geophys. Res., 103, 1443-1454, 1998. • Limbeck, A., M. Kulmala, and H. Puxbuam, Secondary organic aerosol formation in the atmosphere via heterogeneous reaction of gaseous isoprene on acidic particles, Geophys. Res. Lett.,30 (19), 1996, 2003. doi: 10.1029/2003GL017738 • Otter, L.B., Guenther, A., Greenber, J., Seasonal and spatial vatirations in biogeneic hydrocarbon emissions from southern African savannas and woodlands, Atmospheric Enirmonmet, 36, 4265-4275, 2002. • Pétron, G., P. Harley, J. Greenberg, A. Guenther, Seasonal temperature variations influence isoprene emission, Geophys. Res. Lett., 28, 1707-1710, 2000. • Pirjola Liisa, Effects of the increased UV radiation and biogenic VOC emissions on Ultra fine sulphate aerosol Formation, J.Aerosol Sci., 30, 3, 355-367, 1999. • Roberts, G. C., M. O. Andreae, J. Zhou, P. Artaxo, Cloud condensation nuclei in the Amazon Basin: Marine conditions over a continent?, Geophys. Res. Lett., 28, 2807-2810, 2001. • Seinfeld, J., and N. Pandis, Atmospheric Chemistry and Physics: From air pollution to climate change, John Wiley & Sons, Inc., New York, NY 1998.

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