Grantee Research Project Results
2001 Progress Report: Predicting Day and Nighttime Aerosol Yields from Biogenic Hydrocarbons with a GasBParticle Phase Kinetic Model
EPA Grant Number: R828176Title: Predicting Day and Nighttime Aerosol Yields from Biogenic Hydrocarbons with a GasBParticle Phase Kinetic Model
Investigators: Kamens, Richard M.
Institution: University of North Carolina at Chapel Hill
EPA Project Officer: Hahn, Intaek
Project Period: July 17, 2000 through July 16, 2002 (Extended to July 16, 2003)
Project Period Covered by this Report: July 17, 2000 through July 16, 2001
Project Amount: $225,000
RFA: Exploratory Research - Engineering, Chemistry, and Physics) (1999) RFA Text | Recipients Lists
Research Category: Air Quality and Air Toxics , Water , Land and Waste Management , Air , Safer Chemicals
Objective:
The objective of this research project is to describe a methodology to develop a predictive model for biogenic aerosol formation from the reaction of three terpenes (-pinene, -pinene, and d-limonene) in the presence of OH, NOx, and natural sunlight. Once we have developed models and experimentally tested them with outdoor chamber data, they can be extended to the aerosol forming potential of almost all other terpenes.
We had proposed to study three compounds (-pinene, -pinene, and d-limonene) as well as conduct approximately 14 chamber experiments. Given the reduction in the award level to 225K for 2 years, this approach has been scaled back to 10 experiments because we still need to focus efforts on methods development for products.
Progress Summary:
The reactions of monoterpenes in the gas and particle phases have received much attention during the past 10 years. The rate constants for the gas-phase reactions of many monoterpenes have been summarized by Atkinson, 1997.1 There also have been several laboratory investigations on the atmospheric oxidation of terpenes.2-15 Despite recent progress, however, the reaction mechanisms of monoterpenes are far from being sufficiently understood, even for the case of -pinene and -pinene. In addition, very few studies have addressed the pathways leading to the gas-particle conversion of terpenes.16 ß-Pinene together with -pinene, d-limonene, -3-carene, 1,8-cineole, -phellandrene, mycrene, camphene, and sabinene account for most of the emitted terpene mass from biogenic sources in the United States.17-20 The biochemical mechanisms of their formation in plants are closely linked, so that emissions of more than one monoterpene often occur together.21-22 In previous papers, we reported the time-series development of a wide range of reaction products from the oxidation of -pinene, with O3 and NOx, in the presence of natural sunlight,14,16 as well as the time-series development of a wide range of reaction products from the oxidation of -pinene with NOx, in the presence of natural sunlight, and from the oxidation of -pinene with O3 in the nighttime.15 The identification of a wide range of products and their time-series evolution for the oxidation of a mixture of -pinene and -pinene by O3 and/or OH radicals in the presence of NOx, can give valuable insights into the detailed mechanism of this system.16 This is supported by a study of the aerosol composition in forested areas by Kavouras, et al.23-25 They identified cis- and trans-pinonic acids, as well as pinonaldehyde from the oxidation of -pinene by OH, O3, and NO3, and nopinone from the oxidation of -pinene in particles in a forest in Portugal. The objective of this work focuses on the characterization of gas and particle phase reaction products from the oxidation of -pinene + -pinene, with ozone and -pinene + -pinene, and with OH radicals in the presence of NOx and natural sunlight. The mixture of -pinene and -pinene was selected as representative of terpenes released naturally20; -pinene is representative of cyclic terpenes containing an endocyclic C=C double bond (3-carene, 2-carene, limonene, -phellandrene, -phellandrene, -terpinene), and -pinene of terpenes containing an exocyclic C=C double bond (sabinene, camphene, limonene, -phellandrene, -caryophyllene). To our knowledge, there have been no studies that determine yields of gaseous and particulate products from the simultaneous oxidation of terpene mixtures.
The analytical results from this study will allow the development and testing of numerical kinetic mechanism models16,26 suitable for use in regional atmospheric chemistry models and in the determination of partitioning of products between the gas and particle phase. Here, we report the yields of reaction products in both gas and aerosol phases over the course of the -pinene + -pinene mixture oxidation with O3 in the absence of light and with oxides of nitrogen NOx in the presence of natural sunlight and air.
References:
1. Atkinson R. Gas-phase tropospheric chemistry of organic compounds. Issues
In Environmental Science and Technology 1995;4:65-90.
2. Hakola H, Arey J, Aschmann SM, Atkinson RJ. Product formation from the gas-phase reaction of OH radicals and O3 with a series of monoterpenes. Journal of Atmospheric Chemistry 1994;18:75-102.
3. Calogirou A, Kotzias D, Kettrup A. Atmospheric oxidation of linalool. Naturwissenschaften 1995;82(6):288-289.
4. Calogirou A, Duane M, Kotzias M, Lahaniati M, Larsen BR. Polyphenylenesulfide, noxon®, an ozone scavenger for the analysis of oxygenated terpenes in air. Atmospheric Environment 1997;31(17):2741-2751.
5. Berndt T, Böge O. Products and mechanism of the gas phase reaction of NO3 radicals with -pinene. Journal of the Chemical Society, Faraday Transactions 1997;93:3021-3027.
6. Grosjean E, Grosjean D. The gas phase reaction of unsaturated oxygenates with ozone: carbonyl products and comparison with the alkene-ozone reaction. Journal of Atmospheric Chemistry 1997;27(3):271-289.
7. Hallquist M, Wangberg E, Ljungstrom E. Atmospheric fate of carbonyl oxidation products originating from -pinene and -3-carene: determination of rate of reaction with OH and NO3 radicals, UV adsorption cross sections and vapor pressures. Environmental Science and Technology 1997;31(11):3166-3172.
8. Shu Y, Kwork ES, Tuazon EC, Atkinson R, Arey J. Products of the gas-phase reactions of linalool with OH radicals, NO3 radicals, and O3. Environmental Science and Technology 1997;31(3):896-904.
9. Vinckier C, Compernolle F, Saleh AM. Qualitative determination of the non-volatile reaction products of the -pinene reaction with hydroxyl radicals. Bull. Aos. Chim. Belg. 1998;106:501-513.
10. Wängberg I, Barnes I, Becker KH. Product and mechanistic study of the reaction of NO3 radicals with -pinene. Environmental Science and Technology 1997;31(7):2130-2135.
11. Alvarado A, Tuazon EC, Aschmann SM, Atkinson R, Arey J. Product of the gas phase reactions of O(3P) atoms and O3 with -pinene and 1,2-dimethyl-1-cyclo-hexene. Journal of Geophysical Research 1998;103:25541-25551.
12. Noziere B, Barnes I, Becker K. Product study and mechanisms of the reactions of -pinene and of pinonaldehyde with OH radicals. Journal of Geophysical Research 1999;104:23645-23658.
13. Jang M, Kamens RM. Newly characterized products and composition of secondary aerosols from reaction of -pinene with ozone. Atmospheric Environment 1999;33(3):459-474.
14. Jaoui M, Kamens RM. Mass balance of gaseous and particulate products analysis from -pinene/NOx/air in the presence of natural sunlight. Journal of Geophysical Research: Atmosphere 2001a;106:12541-12558.
15. Jaoui M, Kamens RM. Mass balance of gaseous and particulate products from -pinene/O3/Air in the absence of light and -pinene/NOx/Air in the presence of natural sunlight. Journal of Geophysical Research: Atmosphere (submitted, 2001).
16. Kamens RM, Jaoui M. Modeling aerosol formation from -pinene + NOx in the presence of natural sunlight using gas-phase kinetics and gas-particle partitioning theory. Environmental Science and Technology 2001;35(7):1394-1405.
17. Lamb B, Gay D, Westberg H, Pierce T. A biogenic hydrocarbon emission inventory for the U.S.A. using a sample forest canopy model. Atmospheric Environment Part A 1993;27:1673-1690.
18. Guenther A, Zimmerman P, Wildermuth M. Natural volatile organic compounds emission rate estimates for U.S. woodland landscapes. Atmospheric Environment 1994;28:1147-1210.
19. Geron C, Rasmusssen R, Arnts R, Guenther A. A review and synthesis of monoterpene speciation from forests in the United States. Atmospheric Environment 2000;34(11):1761-1781.
20. Seufert G, ed. BEMA, a European commission project on biogenic emission in the Mediterranean area. Atmospheric Environment 1997;31(S1):1-256.
21. Fall R. Biogenic emissions of volatile organic compounds from higher plants, in reactive hydrocarbons in the atmosphere. Hewitt CN, ed. San Diego, CA: Academic Press, 1999, Chapter 2, pp. 41-96.
22. Finlayson-Pitts BJ, Pitts JN. Upper and lower atmosphere: theory, experiments, and applications. Academic Press, 2000.
23. Kavouras IG, Mihalopoulos N, Stephanou EG. Formation of atmospheric particles from organic acids produced by forest. Nature 1998;395:683-686.
24. Kavouras IG, Mihalopoulos N, Stephanou EG. Secondary organic aerosol formation versus primary organic aerosol emission: in situ evidence for the chemical coupling between monoterpene acidic photooxidation products and new particle formation over forests. Environmental Science and Technology 1999;33(7):1028-1037.
25. Kavouras IG, Mihalopoulos N, Stephanou EG. Formation and gas/particle partitioning of monoterpenes photooxidation products over forests. Geophysical Research Letters 1999;26:55-58.
26. Barthelmie RJ, Pryor SC. A model mechanism to describe oxidation of monoterpenes leading to secondary organic aerosol 1. α-pinene and β-pinene. Journal of Geophysical Research 1999;104:23657-23669.
Future Activities:
During the first year of the project, we conducted one -pinene experiment, two -pinene experiments, and one d-limonene experiment. We now are analyzing the data from these experiments and constructing mechanistic models for -pinene and d-limonene. These experiments fit in with the central goals of the project, which are to elucidate the atmospheric chemistry of terpenoid material.
Journal Articles:
No journal articles submitted with this report: View all 17 publications for this projectSupplemental Keywords:
secondary organic aerosols, terpenes, -pinene, terpene products, mass balance., RFA, Scientific Discipline, Air, particulate matter, Environmental Chemistry, Environmental Monitoring, Engineering, Chemistry, & Physics, ambient aerosol, gas/particle partitioning, aerosol formation, nitrates, oxygenates, kinetic models, biogenic hydrocarbons, photolysis wavelength, terpenes, biogenic aerosols, atmospheric modelsProgress and Final Reports:
Original AbstractThe perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.