Grantee Research Project Results
2002 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, 2001 through July 16, 2002
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. The originally proposed work was based on an approximately $300,000 budget for 2 years. The level of effort had to be reduced to be commensurate with $225,000. 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, 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. There also have been several laboratory investigations on the atmospheric oxidation of terpenes. 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, few studies have addressed the pathways leading to the gas-particle conversion of terpenes. -pinene, together with - pinene, d-limonene, -carene, 1,8-cineole, -phellandrene, mycrene, camphene, and sabinene, account for most of the emitted terpene mass from biogenic sources in the United States. The biochemical mechanisms of their formation in plants are closely linked, so that emissions of more than one monoterpene often occur together. 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, 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. 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. This is supported by a study of the aerosol composition in forested areas by Kavouras, et al., 1998, 1999a,b. 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, with OH radicals in the presence of NOx and natural sunlight. The mixture of -pinene and -pinene was selected as representative of terpenes released naturally; -pinene is representative of cyclic terpenes containing an endocyclic C=C double bond (3-carene, 2-carene, d-limonene, -phellandrene, -phellandrene, -terpinene), and -pinene of terpenes containing an exocyclic C=C double bond (sabinene, camphene, d-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 models 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.
-pinene Experiments. The gas and particle phase products of the reaction of -pinene, with the atmospheric oxidants O3 and OH radicals (atmospheric air), in the presence of NOx, were investigated for identification and quantification of reaction products using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). A two-stage 47 mm Teflon-impregnated glass fiber filter, followed by a 40-cm 5-channel denuder (coated with XAD-4) sampling train, was used to collect reaction products in particle and gas phases, respectively. Particle formation was monitored using a Scanning Mobility Particle Sizer (SMPS). The nighttime oxidation of -pinene in the presence of O3/air and the daytime oxidation of -pinene in the presence of NOx/air and natural sunlight, were carried out in the University of North Carolina's large outdoor smog chamber (190 m3), located in Chatham County, NC. The mass balance of reacted products versus ß-pinene reaction was 71 percent for the O3 dark experiment, and ranged from 6-57 percent for the two daytime NOx experiments.
-Pinene and -Pinene Mixture Experiments. Mixture experiments with -pinene and -pinene in the presence of O3/air, and the daytime oxidation of a mixture of -pinene + -pinene with NOx/air in the presence of natural sunlight, also were conducted. Mass balances for gaseous and aerosol reaction products are reported over the course of the reaction. The gas and particle phase reaction products of a mixture of the atmospherically important terpenes -pinene and -pinene, with the atmospheric oxidants O3 and OH/NOx, were investigated using the GC-MS. More than 29 products were identified and/or quantified in this study in the gas and aerosol phases from the oxidation of -pinene + -pinene mixture, with NOx in the presence of natural sunlight, and with O3 in the nighttime. -Pinene and -pinene are both bicyclic, having an internal double bond for -pinene and an external double bond for -pinene. However, most reaction products observed in their oxidation by ozone or OH radicals in the presence of NOx and natural sunlight, are similar. The yield for each reaction product arising from the mixture appears to be independent of the presence of the second terpene for products that rise only from one of them (pinonaldehyde from -pinene, nopinone from -pinene). However, the yields for reaction products that arise from both terpenes (e.g., pinic acid, pinonic acid, 10-hydroxypinonic acid, 10-hydroxypinonaldehyde) appear to be dependent on the nature of the parent hydrocarbon. Keto-or and hydroxy-pinonic acid/pinonaldehyde, pinalic-3-acid, and 4-hydroxypinalic-3-acid were observed in the early stages of aerosol formation.
Yields for individual products identified in both gas and/or particle phases have been determined or estimated, thus providing a direct measure of the gas-particle partitioning of each product. Identified products in both gas and particle phases are estimated to account for about 67 percent to 80 percent of the total reacted mass -pinene + -pinene mixture, and their partitioning depends on the nature of the parent monoterpene and the oxidant.
Experiments with d-limonene. Among the monoterpenes, d-limonene (on a mass basis) has the highest aerosol formation potential, however, there are very few studies about its atmospheric reaction products and mechanism. As with and pinene, products of d-limonene reactions with ozone in the absence of sunlight and with OH in the presence of oxides NOx under natural sunlight, are presented. The reactions took place in a large outdoor smog chamber (190 m3). GC, flame ionization detector (FID) was used to monitor d-limonene disappearance. The samples were extracted and analysed with GC-MS. To aid the identification, derivatization techniques also were used. The limononaldehyde standard was synthesized with a purity greater than 90 percent. Results show that limononaldehyde, which partitions between gas and particle phases, was one of the major products from d-limonene oxidation with both O3 and OH. Some of the ring retaining products (e.g., limonaketone) and ring opening products (e.g., keto-carboxylic acid, dicarboxylic acid,hydroxy/oxo-aldehyde/carboxylic acid) were tentatively identified. A chemical mechanism was developed to explain the observed reaction products and a kinetic model of d-limonene using the Morpho Kinetic Solver (Jeffries and Kessler, 1999), was implemented.
References:
Atkinson R. Gas-phase tropospheric chemistry of organic compounds. Alkanes and
alkenes. Issues In Environmental Science and Technology 1995;4:65-90.
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(4):75-102.
Calogirou A, Kotzias D, Kettrup A. Atmospheric oxidation of linalool. Naturwissenschaften 1995;82(6):288-289.
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.
Berndt T, Böge O. Products and mechanism of the gas phase reaction of NO3 radicals with a-pinene. Journal of the Chemical Society, Faraday Transactions 1997;93:3021-3027.
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.
Hallquist M, Wangberg E, Ljungstrom E. Atmospheric fate of carbonyl oxidation products originating from a-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.
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.
Vinckier C, Compernolle F, Saleh AM. Qualitative determination of the non-volatile reaction products of the a-pinene reaction with hydroxyl radicals. Bull. Aos. Chim. Belg. 1998;106:501-513.
Wängberg I, Barnes I, Becker KH. Product and mechanistic study of the reaction of NO3 radicals with a-pinene. Environmental Science and Technology 1997;31(7):2130-2135.
Alvarado A, Tuazon EC, Aschmann SM, Atkinson R, Arey J. Product of the gas phase reactions of O3(P) atoms and O3 with a-pinene and 1,2-dimethyl-1-cyclo-hexene. Journal of Geophysical Research 1998;103(25):541-551.
Noziere B, Barnes I, Becker K. Product study and mechanisms of the reactions of alpha-pinene and of pinonaldehyde with OH radicals. Journal of Geophysical Research 1999;104 (D19):23645-23658.
Jang M, Kamens RM. Newly characterized products and composition of secondary aerosols from reaction of alpha-pinene with ozone. Atmospheric Environment 1999;33(3):459-474.
Jaoui M, Kamens RM. Mass balance of gaseous and particulate products analysis from alpha-pinene/NOx/air in the presence of natural sunlight. Journal of Geophysical Research 2001;106 (12):12541-12558.
Kamens RM, Jaoui M. Modeling aerosol formation from a-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.
Lamb B, Gay D, Westberg H, Pierce T. A biogenic hydrocarbon emission inventory for the USA using a sample forest canopy model. Atmospheric Environment 1993;27(11):1673-1690.
Guenther A, Zimmerman P, Wildermuth M. Natural volatile organic compounds emission rate estimates for U.S. woodland landscapes. Atmospheric Environment 1994;28(6):1197-1210.
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.
Seufert G, (ed.) BEMA, a European commission project on biogenic emission in the Medeteranian area. Atmospheric Environment 1997;31(S1):1-256.
Fall R. Biogenic emissions of volatile organic compounds from higher plants, in reactive hydrocarbons in the atmosphere. Hewitt CN, ed. Reactive Hydrocarbons in the Atmosphere San Diego, CA: Academic Press, 1999, Chapter 2, pp. 41-96.
Finlayson-Pitts BJ, Pitts JN. Upper and lower atmosphere: theory, experiments, and applications. Academic Press, 2000.
Kavouras IG, Mihalopoulos N, Stephanou EG. Formation of atmospheric particles from organic acids produced by forest. Nature 1998;395:683-686.
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.
Kavouras IG, Mihalopoulos N, Stephanou EG. Formation and gas/particle partitioning of monoterpenes photooxidation products over forests. Geophysical Research Letters 1999;26(1):55-58.
Barthelmie RJ, Pryor SC. A model mechanism to describe oxidation of monoterpenes leading to secondary organic aerosol 1. alpha and beta pinene. Journal of Geophysical Research 1999;104 (D19):23657-23669.
Kamens RM, Jang M, Chien CJ, Leach K. Aerosol formation from the reaction of alpha pinene and ozone using a gas-phase kinetics aerosol partitioning model. Environmental Science and Technology 1999;33(9):1430-1438.
Jang M, Kamens RM. A thermodynamic approach for modeling partitioning of semivolatile organic compounds on atmospheric particulate matter: humidity effects. Environmental Science and Technology 1998;32(9):1237-1243.
Andersson-Skold Y, Simpson D. Secondary organic aerosol formation in Northern Europe: a model study. Journal of Geophysical Research 2001;106(D7):7357-7374.
Pankow JF, Storey JME, Yamasaki W. Effects of relative humidity on gas/particle partitioning of semivolatile organic compounds to urban particulate matter. Governmental Science and Technology. Environmental Science and Technology 1993;27(10):2220-2226.
MacKay D, Bobra A, Chan DW, Shiu WY. Vapor-pressure correlations for low-volatility environmental chemicals. Environmental Science and Technology 1982;16(10):645-649.
Jang M, Kamens RM, Leach K, Strommen MR. A thermodynamic approach using group contribution methods to model the partitioning of semivolatile organic compounds on atmospheric particulate matter. Environmental Science and Technology 1997;31(10):2805-2811.
Kamens RM, Jang M, Chien CJ, Leach K. Aerosol formation from the reaction of alpha pinene and ozone using a gas-phase kinetics aerosol partitioning model. Environmental Science and Technology 1999;33(9):1340-1352.
Future Activities:
We currently are modeling all of the above described experiments, and plan to conduct 3-5 more d-limonene experiments, and a few susquiterpenene experiments. The kinetics modeling approach that we have developed for secondary organic aerosol (SOA) formation involves the production of semi-volatile compounds (SOCs) from the reactions of terpenes with OH, O3, and NO3. These SOCs then dynamically partition on and off existing aerosol mass depending on the thermodynamic properties of the aerosol and the concentration in the gas and particle phases.
The gas-particle partitioning of gas phase semivolatile a-pinene products were assumed to be governed by an equilibrium between the surrounding gas and a liquid phase particle. This is supported by previous investigations showing that -pinene-O3 aerosols can be treated using an absorptive equilibrium (gas-liquid) partitioning model. The equilibrium constant, Kp, for a given product SOC is equal to the ratio of the rate constants for the forward (absorption reaction or process) kon and backward (desorption) koff reactions (see Equation 1).
Kp = kon / koff | (1) |
Kp and koff can
be estimated by previously described methods, which then permits an estimate
of kon. These are used as a guide and adjusted
to give the best possible fits to experimental gas and particle phase product
data.
In the model, aerosol surfaces are available for partitioning from existing urban or rural aerosols called seed. In addition, to permit self-nucleation in the model, stabilized Criegee biradicals from the reaction of terpenes with O3 (called stabcrieg1 and stabcrieg2) are permitted to react with the carbonyl portion of product compounds such as pinald, oxypinonaldehydes, and pinalic acid to produce secondary ozonide products. The large dimer type molecules have estimated vapor pressures as low as 10-15 torr. It also is possible to form anhydride-dimer type products by reacting the Criegee with a dicarboxylic acid and alkoxy hydroperoxy acids from reaction with alcohols. These dimers called seed particles are available from the gas particle partitioning of more volatile compounds (see Equation 2-4).
stabcrieg1 + pinaldgas seed1 | (2) |
diacidgas + se ed1 diacidpart + seed1 | (3) |
diacidgas + se ed diacidpart + seed | (4) |
Other low vapor pressure products, such as gas phase pinic acid (diacidgas),
can now migrate to these particles and contribute their mass to the particle
phase (diacidpart in equations 6 and 7). This
creates more mass for further partitioning. Hence, gas phase hydroxypinan-nitrate
compounds (apOH-NO3gas) can migrate to the diacid
particle phase (diacidpart) and seed and seed1;
kinetically for the diacidpart. This process is represented
in Equation 5 and 6.
OH-apNO3gas + diacidpart OH-apNO3part + diacidpart rate constant = kon | (5) |
To maintain equilibrium, OH-apNO3part can back
react or "off-gases" from the particle to give back gas phase OH-apNO3gas
OH-apNO3part OH-apNO3gas rate constant = koff | (6) |
A similar set of reactions can be written for all of the partitioning products
including the PAN analog products. By keeping track of the amount of mass that
appears in the particle phase from each of the products, an estimate of the
overall particle mass yield can be made over a range of temperature conditions.
Because we have had to rebuild the smog chamber, in which the additional experiments will be conducted, there has been a delay in our progress. The chamber is currently under construction and will soon be done. We anticipate another 6 months of experiments and 4 months of modeling beyond the current ending date of this proposal.
A number of investigators are beginning to use our SOA modeling approach both in the United States and in Europe. Some of our results may also have been included in the new PM2.5 U.S. Environmental Protection Agency Criteria document and the new, North American Research Strategy for Tropospheric Ozone report.
Journal Articles on this Report : 5 Displayed | Download in RIS Format
Other project views: | All 17 publications | 17 publications in selected types | All 17 journal articles |
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Type | Citation | ||
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Dalton CN, Jaoui M, Kamens RM, Glish GL. Continuous real-time analysis of products from the reaction of some monoterpenes with ozone using atmospheric sampling glow discharge ionization coupled to a quadrupole ion trap mass spectrometer. Analytical Chemistry 2005;77(10):3156-3163. |
R828176 (2002) R828176 (Final) R826771 (Final) |
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Jang M, Kamens RM. Atmospheric secondary aerosol formation by heterogeneous reactions of aldehydes in the presence of a sulfuric acid aerosol catalyst. Environmental Science & Technology 2001;35(24):4758-4766. |
R828176 (2002) R828176 (Final) |
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Jaoui M, Leungsakul S, Kamens RM. Gas and particle products distribution from the reaction of β-caryophyllene with ozone. Journal of Atmospheric Chemistry 2003;45(3):261-287. |
R828176 (2002) R828176 (Final) |
Exit |
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Jaoui M, Kamens RM. Gas and particulate products distribution from the photooxidation of α-humulene in the presence of NOx, natural atmospheric air and sunlight. Journal of Atmospheric Chemistry 2003;46(1):29-54. |
R828176 (2002) R828176 (Final) |
Exit |
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Kamens RM, Jaoui M. Modeling aerosol formation from α-pinene + NOx in the presence of natural sunlight using gas-phase kinetics and gas-particle partitioning theory. Environmental Science & Technology 2001;35(7):1394-1405. |
R828176 (2002) R828176 (Final) R826771 (2000) R826771 (Final) |
Exit Exit Exit |
Supplemental Keywords:
secondary organic aerosols, terpenes, α-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.