Grantee Research Project Results
Final 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 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 was 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, NO, 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 originally proposed to study three compounds—-pinene, -pinene, and d-limonene—as well as conduct approximately 14 chamber experiments. Because of a reduction in the award amount (compared to the proposed amount), this approach was scaled back to 10 experiments, to allow us to focus efforts in methods development for products. A no-cost extension of the project was granted for 1 year because of the rebuilding of our outdoor smog chamber.
Summary/Accomplishments (Outputs/Outcomes):
The reactions of monoterpenes in the gas and the particle-phases have received much attention during the last decade. The rate constants for the gas-phase reactions of many monoterpenes have been summarized by Atkinson in 1997 (Atkinson, 1997). There also have been several laboratory investigations on the atmospheric oxidation of terpenes (Hakola, et al., 1994; Calogirou, et al., 1995, 1997; Berndt and Böge, 1997; Grosjean and Grosjean, 1997; Hallquist, et al., 1997; Shu, et al., 1997; Vinckier, et al., 1998; Wängberg, et al., 1997; Alvarado, et al., 1998; Atkinson, 1997; Noziere, et al., 1999; Kamens, et al., 1999; Jang and Kamens, 1999, Jaoui and Kamens, 2001a, c). Despite recent progress, however, the reaction mechanisms of monoterpenes are far from being sufficiently understood, even for the case of a-pinene and b-pinene. In addition, very few studies have addressed the pathways leading to the gas-particle conversion of terpenes (Kamens, et al., 1999; Kamens and Jaoui, 2001). -pinene, together with -pinene, d-limonene, 3-carene, 1,8-cineole, b-phellandrene, mycrene, camphene, and sabinene, account for most of the emitted terpene mass from biogenic sources in the United States of America (Lamb, et al., 1993; Guenther, et al., 1994; Geron, et al., 2000; Seufert, 1997). The biochemical mechanisms of their formation in plants are closely linked so that emissions of more than one monoterpene often occur together (Fall, 1999; Finlayson-Pitts and Pitts, 2000). 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 (Jaoui and Kamens, 2001a, b; Kamens and Jaoui, 2001), 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 (Jaoui and Kamens, 2001c). The identification of a wide range of products and their time series evolution for the oxidation of -pinene, -pinene, and d-limonene by O3 and/or OH radicals in the presence of NOx can give valuable insights into the detailed mechanism of this system (Andersson-Sköld and Simpson, 2001; Kamens, et al., 1999; Kamens and Jaoui, 2001). 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 analytical results from this project permitted the development and testing of a kinetic mechanism model (Kamens and Jaoui, 2001) that is suitable for use in regional atmospheric chemistry models (Andersson-Sköld and Simpson, 2001) and in the determination of partitioning of products between the gas and particle-phase.
Kinetics Modeling Approach
In our current kinetics model, secondary organic aerosol (SOA) formation involves the production of semivolatile organic compounds (SOCs) from the reactions of terpenes with OH, O3, and NO3. These SOCs 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 was assumed to be governed by an equilibrium between the surrounding gas and a liquid phase particle (Jang and Kamens, 1999). This is supported by previous investigations by our group (Jang, et al., 1997) showing that -pinene-O3 aerosols can be treated using an absorptive equilibrium (gas-liquid) partitioning model. The equilibrium constant, Kp, for a given product semivolatile compound is equal to the ratio of the rate constants for the forward (absorption reaction or process) kon and backward (desorption) koff reactions.
Kp = kon / koff (1)
Kp and koff can be estimated by previously described methods (Jang and Kamens, 1999; Jang, et al., 1997; Pankow, et al., 1994; Jang and Kamens, 1998; Mackay, et al., 1982; Matsumoto, et al., 1994), which then permits an estimate of kon. These are used as a guide, and they are 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 aerosols urban or rural aerosols, and these are called seed. In addition, to permit self-nucleation in the model, stabilized Criegee bi-radicals from the reaction of terpenes with O3 (called stabcrieg1 and stabcrieg2) are permitted to react with the carbonyl portion of product compounds. For the -pinene system pinonaldehyde (called pinaldin the model), oxypinonaldehydes and pinalic acid produced secondary ozonide products. The large dimer type molecules have estimated vapor pressures as low as 10-15 torr (Jang and Kamens, 1999). It also is possible to form anhydride-dimer type products from the reaction of the Criegee with dicarboxylic acids (Neeb, et al., 1995) and alkoxy hydroperoxy acids from reaction with alcohols. These dimers are called "seed1" particles and are available to "react" with gas-phase accommodated products to become particle-phase species. This is illustrated in reaction (3) below, where a gas-phase product such as pinic acid, diacidgas, reacts with seed1 to form its analog particle-phase product, diacidpart.
stabcrieg1 + pinaldgas —> seed1 | (2) |
diacidgas + seed1 —> diacidpart + seed1 | (3) |
diacidgas + seed —> diacidpart + seed | (4) |
Hence, low vapor pressure products such as gas-phase pinic acid (diacidgas) can now migrate in the model to existing particle mass, which is dynamically changing, 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 (apOHNO3gas) can migrate to the diacid particle-phase (diacidpart) and seed and seed1; kinetically for the diacidpart, this process is represented as:
OH-apNO3gas+ diacidpart —> OH-apNO3part + diacidpart rate constant = kon | (5) |
To maintain equilibrium, OH-apNO3part can back react or "off-gas" 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.
-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 using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC) for identification of -pinene in the presence of O3/air and the daytime oxidation of -pinene in the quantification of reaction products. 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 presence of NOx/air and natural sunlight were conducted in the University of North Carolina's large outdoor smog chamber (190 m3) located in Chatham County, North Carolina (see Table 1). The mass balance of reacted products versus -pinene reacted was 71 percent for the O3 dark experiment, and ranged from 57 to 6 percent for the two daytime NOx experiments (see Table 2).
Table 1. Conditions for the Outdoor 190,000-L Smog Chamber Experiments for the Oxidation of -Pinene With Ozone in the Nighttime and Daytime in the Presence of NOx
Date |
Initial -pinene (ppmV) |
Initial NO + NO2 (ppmv) |
Initial Ozone (ppmv) |
Chamber Temperature (K) |
Relative Humidity |
April 10, 2000 |
1.0 |
- |
1.0 |
285-290 |
40-50% |
May 15, 2000 |
1.9 |
0.9 |
- |
297-304 |
45-55% |
July 16, 2000 |
2.0 |
- |
1.0 |
293-295 |
49-51% |
Table 2. Maximum Molar Yields of Quantified Compounds Observed in the Gas and Aerosol Phases
Maximum Molar Yield Observed (%) |
|||||||||
Gas |
Aerosol |
Total |
|||||||
Product |
April 10, 2000 |
May 15, 2000 |
July 16, 2000 |
April 10, 2000 |
May 15, 2000 |
July 16, 2000 |
April 10, 2000 |
May 15, 2000 |
July 16, 2000 |
Nopinone | 21.2 |
15.2 |
19.8 |
6.2 |
4.1 |
6.0 |
27.4 |
19.3 |
25.8 |
Pinic acid | ND |
ND |
ND |
4.8 |
6.2 |
5.1 |
4.8 |
6.2 |
5.1 |
Pinonic acid | < 0.1 |
0.5 |
< 0.1 |
1.7 |
2.5 |
1.5 |
1.7 |
3.0 |
1.5 |
Acetone | 5.2 |
6.5 |
5.4 |
5.2 |
6.5 |
5.4 |
|||
Formaldehyde | 76.7 |
30.3 |
76.5 |
76.7 |
30.3 |
76.5 |
|||
-Pinene oxide | 0.9 |
1.0 |
0.7 |
< 0.1 |
0.1 |
< 0.1 |
0.9 |
1.1 |
0.7 |
1-Hydroxynopinone | 4.1 |
3.1 |
4.9 |
2.8 |
2.2 |
2.1 |
6.9 |
5.3 |
7.0 |
3-Hydroxynopinone | 3.5 |
2.2 |
3.2 |
2.4 |
< 0.1 |
1.8 |
5.9 |
2.2 |
5.0 |
10-Hydroxypinonic acid | < 0.1 |
0.9 |
< 0.1 |
2.8 |
3.1 |
2.5 |
2.8 |
4.0 |
2.5 |
3-Oxonopinone | 2.8 |
0.9 |
3.0 |
0.5 |
< 0.1 |
0.8 |
3.3 |
0.9 |
3.8 |
Pinalic-3-acid | 1.5 |
0.9 |
1.4 |
2.2 |
1.1 |
1.9 |
3.7 |
2.0 |
3.3 |
4-Hydroxy-3-pinalic acid | 0.8 |
1.0 |
1.2 |
0.9 |
1.2 |
2.5 |
1.7 |
2.2 |
3.7 |
3,7-Dihydroxynopinone | 1.5 |
< 0.1 |
1.8 |
1.7 |
< 0.1 |
1.5 |
3.2 |
< 0.1 |
3.3 |
Myrtanal | 1.8 |
0.9 |
1.8 |
0.4 |
0.4 |
0.5 |
2.2 |
1.3 |
2.3 |
Myrtenol | 0.8 |
Trace |
0.5 |
ND |
Trace |
ND |
0.8 |
Trace |
0.5 |
Total/molar yield, % | 120.8 |
63.4 |
120.2 |
26.4 |
20.9 |
26.2 |
147.2 |
84.3 |
146.4 |
Total/carbon yield, % | 50.9 |
44.1 |
48.2 |
19.9 |
13.1 |
18.6 |
70.8 |
57.3 |
66.8 |
ND: not detected |
-Pinene Experiments
The gas-and particle-phase products of the reaction of a-pinene with the atmospheric oxidants O3 and OH radicals in the presence of NOx were investigated at lower concentrations than have been previously investigated (Lamb, et al., 1993). Instead of permitting the self-nucleation of particles, we started with background seed aerosols in the 25-50 µg/m3 range. No nucleation of -pinene reaction products occurred in the presence of (NH4)2SO4 particles. The mean diameter of preexisting (NH4)2SO4 particles increased from 70 nm to 250 nm when all the gas-phase a-pinene was consumed. The SOA formation in the presence of (NH4)2SO4 particles can be one of the last two cases: heterogeneously mixed aerosols or homogeneously and internally mixed aerosols. It has been reported that the amount of organic compounds dissolved in (NH4)2SO4 solution particles is negligible because of the "salting-out" effect. Thus, the gas-phase products initially prefer to partition onto the surface of (NH4)2SO4 particles by adsorption. As the photo-oxidation progresses in the gas phase, secondary organic products would partition through an absorption process and coat the (NH4)2SO4 particles with the SOA layer. From the SMPS measurement, SOAs on (NH4)2SO4 particles grow enough so that multilayer organics exist. Therefore, the activity coefficients of SOA products can be reasonably estimated with a pure SOA composition. Hence, to model this system we used our existing a-pinene model (Lamb, et al., 1993) without any changes, and we used the concentration of (NH4)2SO4 as initial seed inputs.
-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 (see Table 3). 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 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 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 (see Table 4).
Table 3. Conditions During the Outdoor 190-m3 Smog Chamber Experiments for the Oxidation of -Pinene + -Pinene With NOx in the Presence of Natural Sunlight and With Ozone in the Nighttime
Date | Initial -Pinene ppmv |
Initial -Pinene ppmv |
Initial O3 ppmv |
Initial NO/NO2 ppmv |
Chamber Temperature K |
Chamber H2O ppmv |
TSP (mg m-3) (Maximum concentration) |
September 21, 2000 | 0.317 |
0.643 |
0.686 |
- |
296-303 |
11,435-12,008 |
1.043 |
September 27, 2000 | 0.091 |
0.048 |
0.2 |
- |
282-285 |
10,435-10,753 |
0.065 |
October 3, 2000 | 0.15 |
0.31 |
- |
1.03/0.003 |
296-311 |
14,676-20,043 |
0.588 |
October 11, 2000 | 0.16 |
0.096 |
- |
0.26/0.002 |
291-302 |
10,151-11,210 |
NM |
NM: not measured |
Maximum Carbon Yield Observed (%) |
||||||
Products |
Gas |
Aerosol |
Total |
|||
October 3, 2000 |
October 11, 2000 |
October 3, 2000 |
October 11, 2000 |
October 3, 2000 |
October 11, 2000 |
|
Pinonaldehyde | 17.1 |
18.1 |
2.1 |
2.7 |
19.2 |
20.2 |
Norpinonaldehyde | 1.2 |
1.8 |
0.7 |
0.9 |
1.9 |
2.7 |
-Campholenal | 0.7 |
0.9 |
0.1 |
0.1 |
0.8 |
1.0 |
Nopinone | 15.5 |
15.9 |
2.1 |
2.9 |
17.6 |
18.8 |
3-Hydroxynopinone | 1.1 |
1.3 |
0.7 |
0.9 |
1.8 |
2.2 |
1-Hydroxynopinone | 1.5 |
1.3 |
1.1 |
1.3 |
2.6 |
2.6 |
3-Oxonopinone | 0.5 |
0.7 |
< 0.1 |
< 0.1 |
0.5 |
0.7 |
3,7-Dihydroxynopinone | 0.1 |
0.2 |
0.1 |
0.1 |
0.2 |
0.3 |
2-Hydroxy-3-pinanone | 0.3 |
0.4 |
ND |
ND |
0.3 |
0.4 |
2-H--Pinane-3-one | 0.1 |
0.1 |
ND |
ND |
0.1 |
0.1 |
Myrtanal | 0.7 |
0.9 |
0.4 |
0.5 |
1.1 |
1.4 |
Pinic acid | ND |
ND |
5.6 |
6.1 |
5.6 |
6.1 |
Norpinic acid | ND |
ND |
< 0.1 |
< 0.1 |
< 0.1 |
< 0.1 |
Pinonic acid | 3.5 |
4.1 |
3.4 |
3.9 |
6.9 |
8.0 |
Norpinonic acid | 0.8 |
0.9 |
0.9 |
1.0 |
1.7 |
1.9 |
Pinalic-3-acid/Pinalic-4-acid | 1.8 |
1.9 |
1.5 |
1.7 |
3.3 |
3.6 |
10-Hydroxypinonaldehyde | < 0.1 |
< 0.1 |
1.1 |
1.0 |
1.1 |
1.0 |
1-Hydroxypinonaldehyde | 0.5 |
0.2 |
0.6 |
0.7 |
1.1 |
0.9 |
4-Oxopinonaldehyde | ND |
ND |
0.7 |
0.8 |
0.7 |
0.8 |
10-Hydroxypinonic acid | ND |
ND |
0.4 |
0.6 |
0.4 |
0.6 |
4-Oxopinonic acid | ND |
ND |
0.4 |
0.6 |
0.4 |
0.6 |
10-Oxopinonic acid | ND |
ND |
0.3 |
0.5 |
0.3 |
0.5 |
Acetone | 1.1 |
1.0 |
1.1 |
1.0 |
||
Formaldehyde | 5.3 |
4.9 |
5.3 |
4.9 |
||
Acetaldehyde | 0.3 |
0.4 |
0.3 |
0.4 |
||
Total/carbon yield (%) | 52.1 |
55 |
22.2 |
26.3 |
74.3 |
81.3 |
ND: not detected |
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. The reactions took place in a large outdoor smog chamber (190 m3). Gas chromatography-flame ionization detection was used to monitor d-limonene disappearance. The samples were extracted and analyzed 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 (i.e., 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.
Acid Catalyzed Particle-Phase Reactions
According to evidence from our laboratory, acidic surfaces on atmospheric aerosols lead to potentially multifold increases in SOA mass. Experimental observations using a multichannel flow reactor, Teflon bag batch reactors, and outdoor Teflon smog chambers strongly confirm that inorganic acids, such as sulfuric acid, catalyzed particle-phase heterogeneous reactions of atmospheric organic carbonyl species. The net result is a large increase in SOA mass and stabilized organic layers as particles age. If acid-catalyzed heterogeneous reactions of SOA products are included in current models, the predicted SOA formation will be greater, and perhaps will have a larger impact on climate-forcing effects than we now predict.
The accommodation properties of organic species on the aerosol phase (and, SOA mass) have been primarily addressed by condensation or thermodynamic gas-particle partitioning (Jang, et al., 1997; Jang and Kamens, 1999; Pankow, 1994). However, these theories do not account for heterogeneous reactions, such as acid-catalyzed carbonyl chemistry that occurs in the particle-phase. Such chemistry includes diverse acid-catalyzed reactions such as hydration, polymerization, hemiacetal/acetal formation, aldol condensation, ring opening of terpenoid carbonyls, and cross-linking in aerosol media. The key players in these reactions are atmospheric carbonyls, the water content of aerosols, inorganic acids, and possibly alcohols. For example, it is known that the equilibrium between an aldehyde and its hydrate is quickly established, and often favors the hydrate form. Carbonyls may further react with the hydroxy groups of hydrates, resulting in higher molecular weight dimers, trimers, and polymers (Barton and Ollis, 1979; Jang and Kamens, 2001). Hemiacetal formation often is unstable and exists only in equilibrium. In the presence of acids, further reaction of hemiacetals leads to acetals, which are much more stable (Carey and Sundberg, 2000).
Sources of the atmospheric acids, HNO3 and H2SO4, are ultimately associated with the burning of fossil fuels. For example, diesel combustion is a significant contributor of SO2, which results in acidic soot particles, and it is presently known that H2SO4 comprises 1.2-5.3 percent of the mass of the small (mass median diameter of approximately 40 nm) diesel particles at 40 percent engine load. The current average sulfur content in diesel fuels of the United States is capped at 500 ppm; however, further reductions to 15 ppm are being considered for as early as 2006. These acids also are scavenged with ammonia, forming ammonium sulfate and ammonium nitrate.
A rather striking attribute of the Fourier Transform Infrared Spectroscopy (FTIR) spectra of the ozone reaction products of isoprene and acrolein is that they all have absorption peaks similar to the glyoxal/acid-catalyst aerosols. These similarities are evidence that dicarbonyl products of isoprene and acrolein reactions react heterogeneously to form polymeric structures or hydrates in the particle-phase. Additionally, the FTIR spectra from size-resolved particle samples collected from the Southeastern Aerosol Visibility Study in the Smoky Mountains at Look Rock, by Blando et al. (1998) also show similar peaks at 589, 878, 1,049, and 1,182 cm-1. This spectrum suggests that the organics comprising SOAs from the Smoky Mountains natural aerosol also have similar functional group transformation as our laboratory isoprene and acrolein aerosols. We believe that these transformations are because of acid-catalyzed heterogeneous reactions, which are, therefore, a major contributor to SOA formation in natural systems.
Reaction of -Caryophyllene With Ozone
Gas- and particulate-reaction products from the ozonolysis of -caryophyllene (I) in the presence of atmospheric air were investigated using a combination of GC-MS and HPLC. An SMPS system (3936, TSI) and a Condensation Particle Counter (3025A, TSI) were used to study the SOA formation. The nighttime oxidation was conducted in a large outdoor smog chamber (190 m3). A wide range of ring-retaining and ring-opening products in the gas and particle phase are reported over the course of the reaction. On average, measured gas- and particle-phase products accounted for approximately 64 percent of the reacted -caryophyllene (I) carbon. Measurements show that a number of reaction products with low vapor pressure (e.g., -caryophyllone aldehyde, -norcaryophyllone aldehyde, -caryophyllonic acid, -14-hydroxycaryophyllonic acid) were found in the sample taken during the first 20 minutes of the reaction, and they may play an important role in the early formation of an SOA. A detailed mechanism is proposed to account for most products observed in this investigation.
Impact of This Work
Several investigators are beginning to use our SOA modeling approach both in the United States and in Europe. Some of our results also may have been included in the new PM2.5 U.S. Environmental Protection Agency Criteria Document and the Fine Particle NARSTO report of February 2003.
References:
Atkinson R. Gas-phase tropospheric chemistry of organic compounds, 1. Alkanes and alkenes. Journal of Physical Chemistry Reference Data Monograph 1997;2:1-216.
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.
Calogirou A, Kotzias D, Kettrup A. Atmospheric oxidation of linalool. Naturwissenschaften 1995;82:288-289.
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;31:172741-172751.
Berndt T, Böge O. Products and mechanism of the gas-phase reaction of NO3 radicals with -pinene. Journal of the Chemical Society, London. Faraday Transactions 2 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;27:271-289.
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 section and vapor pressures. Environmental Science and Technology 1997;31:3166-3172.
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;31:896-904.
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 -pinene. Environmental Science and Technology 1997;31:2130-2135.
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.
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;104:23645-23658.
Kamens RM, Jang M, Chien CJ, Leach K. Environmental Science and Technology 1999;33:1340-1349.
Jang M, Kamens RM. Newly characterized products and composition of secondary aerosols from reaction of -pinene with ozone. Atmospheric Environment 1999;33:459-474.
Jaoui M, Kamens RM. Mass balance of gaseous and particulate products analysis from a-pinene/NOx/air in the presence of natural sunlight. Journal of Geophysical Research: Atmospheres 2001a;106:12541-12558.
Jaoui M, Kamens RM. Mass balance of gaseous and particulate products from b-pinene/O3/air in the absence of light and -pinene/NOx/air in the presence of natural sunlight. Journal of Geophysical Research: Atmospheres (submitted, 2001).
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;35:1394-1405.
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.
Guenther A, Zimmerman P, Wildermuth M. Natural volatile organic compounds emission rate estimates for U.S. woodland landscapes. Atmospheric Environment 1994;28:1147-1210.
Geron C, Rasmusssen R, Arnts R, Guenther A. A review and synthesis of monoterpene speciation from forests in the United States. Atmospheric Environment 2000;34:1761-1781.
Seufert G. BEMA, a European Commission project on biogenic emission in the Mediterranean area. Guest, ed. Atmospheric Environment 1997;31(S1):1-256.
Fall R. Biogenic emissions of volatile organic compounds from higher plants, in reactive hydrocarbons in the atmosphere. In: Hewitt CN, ed. 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.
Andersson-Skold Y, Simpson D. Secondary organic aerosol formation in Northern Europe: a model study. Journal of Geophysical Research 2001;106:7357-7374.
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 photo-oxidation products and new particle formation over forests. Environmental Science and Technology 1999a;33:1028-1037.
Kavouras IG, Mihalopoulos N, Stephanou EG. Formation and gas/particle partitioning of monoterpenes photo-oxidation products over forests. Geophysical Research Letters 1999b;26:55-58.
Jang M, Kamens RM, Leach K, Strommen MR. A thermodynamic approach using group contrilsation methods to model the partitioning of semivolatile organic compounds on atmospheric particulate matter. Environmental Science and Technology 1997;31:2805-2811.
Pankow JF, Storey JME, Yamasaki H. Environmental Science and Technology 1994;27:2220-2226.
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;32:1237-1243.
Mackay D, Bobra A, Chan DW, Shiu WY. Environmental Science and Technology 1982;16:16645-16649.
Matsumoto M, Yasuoka K, Kataoka Y. Journal of Chemical Physics 1994;101:7904-7911.
Neeb P, Horie O, Mortgot GK. The nature of the transitory product in the gas phase ozonolysis of ethane. Chemical Physics Letter 1995;246:150-156.
Pankow JF. An absorption model of gas/particle partitioning of organic compounds in the atmosphere. Atmospheric Environment 1994;28:185-188.
Barton D, Ollis WD, ed. Comprehensive Organic Chemistry: The Synthesis and Reactions of Organic Compounds. New York: Pergamond Press, 1979:960-1013.
Jang M, Kamens RM. Atmospheric secondary aerosol formation by heterogeneous reactions of aldehydes in the presence of a sulfuric acid aerosol catalyst. Environmental Science and Technology 2001;35:4758-4766.
Carey FA, Sundberg RJ. Advanced organic chemistry: part A structure and mechanisms. New York: Plenum Press, 4th edition, 2000.
Blando JD, Porcja RJ, Li TH, Bowman D, Lioy PJ, Turpin BJ. Secondary formation and the Smoky Mountain organic aerosol: an examination of aerosol polarity and functional group composition during SEAVS. Environmental Science and Technology 1998;32:604-613.
Journal Articles on this Report : 17 Displayed | Download in RIS Format
Other project views: | All 17 publications | 17 publications in selected types | All 17 journal articles |
---|
Type | Citation | ||
---|---|---|---|
|
Chandramouli B, Jang M, Kamens RM. Gas-particle partitioning of semi-volatile organics on organic aerosols using a predictive activity coefficient model:analysis of the effects of parameter choices on model performance. Atmospheric Environment 2003;37(6):853-864. |
R828176 (Final) R826771 (2000) |
Exit Exit Exit |
|
Chandramouli B, Jang M, Kamens RM. Gas-particle partitioning of semivolatile organic compounds (SOCs) on mixtures of aerosols in a smog chamber. Environmental Science & Technology 2003;37(18):4113-4121. |
R828176 (Final) R826771 (Final) |
Exit Exit Exit |
|
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) |
Exit Exit Exit |
|
Jang M, Carroll B, Chandramouli B, Kamens RM. Particle growth by acid-catalyzed heterogeneous reactions of organic carbonyls on preexisting aerosols. Environmental Science & Technology 2003;37(17):3828-3837. |
R828176 (Final) |
Exit Exit Exit |
|
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) |
Exit Exit Exit |
|
Jang M, Czoschke NM, Lee S, Kamens RM. Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions. Science 2002;298(5594):814-817. |
R828176 (Final) |
Exit Exit Exit |
|
Jang M, Lee S, Kamens RM. Organic aerosol growth by acid-catalyzed heterogeneous reactions of octanal in a flow reactor. Atmospheric Environment 2003;37(15):2125-2138. |
R828176 (Final) |
Exit Exit Exit |
|
Jang M, Czoschke NM, Northcross AL. Atmospheric organic aerosol production by heterogeneous acid-catalyzed reactions. ChemPhysChem 2004;5(11):1647-1661. |
R828176 (Final) |
Exit |
|
Jaoui M, Kamens RM. Gas phase photolysis of pinonaldehyde in the presence of sunlight. Atmospheric Environment 2003;37(13):1835-1851. |
R828176 (Final) R826771 (1999) R826771 (Final) |
Exit Exit Exit |
|
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 |
|
Jaoui M, Kamens RM. Mass balance of gaseous and particulate products from β-pinene/O3/air in the absence of light and β-pinene/NOx/air in the presence of natural sunlight. Journal of Atmospheric Chemistry 2003;45(2):101-141. |
R828176 (Final) |
Exit |
|
Jaoui M, Kamens RM. Gaseous and particulate oxidation products analysis of a mixture of α-pinene + beta-pinene/O3/air in the absence of light and α-pinene + β-pinene/NOx/air in the presence of natural sunlight. Journal of Atmospheric Chemistry 2003;44(3):259-297. |
R828176 (Final) |
Exit |
|
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 |
|
Jaoui M, Sexton KG, Kamens RM. Reaction of α-cedrene with ozone: mechanism, gas and particulate products distribution. Atmospheric Environment 2004;38(17):2709-2725. |
R828176 (Final) R826771 (Final) |
Exit Exit Exit |
|
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 |
|
Leungsakul S, Jaoui M, Kamens RM. Kinetic mechanism for predicting secondary organic aerosol formation from the reaction of d-limonene with ozone. Environmental Science & Technology 2005;39(24):9583-9594. |
R828176 (Final) R831084 (2007) |
Exit Exit Exit |
|
Leungsakul S, Jeffries HE, Kamens RM. A kinetic mechanism for predicting secondary aerosol formation from the reactions of d-limonene in the presence of oxides of nitrogen and natural sunlight. Atmospheric Environment 2005;39(37):7063-7082. |
R828176 (Final) R831084 (2005) R831084 (2006) R831084 (2007) R831084 (Final) |
Exit Exit Exit |
Supplemental Keywords:
secondary organic aerosols, terpenes, a-pinene, α-pinene, δ-limonene, gas-particle partitioning, terpene products, mass balance, biogenic aerosols, kinetic model,, 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.