Final Report: MIT Center for Airborne Organics

EPA Grant Number: R824970
Center: EERC - Center for Airborne Organics (MIT)
Center Director: Seinfeld, John
Title: MIT Center for Airborne Organics
Investigators: Howard, Jack B. , Molina, Mario J. , Pfeffer, Robert , Seinfeld, John
Institution: Massachusetts Institute of Technology
EPA Project Officer: Shapiro, Paul
Project Period: October 1, 1992 through September 30, 2002
Project Amount: $5,745,000
RFA: Center on Airborne Organics (1993) Recipients Lists
Research Category: Air Quality and Air Toxics , Targeted Research

Objective:

The Center on Airborne Organics had three objectives: (1) to provide new tools for characterizing the generation, fate and transport, source attribution, and control of combustion generated organic pollutants; (2) to become an entity greater than the sum of its parts, by fostering cross-fertilization between the various investigators; and (3) to provide neutral forums for discussions on the scientific basis for some of the more contentious issues facing policymakers. The Center was founded and operated at the Massachusetts Institute of Technology (MIT), the California Institute of Technology (CIT), and the New Jersey Institute of Technology (NJIT), with support from the U.S. Environmental Protection Agency (EPA). The Center's Scientific Advisory Committee (SAC) guided the Center's focus in three principal areas: (1) sources and control; (2) transport and transformation; and (3) monitoring and source attribution.

Summary/Accomplishments (Outputs/Outcomes):

The Center's research and outreach has contributed to a better understanding of airborne organics in the three research areas.

Sources and Control

Research on source and control concentrated in three subsets: combustion sources, kinetics and mechanisms of formation, and methods for controlling emissions.

Combustion Sources. The goal of combustion sources research was to develop models and experimental data sets for the formation of particulate matter (PM) in combustion engines. Combustion sources are major precursors to ozone, air toxics, and visibility degradation. The combustion sources research had both experimental and modeling components. Experimental research subjected combustion engines to typical loads, and analyzed the resulting hydrocarbon emissions and formation of PM. Modeling research combined chemical kinetic and fluid mechanic models to predict combustion products. Professor Heywood and Hochgreb (MIT) developed a model for combustion chamber deposit effects on hydrocarbon emissions. Professor Hochgreb also developed a model that explains the products of incomplete combustion in spark-ignited engines. Further more, Professor Hochgreb and Lafleur (MIT) developed a database and model to characterize PM formation in spark-ignited engines.

Kinetics and Mechanisms of Formation of Airborne Organics. The goal of research in kinetics and mechanisms of formation was to provide quantitative predictions of airborne organics behavior. Understanding the kinetics and mechanisms of formation of airborne organics can lead to methods for manipulating the chemistry to minimize production, as well as provide a better assessment of chemical signature for use in source apportionment. Again, research in this area had experimental and modeling components. Experiments focused on the formation of hydrocarbons and soot. Models used elementary reactions to describe the chemistry. In the area of polycyclic aromatic hydrocarbon (PAH) mechanisms, Professor Green (MIT) developed a method for the computer generation of detailed kinetic models, which he is applying to PAH formation. Professor Howard (MIT) developed a model that predicts PAH concentrations and the contribution of PAH to soot formation in flames. In the area of computational kinetic modeling, Professors Barton and Green (MIT) developed new methods for the numerical analysis of large-scale kinetic models. In the area of soot formation, Professor Béer (MIT) determined pathways leading to soot mass growth in stationary combustion systems, and Professor Howard (MIT) developed a model to characterize fine soot particles in combustion. Professors Barton and Howard (MIT) extended this research in PAH and soot formation to premixed flames with axial diffusion. In the area of PM formation, Professor Cheng (MIT) developed a set of kinetics data for future use in kinetics modeling.

Methods for Controlling Emissions. The Center's goal was to develop methods for controlling emissions. This would allow for the control of problematic pollutants from stationary and mobile engines. Research at the Center in this area included the simultaneous removal of soot and NOx from diesel engines. Experimental and modeling efforts concentrated on catalyst research and the mechanism and competitive kinetics of soot reactions with oxidants. Professors Shaw and Pfeffer (NJIT) showed that it may be possible to lower NOx emissions from diesel vehicles by promoting chemical reactions between the NOx and carbon monoxide emitted by the engine.

Transport and Transformation

Research in transport and transformation concentrated in four subsets: formation of PM, improving the predictive capability of air quality models, reactions of primary and secondary oxidation products and their impact on ozone, and reactions of peroxides.

Formation of Particulate Matter. The goal of PM formation research was to characterize the photo-oxidation mechanisms of volatile organic compounds forming atmospheric aerosols. Such research would allow for the development of predictive models for ozone and smog formation. Models were developed to predict the kinetics of aerosol particle growth. Experiments observing the kinetic profiles were then conducted to validate the models. In addition, photochemical smog chambers were used to determine the yields and chemical composition of the aerosol particles formed. Professors Seinfeld and Flagan (Caltech) developed models and comprehensive data sets on the gas-to-particle conversion of volatile organic compounds in the atmosphere. In addition, Professor Krasnoperov (NJIT) developed a new method for characterizing the very initial stages of aerosol particle formation.

Improving the Predictive Capability of Air Quality Models. The goal of this research area was to construct new mathematical and computational frameworks describing the transport and transformation of airborne organics, building on past approaches and experimental data sets. By improving the predictive capability of air quality models, one can better describe the complex reaction schemes characterizing the photochemistry of airborne organics. Novel data analysis and modeling techniques were developed. Professor McRae (MIT) showed that the predictive capability of airshed models can be diminished by uncertainties in critical input parameters. Professor Cass (Caltech) developed a new air quality model predicting the evolution of single particles in the atmosphere.

Reactions of Primary and Secondary Oxidation Products and their Impact on Ozone. The goal of research into oxidation products was to quantitatively characterize the intermediates of such reactions and develop kinetic models. The atmospheric oxidation of aromatic compounds plays a crucial role in the generation of pollutants in the atmosphere. Characterizing the oxidation products is necessary for the development of predictive models of ozone and smog formation. Modeling proceeded by developing reaction mechanisms from elementary kinetic parameters and determining thermodynamic properties via literature evaluation or calculation. Experimental approaches either applied sensitive ultraviolet spectroscopy, or chemical ionization mass spectroscopy via a steady state turbulent flow reactor. Professors Bozzelli and Lay (NJIT) developed reaction mechanisms and kinetic understanding of the atmospheric photochemical oxidation of certain aromatic and oxygenated aromatic compounds. Professor Krasnoperov (NJIT) developed kinetic and thermochemistry methods to characterize the oxidation of airborne organic compounds. Professor Molina (MIT) identified intermediates in the atmospheric oxidation of aromatic hydrocarbons.

Reactions of Peroxides. The goal of peroxide research was to characterize the photochemistry of organic peroxides. Hydrogen peroxide and other organic peroxides are important trace constituents in the atmosphere. They are the dominant oxidants of SO2 found in clouds, fog, or rain in the atmosphere, and may contribute to forest damage due to their phytotoxic properties. Research evaluated the importance of photochemical destruction of organic peroxides with photolysis and assessing ultraviolet absorption cross sections. Professor Wennberg (Caltech) measured the absorption cross section and photodissociation quantum yield (action spectra) of hydrogen peroxide and other organic peroxides.

Monitoring and Source Attribution

Research in monitoring and source attribution concentrated in three subsets: application of methodologies, development and application of new measurement methods and analytical techniques, and identifying and measuring new classes of compounds that serve as tracers for specific source types.

Application of Methodologies. The goal of this area of research was to provide quantifiable data on the transformation of atmospheric particles for testing future air quality models. Such research can further the understanding of source/receptor relationships for atmospheric organic compounds. We collected source and ambient fine PM and made comparisons on the basis of chemical composition and mutagenicity by experimental techniques, including high performance liquid chromatography (HPLC) and gas chromatography/mass spectroscopy (GCMS). Professor Cass (Caltech) conducted field experiments that measured changes in the chemical composition of atmospheric aerosols in Southern California.

Development and Application of New Measurement Methods and Analytical Techniques. The goal of measurement methods research was to develop new types of equipment to measure airborne contaminants. This research can assist scientists in extending monitoring and source attribution to new classes of organic compounds, identifying potential public health hazards, and assisting policymakers with a firmer analytical ground for their decisions. The research included fabrication of new sensors and sampling systems, performance evaluation, and sensitivity analysis. Several new measurement methods and techniques were developed at the Center. Professors Carr and Farmer (Caltech) developed a mass spectrometer to measure airborne contaminants, Professors Kebbekus and Zaitsev (NJIT, Moscow State) developed a sensor to measure organic vapors, Professors Mitra and Kebbekus (NJIT) designed novel sampling and analytical techniques for polar atmospheric volatile organic compounds, and Professors Mitra and Misra (NJIT) developed a microconcentrator interface for real-time volatile organic compound sensors.

Identifying and Measuring Classes of Compounds that Serve as Tracers for Specific Source Types. The goal of this research area was to develop quantitative methods for the source attribution of organic compounds. This would allow for a reliable means of identifying and measuring the true sources of airborne contaminants, and assist policymakers in designing effective strategies against the principal sources. The research included experimental determination of soot microstructure with respect to varying conditions, and the development of methods for measuring soot microstructure and composition. Professors Sarofim and Vander Sande (MIT) introduced a potentially quantitative method to fingerprint sources of airborne soot and began the development of a library of soot structures for use in future emissions source attribution studies.

Outreach and Policymaking Impact of Center Research

Outreach Through Summer Symposia. The Center held annual summer symposia on topics of large current interest to the airborne organics community in general, and especially to the policymakers of this community. The goal of the symposia was to bring together many of the key researchers and policymakers to focus on key topics of current interest at the interface of technology and policy in the field of airborne organics. The symposia provided opportunities for informal and sometimes spirited discussions between the participants in informal surroundings. The symposia, held at Endicott House, were well attended by federal, state, and local regulators, representatives from industrial and other nongovernmental organizations, and members of the academic research community. The symposia were very successful in providing neutral forums for discussions of the scientific bases for some of the more contentious issues being faced by policymakers.

Policy Making Regarding EPA Research and Monitoring of Particulate Emissions. The work of Glen Cass (deceased) at Caltech has made a significant impact on policymaking regarding EPA research and monitoring of particulate emissions. The Center-sponsored work in which Glen Cass and students at Caltech measured and then modeled fine particle formation (fate and transport) in the Los Angeles area has been the basis for control strategy planning and design for fine particles of different types (sulfates and nitrates, primary and secondary organics, etc.). The importance of this work and its increasing significance are reflected in current national and international trends in PM policy decisionmaking. His measurement work on ambient PM2.5 (by speciation, elemental carbon, organic carbon, nitrates, sulfates, crustal material, trace elements, etc.) was the major reason that the EPA chose to pursue work beyond the measurement of only mass for PM. For this work, the EPA has established a speciation network specializing in the complete chemistry of fine particles. This can be considered a major example of the use of sound science into policy formulation.

Policy Focus on the Coupling of Atmospheric Pollutants. The work of Gregory McRae at MIT initiated a policy focus on the coupling of atmospheric pollutants. Gregory McRae's Center-funded project entitled, "Direct Treatment of Uncertainties in Mathematical Models of the Transport and Fate of Airborne Organics," was strongly technical, but highly significant to policy. One of the consequences of using models to describe the formation and transport of the photochemical air pollution is that approximations are involved. The goal of this research was to identify the inputs that contribute most to the uncertainty in predictions. A new approach was developed and termed the Deterministically Equivalent Modeling Method (DEMM). Uncertain parameters were treated as random variables that, in turn, were approximated using orthogonal basis function expansions in the probability space. The project had two major accomplishments:

· The predictions from three different mechanisms were indistinguishable, given current levels of parametric uncertainties.

· Because the chemical mechanisms investigated as well as the three-dimensional Caltech airshed model are sensitive to the same set of parameters, reducing parametric uncertainties should be a key research priority for model improvement purposes.

This work provided the centerpiece for discussions of "Advanced Instrumentation for Air Quality Measurements" at the 1996 Summer Symposium and "Cost and Benefits Estimation in Air Quality Regulations" at the 1998 Summer Symposium. At these Symposia, which were organized by the Center to provide a neutral setting for discussion of policy issues and pertinent research results, McRae demonstrated that improved estimations of emissions are necessary for an accurate cost-benefit analysis. In 1999, the topic was EPA's Urban Air Toxics Strategy, where McRae's research showed that a quantitative approach to uncertainty and variability is needed when conducting risk assessment. One of the key points in EPA's Urban Air Toxics Strategy is the risk management of air toxics.


Journal Articles: 89 Displayed | Download in RIS Format

Other center views: All 125 publications 92 publications in selected types All 89 journal articles
Type Citation Sub Project Document Sources
Journal Article Allen JO, Fergenson DP, Gard EE, Hughes LS, Morrical BD, Kleeman MJ, Gross DS, Galli ME, Prather KA, Cass GR. Particle detection efficiencies of aerosol time of flight mass spectrometers under ambient sampling conditions. Environmental Science & Technology 2000;34(1):211-217. R824970 (Final)
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  • Journal Article Andino JM, Smith JN, Flagan RC, Goddard WA, Seinfeld JH. Mechanism of atmospheric photooxidation of aromatics: a theoretical study. Journal of Physical Chemistry 1996; 100(26):10967-10980. R824970 (Final)
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  • Journal Article Bhattacharjee B, Schwer DA, Barton PI, Green Jr. WH. Optimally-reduced kinetic models: reaction elimination in large-scale kinetic mechanisms. Combustion and Flame 2003;135(3):191-208. R824970 (Final)
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  • Journal Article Bowman FM, Odum JR, Seinfeld JH, Pandis SN. Mathematical model for gas-particle partitioning of secondary organic aerosols. Atmospheric Environment 1997;31(23):3921-3931. R824970 (Final)
    R823514 (Final)
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  • Journal Article Bozzelli JW, Dean AM. Hydrocarbon radical reactions with oxygen: comparison of allyl, formyl, and vinyl to ethyl. Journal of Physical Chemistry 1993; 97(17):4427-4441. R824970 (Final)
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  • Journal Article Bozzelli JW, Sheng C. Thermochemistry, reaction paths, and kinetics on the hydroperoxy-ethyl radical reaction with O2: new chain branching reactions in hydrocarbon oxidation. Journal of Physical Chemistry A 2002;106(7):1113-1121. R824970 (Final)
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  • Journal Article Bozzelli JW, Chang AY, Dean AM. Molecular density of states from estimated vapor phase heat capacities. International Journal of Chemical Kinetics 1997; 29(3):161-170. R824970 (Final)
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  • Journal Article Chen C-J, Bozzelli JW. Kinetic analysis for HO2 addition to ethylene, propene, and isobutene, and thermochemical parameters of alkyl hydroperoxides and hydroperoxide alkyl radicals. Journal of Physical Chemistry A 2000; 104(21):4997-5012. R824970 (Final)
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  • Journal Article Chen C-J, Wong D, Bozzelli JW. Standard chemical thermodynamic properties of multichloro alkanes and alkenes:a modified group additivity scheme. Journal of Physical Chemistry 1998; 102(24):4551-4558. R824970 (Final)
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  • Journal Article Chen C-J, Bozzelli JW. Analysis of tertiary butyl radical + O2, isobutene + HO2, isobutene + OH, and isobutene-OH adducts + O2: a detailed tertiary butyl oxidation mechanism. Journal of Physical Chemistry A 1999; 103(48):9731-9769. R824970 (Final)
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  • Journal Article Chen C-J Bozzelli JW. Thermochemical property, pathway and kinetic analysis on the reactions of allylic isobutenyl radical with O2:an elementary reaction mechanism for isobutene oxidation. Journal of Physical Chemistry A 2000; 104(43):9715-9732. R824970 (Final)
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  • Journal Article Chesnokov EN, Krasnoperov LN. Complete thermodynamically consistent kinetic model of particle nucleation and growth:numerical study of the applicability of the classical theory of homogeneous nucleation. Journal of Chemical Physics 2007;126(14):144504. R824970 (Final)
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  • Journal Article Christoforou CS, Salmon LG, Hannigan MP, Solomon PA, Cass GR. Trends in fine particle concentration and chemical composition in Southern California. Journal of the Air & Waste Management Association 2000;50(1):43-53. R824970 (Final)
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  • Journal Article DiNaro JL, Howard JB, Green WH, Tester JW, Bozzelli JW. Elementary reaction mechanism for benzene oxidation in supercritical water. Journal of Physical Chemistry A 2000;104(45):10576-10586. R824970 (Final)
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  • Journal Article Forstner HJL, Flagan RC, Seinfeld JH. Molecular speciation of secondary organic aerosol from photooxidation of the higher alkenes:1-octene and 1-decene. Atmospheric Environment 1997;31(13):1953-1964. R824970 (Final)
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  • Journal Article Forstner HJL, Flagan RC, Seinfeld JH. Secondary organic aerosol from the photooxidation of aromatic hydrocarbons: molecular composition. Environmental Science & Technology 1997;31(5):1345-1358. R824970 (Final)
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  • Journal Article Gard EE, Kleeman MJ, Gross DS, Hughes LS, Allen JO, Morrical BD, Fergenson DP, Dienes T, Galli ME, Johnson RJ, Cass GR, Prather KA. Direct observation of heterogeneous chemistry in the atmosphere. Science 1998;279(5354):1184-1187. R824970 (Final)
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  • Journal Article Glarborg P, Kubel D, Dam-Johansen K, Chiang H-M, Bozzelli JW. Impact of SO2 and NO on CO oxidation under post-flame conditions. International Journal of Chemical Kinetics 1996;28(10):773-790. R824970 (Final)
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  • Journal Article Green WH, Barton PI, Bhattacharjee B, Matheu DM, Schwer DA, Song J, Sumathi R, Carstensen H-H, Dean AM, Grenda JM. Computer construction of detailed chemical kinetic models for gas-phase reactors. Industrial & Engineering Chemistry Research 2001;40(23):5362-5370. R824970 (Final)
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  • Journal Article Griffin RJ, Cocker III DR, Flagan RC, Seinfeld JH. Organic aerosol formation from the oxidation of biogenic hydrocarbons. Journal of Geophysical Research 1999;104(D3):3555-3567. R824970 (Final)
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  • Journal Article Griffin RJ, Dabdub D, Cocker III DR, Seinfeld JH. Estimate of global atmospheric organic aerosol from oxidation of biogenic hydrocarbons. Geophysical Research Letters 1999;26(17):2721-2724. R824970 (Final)
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  • Journal Article Grosjean E, Grosjean D, Seinfeld JH. Atmospheric chemistry of 1-octene, 1-decene, and cyclohexene: gas-phase carbonyl and peroxyacyl nitrate products. Environmental Science & Technology 1996;30(3):1038-1047. R824970 (Final)
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  • Journal Article Grosjean E, Grosjean D, Seinfeld JH. Gas-phase reaction of ozone with trans-2-hexenal, trans-2-hexenyl acetate, ethylvinyl ketone, and 6-methyl-5-hepten-2-one. International Journal of Chemical Kinetics 1996; 28(5):373-382. R824970 (Final)
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  • Journal Article Hannigan MP, Cass GR, Lafleur AL, Longwell JP, Thilly WG. Bacterial mutagenicity of urban organic aerosol sources in comparison to atmospheric samples. Environmental Science & Technology 1994;28(12):2014-2024. R824970 (Final)
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  • Journal Article Hannigan MP, Cass GR, Lafleur AL, Busby Jr WF, Thilly WG. Seasonal and spatial variation of the bacterial mutagenicity of fine organic aerosol in Southern California. Environmental Health Perspectives 1996;104(4):428-436. R824970 (Final)
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  • Journal Article Hoffmann,T, Odum JR, Bowman F, Collins D, Klockow D, Flagan RC, Seinfeld JH. Formation of organic aerosols from the oxidation of biogenic hydrocarbons. Journal of Atmospheric Chemistry 1997;26(2):189-222. R824970 (Final)
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  • Journal Article Hughes LS, Allen JO, Kleeman MJ, Johnson RJ, Cass GR. Size and composition distribution of atmospheric particles in Southern California. Environmental Science & Technology 1999; 33(20):3506-3515. R824970 (Final)
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  • Journal Article Hughes LS, Allen JO, Bhave P, Kleeman MJ, Cass GR, Liu D-Y, Fergenson DP, Morrical BD, Prather KA. Evolution of atmospheric particles along trajectories crossing the Los Angeles basin. Environmental Science & Technology 2000;34(15):3058-3068. R824970 (Final)
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  • Journal Article Jung D, Chen C-J, Bozzelli JW. Structures, rotation barrier, and thermodynamic properties ΔHf°298, S°298, and Cp(T) of chloromethyl hypochlorites CH3OCl, CH2ClOCl, CHCl2OCl, and CCl3OCl. Journal of Physical Chemistry A 2000;104(42):9581-9590. R824970 (Final)
    R826371 (Final)
    R826371C009 (Final)
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  • Journal Article Jungkamp TPW, Seinfeld JH. The mechanism of methoxy radical oxidation: hydrogen abstraction versus trioxy radical formation. Journal of Chemical Physics 1996;263(3-4):371-378. R824970 (Final)
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  • Journal Article Jungkamp TPW, Seinfeld JH. The enthalpy of formation of trioxy radicals ROOO (R=H, CH3, C2H5). An ad initio study. Chemical Physics Letters 1996;257(1-2):15-22. R824970 (Final)
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  • Journal Article Jungkamp TPW, Seinfeld JH. Prediction of bond dissociation energies and transition state barriers by a modified complete basis set model chemistry. Journal of Physical Chemistry 1997;107(5):1513-1521. R824970 (Final)
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  • Journal Article Jungkamp TPW, Smith JN, Seinfeld JH. Atmospheric oxidation mechanism of n-butane:the fate of alkoxy radicals. Journal of Physical Chemistry 1997;101(24):4392-4401. R824970 (Final)
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  • Journal Article Kronholm DF, Howard JB. Analysis of soot surface growth pathways using published plug-flow reactor data with new particle size distribution measurements and published premixed flame data. Proceedings of the Combustion Institute 2000;28(2):2555-2561. R824970 (Final)
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  • Journal Article Lay TH, Bozzelli JW, Dean AM, Ritter ER. Hydrogen-atom bond increments for calculation of thermodynamic properties of hydrocarbon radical species. Journal of Physical Chemistry 1995;99(39):14514-14527. R824970 (Final)
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  • Journal Article Lay TH, Bozzelli JW, Seinfeld JH. Atmospheric photochemical oxidation of benzene:benzene plus OH and the benzene-OH adduct (hydroxyl-2,4-cyclohexadienyl) + O2. Journal of Physical Chemistry 1996;100(16):6543-6554. R824970 (Final)
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  • Journal Article Lay TH. Krasnoperov LN, Venanzi CA, Bozzelli JW, Shokhirev NV. Ab initio study of alpha-chlorinated ethyl hydroperoxides CH3CH2OOH, CH3CHClOOH, and CH3CCl2OOH: conformational analysis, internal rotation barriers, vibrational frequencies, and thermodynamic properties. Journal of Physical Chemistry 1996;100(20):8240-8249. R824970 (Final)
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  • Journal Article Lay TH, Bozzelli JW. Enthalpies of formation of cyclic alkyl peroxides: dioxane, 1,2-dioxetane, 1,2-dioxolane, and 1,2-dioxane. Chemical Physics Letters 1997;268(1-2):175-179. R824970 (Final)
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  • Journal Article Lay TH; Bozzelli JW. Enthalpies of formation and group additivity of alkyl peroxides and trioxides. Journal of Physical Chemistry A 1997;101(49):9505-9510. R824970 (Final)
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  • Journal Article Lay TH, Tsai P-L, Yamada T, Bozzelli JW. Thermodynamic parameters and group additivity ring corrections for three-to-six-membered oxygen heterocyclic hydrocarbons. Journal of Physical Chemistry A 1997;101(13):2471-2477. R824970 (Final)
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  • Journal Article Liang C, Pankow JF, Odum JR, Seinfeld JH. Gas/particle partitioning of semivolatile organic compounds to model inorganic, organic, and ambient smog aerosols. Environmental Science & Technology 1997;31(11):3086-3092. R824970 (Final)
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  • Journal Article Matheu DM, Green Jr. WH, Grenda JM. Capturing pressure-dependence in automated mechanism generation: reactions through cycloalkyl intermediates. International Journal of Chemical Kinetics 2003;35(3):95-119. R824970 (Final)
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  • Journal Article Meng Z, Dabdub D, Seinfeld JH. Chemical coupling between atmospheric ozone and particulate matter. Science 1997;277(5322):116-119. R824970 (Final)
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  • Journal Article Mitra S, Li WF, Kebbekus B. Evaluation of a thermionic ionization detector for selective detection of oxygenated volatile organic compounds. Journal of Chromatographic Science 1995;33(7):405-409. R824970 (Final)
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  • Journal Article Mitra S, Lai A. A sequential valve-microtrap injection system for continuous, online gas-chromatographic analysis at trace levels. Journal of Chromatographic Science 1995;33(6):285-289. R824970 (Final)
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  • Journal Article Molina MJ, Zhang R, Broekhuizen K, Lei W, Navarro R, Molina LT. Experimental study of intermediates from OH-initiated reactions of toluene. Journal of the American Chemical Society 1999;121(43):10225-10226. R824970 (Final)
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  • Journal Article Odum JR, Hoffman, Thorsten, Bownman F, Collins D, Flagan RC, Seinfeld JH. Gas/particle partitioning and secondary organic aerosol yields. Environmental Science & Technology 1996;30(8):2580-2585. R824970 (Final)
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  • Journal Article Odum JR, Jungkamp TPW, Griffin RJ, Flagan RC, Seinfeld JH. The atmospheric aerosol-forming potential of whole gasoline vapor. Science 1997;276(5309):96-99. R824970 (Final)
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  • Journal Article Odum JR, Jungkamp TPW, Griffin RJ, Forstner HJL, Flagan RC, Seinfeld JH. Aromatics, reformulated gasoline, and atmospheric organic aerosol formation. Environmental Science & Technology 1997;31(7):1890-1897. R824970 (Final)
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  • Journal Article Palotas AB, Rainey LC, Feldermann CJ, Sarofim AF, Vander Sande JB. Soot morphology: an application of image analysis in high-resolution transmission electron microscopy. Microscopy Research and Technique 1996;33(3):266-278. R824970 (Final)
  • Abstract from PubMed
  • Abstract: Wiley-Abstract
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  • Journal Article Palotas AB, Rainey LC, Sarofim AF, Vander Sande JB, Ciambelli P. Effect of oxidation on the microstructure of carbon blacks. Energy & Fuels 1996;10(1):254-259. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Journal Article Palotas AB, Rainey LC, Sarofim AF, Vander Sande JB, Flagan RC. Where Did That Soot Come From?. Chemtech 1998; 28(7): 24-30. R824970 (Final)
    not available
    Journal Article Park B-I, Bozzelli JW, Booty MR, Bernhard MJ, Mesuere K, Pettigrew CA, Shi J-C, Simonich SL. Polymer pyrolysis and oxidation studies in a continuous feed and flow reactor: cellulose and polystyrene. Environmental Science & Technology 1999;33(15):2584-2592. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Journal Article Pope CJ, Howard JB. Simultaneous particle and molecule modeling (SPAMM): an approach for combining sectional aerosol equations and elementary gas-phase reactions. Aerosol Science and Technology 1997;27(1):73-94. R824970 (Final)
  • Full-text: Taylor and Francis-Full Text PDF
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  • Abstract: Taylor and Francis-Abstract
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  • Journal Article Procaccini C, Bozzelli JW, Longwell JP, Smith KA, Sarofim AF. Presence of chlorine radicals and formation of molecular chlorine in the post-flame region of chlorocarbon combustion. Environmental Science & Technology 2000;34(21):4565-4570. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Journal Article Qian G-H, Bagyi I, Pfeffer R, Shaw H, Stevens JG. A parametric study of a horizontal rotating fluidized bed using slotted and sintered metal cylindrical gas distributors. Powder Technology 1998;100(2-3):190-199. R824970 (Final)
  • Abstract: ScienceDirect-Abstract
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  • Journal Article Qian G-H, Bagyi I, Pfeffer R, Shaw H, Stevens JG. Particle mixing in rotating fluidized beds: inferences about the fluidized state. AIChE Journal 1999;45(7):1401-1410. R824970 (Final)
  • Abstract: Wiley-Abstract
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  • Journal Article Rainey L, Palotas A, Bolsaitis P, Vander Sande JB, Sarofim AF. Application of high resolution electron microscopy for the characterization and source assignment of diesel particulates. Applied Occupational and Environmental Hygiene 1996;11(7):777-781. R824970 (Final)
  • Abstract: Taylor and Francis-Abstract
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  • Journal Article Richter H, Howard JB. Formation of polycyclic aromatic hydrocarbons and their growth to soot--a review of chemical reaction pathways. Progress in Energy and Combustion Science 2000;26(4-6):565-608. R824970 (Final)
  • Full-text: University of Southern California-Full Text PDF
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  • Abstract: ScienceDirect-Abstract
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  • Journal Article Richter H, Mazyar OA, Sumathi R, Green WH, Howard JB, Bozzelli JW. Detailed kinetic study of the growth of small polycyclic aromatic hydrocarbons 1. 1-naphthyl + ethyne. Journal of Physical Chemistry A 2001;105(9):1561-1573. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Journal Article Roehl CM, Marka Z, Fry JL, Wennberg PO. Near-UV photolysis cross sections of CH3OOH and HOCH2OOH determined via action spectroscopy. Atmospheric Chemistry and Physics 2007;7(3):713-720. R824970 (Final)
  • Full-text: ACP-Full Text PDF
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  • Abstract: ACP-Abstract
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  • Journal Article Schwer DA, Tolsma JE, Green Jr. WH, Barton PI. On upgrading the numerics in combustion chemistry codes. Combustion and Flame 2002;128(3):270-291. R824970 (Final)
  • Full-text: ScienceDirect-Full Text HTML
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  • Abstract: ScienceDirect-Abstract
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  • Journal Article Sheng C, Bozzelli JW. ab initio molecular orbital and density functional analysis of acetylene + O2 reactions with CHEMKIN evaluation. International Journal of Chemical Kinetics 2000;32(10):623-641. R824970 (Final)
  • Abstract: Wiley-Abstract
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  • Journal Article Sumathi R, Carstensen H-H, Green WH. Reaction rate prediction via group additivity Part 1: H abstraction from alkanes by H and CH3. Journal of Physical Chemistry A 2001;105(28):6910-6925. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Sumathi R, Carstensen H-H, Green WH. Reaction rate prediction via group additivity, Part 2: H-abstraction from alkenes, alkynes, alcohols, aldehydes, and acids by H atoms. Journal of Physical Chemistry A 2001;105(39):8969-8984. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Sumathi R, Carstensen H-H, Green WH. Reaction rate predictions via group additivity. Part 3: Effect of substituents with CH2 as the mediator. Journal of Physical Chemistry A 2002;106(22):5474-5489. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Sumathi R, Green Jr. WH. A priori rate constants for kinetic modeling. Theoretical Chemistry Accounts 2002;108(4):187-213. R824970 (Final)
  • Abstract: Springer-Abstract
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  • Journal Article Sumathi R, Green Jr. WH. Oxygenate, oxyalkyl and alkoxycarbonyl thermochemistry and rates for hydrogen abstraction from oxygenates. Physical Chemistry Chemical Physics 2003;5(16):3402-3417. R824970 (Final)
  • Abstract: RSC-Abstract
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  • Journal Article Sun H, Chen C-J, Bozzelli JW. Structures, intramolecular rotation barriers, and thermodynamic properties (enthalpies, entropies and heat capacities) of chlorinated methyl hydroperoxides (CH2ClOOH, CHCl2OOH, and CCl3OOH). Journal of Physical Chemistry A 2000;104(35):8270-8282. R824970 (Final)
    R826371C009 (Final)
  • Full-text: ACS-Full Text HTML
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  • Journal Article Thomson MJ, Lucas D, Koshland CP, Sawyer RF, Wu Y-P, Bozzelli JW. An experimental and numerical study of the high-temperature oxidation of 1,1,1-C2H3Cl3. Combustion and Flame 1994;98(1-2):155-169. R824970 (Final)
  • Abstract: ScienceDirect-Abstract
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  • Journal Article Tolsma JE, Barton PI. DAEPACK: an open modeling environment for legacy models. Industrial Engineering & Chemical Research 2000;39(6):1826-1839. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Tolsma JE, Clabaugh JA, Barton PI. Symbolic incorporation of external procedures into process modeling environments. Industrial Engineering & Chemical Research 2002;41(16):3867-3876. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Tolsma JE, Barton PI. Hidden discontinuities and parametric sensitivity calculations. SIAM Journal on Scientific Computing 2002;23(6):1861-1874. R824970 (Final)
  • Abstract: SIAM-Abstract
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  • Journal Article Tse CW, Flagan RC, Seinfeld JH. Rate constants for the gas-phase reaction of the hydroxyl radical with a series of dimethylbenzaldehydes and trimethylphenols at atmospheric pressure. International Journal of Chemical Kinetics 1997;29(7):523-525. R824970 (Final)
  • Abstract: Wiley-Abstract
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  • Journal Article Wu K-C, Hochgreb S. The roles of chemistry and diffusion on hydrocarbon post-flame oxidation. Combustion Science and Technology 1997;130(1-6):365-398. R824970 (Final)
  • Abstract: Taylor and Francis-Abstract
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  • Journal Article Xiao S, Ma K, Tang X, Shaw H, Pfeffer R, Stevens JG. The lean catalytic reduction of nitric oxide by solid carbonaceous materials. Applied Catalysis B: Environmental 2001;32(1-2):107-122. R824970 (Final)
  • Abstract: ScienceDirect-Abstract
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  • Journal Article Yamada T, Lay TH, Bozzelli JW. Ab initio calculations and internal rotor: contribution for thermodynamics properties S(O)298 and Cp(T)'s (300 < T/K < 1500): group additivity for fluoroethanes. Journal of Physical Chemistry A 1998;102(37):7286-7293. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Yamada T, Bozzelli JW, Berry RJ. Thermodynamic properties (Delta H-f(298), S(298), and C-p(T) (300 <= T <= 1500)) of fluorinated propanes. Journal of Physical Chemistry A 1999;103(28):5602-5610. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Yamada T, Bozzelli JW, Lay T. Kinetic and thermodynamic analysis on OH addition to ethylene: adduct formation, isomerization, and isomer dissociations. Journal of Physical Chemistry A 1999; 103(38):7646-7655. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Journal Article Yamada,T.; Bozzelli,J.W.. Thermodynamic properties Delta H-f degrees(298), S degrees(298), and C-p(T) for 2-fluoro-2-methylpropane, Delta H-f degrees(298) of fluorinated ethanes, and group additivity for fluoroalkanes. Journal of Physical Chemistry A. 1999; 103(36): 7373-7379. R824970 (Final)
    not available
    Journal Article Yamada T, Bozzelli JW, Lay TH. Comparisons of CBS-q and G2 calculations on thermodynamic properties, transition states, and kinetics of dimethyl-ether plus O2 reaction system. International Journal of Chemical Kinetics 2000;32(7):435-452. R824970 (Final)
  • Abstract: Wiley-Abstract
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  • Journal Article Yu J, Flagan RC, Seinfeld JH. Identification of products containing -COOH, -OH, and -C=O in atmospheric oxidation of hydrocarbons. Environmental Science & Technology 1998;32(16):2357-2370. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Yu JZ, Griffin RJ, Cocker DR, Flagan RC, Seinfeld JH, Blanchard P. Observation of gaseous and particulate products of monoterpene oxidation in forest atmospheres. Geophysical Research Letters 1999;26(8):1145-1148. R824970 (Final)
  • Full-text: Wiley-Full Text PDF
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  • Abstract: Wiley-Abstract
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  • Journal Article Yu J, Cocker III DR, Griffin RJ, Flagan RC, Seinfeld JH. Gas-phase ozone oxidation of monoterpenes: gaseous and particulate products. Journal of Atmospheric Chemistry 1999;34(2):207-258. R824970 (Final)
  • Full-text: SemanticsScholar-Full Text PDF
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  • Abstract: Springer-Abstract
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  • Journal Article Zhong X, Bozzelli JW. Thermochemical and kinetic analysis of the H, OH, HO2, O, and O2 association reactions with cyclopentadienyl radical. Journal of Physical Chemistry A 1998;102(20):3537-3555. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Zhong X, Bozzelli JW. Thermochemical and kinetic analysis on the addition reactions of H, O, OH, and HO2 with 1,3 cyclopentadiene. International Journal of Chemical Kinetics 1997;29(12):893-913. R824970 (Final)
  • Abstract: Wiley-Abstract
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  • Journal Article Zhu L, Bozzelli JW, Ho W-P. Reaction of OH radical with C2H3Cl:rate constant and reaction pathway analysis. Journal of Physical Chemistry A 1999;103(39):7800-7810. R824970 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Zhu L, Chen C-J, Bozzelli JW. Structures, rotational barriers, and thermodynamic properties of C2 vinyl and chlorovinyl alcohols and additivity groups. Journal of Physical Chemistry A 2000;104(40):9197-9206. R824970 (Final)
    R826371C009 (Final)
  • Full-text: ACS-Full Text HTML
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  • Abstract: ACS-Abstract
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  • Journal Article Zhu N, Li Z, Mitra S. Application of on-line membrane extraction microtrap gas chromatography (OLMEM-GC) for continuous monitoring of VOC emission. Journal of Microcolumn Separations 1998;10(5):393-399. R824970 (Final)
  • Abstract: Wiley-Abstract
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  • Supplemental Keywords:

    air, ambient air, atmosphere, ozone, mobile sources, stratospheric ozone, tropospheric, adsorption, chemical transport, risk assessment, exposure, chemicals, toxics, toxic substances, toxics, particulates, volatile organic compound, VOC, polycyclic aromatic hydrocarbon, PAH, peptide nucleic acid, PNA, effluent, discharge, environmental chemistry, physics, engineering, modeling, monitoring, analytical, surveys, measurement methods, northeast, Pacific Coast, Atlantic Coast., RFA, Scientific Discipline, Air, Waste, particulate matter, Environmental Chemistry, Analytical Chemistry, Environmental Monitoring, Atmospheric Sciences, Ecology and Ecosystems, Incineration/Combustion, emission control strategies, atmospheric particulate matter, atmospheric particles, air quality models, combustion emissions, air pollution control, airborne organics, airborne particulate matter, air pollution, atmospheric transport, combustion, aerosol dynamics, combustion kinetics

    Relevant Websites:

    http://web.mit.edu/airquality/www/ Exit
    http://lfee.mit.edu/ Exit
    http://lfee.mit.edu/programs/airquality-endicott/ Exit

    Progress and Final Reports:

    Original Abstract
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  • 2001
  • Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
    R824970C001 Chemical Kinetic Modeling of Formation of Products of Incomplete Combustion from Spark-ignition Engines
    R824970C002 Combustion Chamber Deposit Effects on Engine Hydrocarbon Emissions
    R824970C003 Atmospheric Transformation of Volatile Organic Compounds: Gas-Phase Photooxidation and Gas-to-Particle Conversion
    R824970C004 Mathematical Models of the Transport and Fate of Airborne Organics
    R824970C005 Elementary Reaction Mechanism and Pathways for Atmospheric Reactions of Aromatics - Benzene and Toluene
    R824970C006 Simultaneous Removal of Soot and NOx from the Exhaust of Diesel Powered Vehicles
    R824970C007 Modeling Gas-Phase Chemistry and Heterogeneous Reaction of Polycyclic Aromatic Compounds
    R824970C008 Fundamental Study on High Temperature Chemistry of Oxygenated Hydrocarbons as Alternate Motor Fuels and Additives
    R824970C009 Markers for Emissions from Combustion Sources
    R824970C010 Experimental Investigation of the Evolution of the Size and Composition Distribution of Atmospheric Organic Aerosols
    R824970C011 Microengineered Mass Spectrometer for in-situ Measurement of Airborne Contaminants