Modelling the Evolution of Organic Carbon Modelling the Evolution of Organic Carbon during Its Gas-phase Tropospheric Oxidation: Development of an Explicit Model Based on a Self Generating Approach Acpd Modelling the Evolution of Organic Carbon

Abstract. Organic compounds emitted in the atmosphere are oxidized in complex reaction sequences that produce a myriad of intermediates. Although the cumulative importance of these organic intermediates is widely acknowledged, there is still a critical lack of information concerning the detailed composition of the highly functionalized secondary organics in the gas and condensed phases. The evaluation of their impacts on pollution episodes, climate, and the tropospheric oxidizing capacity requires modelling tools that track the identity and reactivity of organic carbon in the various phases down to the ultimate oxidation products, CO and CO2. However, a fully detailed representation of the atmospheric transformations of organic compounds involves a very large number of intermediate species, far in excess of the number that can be reasonably written manually. This paper describes (1) the development of a data processing tool to generate the explicit gas-phase oxidation schemes of acyclic hydrocarbons and their oxidation products under tropospheric conditions and (2) the protocol used to select the reaction products and the rate constants. Results are presented using the fully explicit oxidation schemes generated for two test species: n-heptane and isoprene. Comparisons with well-established mechanisms were performed to evaluate these generated schemes. Some preliminary results describing the gradual change of organic carbon during the oxidation of a given parent compound are presented.

[1]  M. Rossi.  Evaluated kinetic and photochemical data for atmospheric chemistry , 2010 .

[2]  S. Madronich,et al.  Assessment of the reduction methods used to develop chemical schemes: building of a new chemical scheme for VOC oxidation suited to three-dimensional multiscale HO x -NO x -VOC chemistry simulations , 2005 .

[3]  Michael E. Jenkin,et al.  Modelling the formation and composition of secondary organic aerosol from α- and β-pinene ozonolysis using MCM v3 , 2004 .

[4]  U. Lohmann,et al.  How efficient is cloud droplet formation of organic aerosols? , 2004 .

[5]  U. Baltensperger,et al.  Identification of Polymers as Major Components of Atmospheric Organic Aerosols , 2004, Science.

[6]  F. J. Cox,et al.  Formation of oligomers in secondary organic aerosol. , 2004, Environmental science & technology.

[7]  T. Wallington,et al.  The atmospheric chemistry of alkoxy radicals. , 2003, Chemical reviews.

[8]  Roger Atkinson,et al.  Atmospheric degradation of volatile organic compounds. , 2003, Chemical reviews.

[9]  A. Mellouki,et al.  Kinetics and mechanisms of the oxidation of oxygenated organic compounds in the gas phase. , 2003, Chemical reviews.

[10]  Mark Bydder,et al.  CAPRAM 2.4 (MODAC mechanism): An extended and condensed tropospheric aqueous phase mechanism and its application , 2003 .

[11]  Stephen Pascoe,et al.  Development and preliminary test results of an expert system for the automatic generation of tropospheric VOC degradation mechanisms , 2003 .

[12]  W. Leaitch,et al.  Effect of organics of low solubility on the growth rate of cloud droplets , 2003 .

[13]  Donald Dabdub,et al.  A Coupled Hydrophobic-Hydrophilic Model for Predicting Secondary Organic Aerosol Formation , 2003 .

[14]  A. A. Boyd,et al.  Rate Constants for RO2 + HO2 Reactions Measured under a Large Excess of HO2 , 2003 .

[15]  R. Derwent,et al.  Atmospheric Chemistry and Physics Protocol for the Development of the Master Chemical Mechanism, Mcm V3 (part B): Tropospheric Degradation of Aromatic Volatile Organic Compounds , 2022 .

[16]  Christian Seigneur,et al.  Secondary organic aerosol 2. Thermodynamic model for gas/particle partitioning of molecular constituents , 2002 .

[17]  J. Seinfeld,et al.  Secondary organic aerosol 1. Atmospheric chemical mechanism for production of molecular constituents , 2002 .

[18]  James G. Anderson,et al.  Gas-phase ozonolysis of alkenes: formation of OH from anti carbonyl oxides. , 2002, Journal of the American Chemical Society.

[19]  S. Paulson,et al.  Production of OH radicals from the reactions of C4–C6 internal alkenes and styrenes with ozone in the gas phase , 2002 .

[20]  S. Solberg,et al.  Atmospheric Chemistry and Physics , 2002 .

[21]  J. Troe.  Analysis of the Temperature and Pressure Dependence of the Reaction HO + NO2 + M HONO2 + M. , 2001 .

[22]  A. Hofzumahaus,et al.  Direct measurement of OH radicals from ozonolysis of selected alkenes: a EUPHORE simulation chamber study. , 2001, Environmental science & technology.

[23]  I. J. Ackermann,et al.  Modeling the formation of secondary organic aerosol within a comprehensive air quality model system , 2001 .

[24]  R. A. Cox,et al.  Atmospheric chemistry of small organic peroxy radicals , 2001 .

[25]  J. Orlando,et al.  The Atmospheric Chemistry of Glycolaldehyde , 2001 .

[26]  I. Bey,et al.  A modeling study of the nighttime radical chemistry in the lower continental troposphere: 1. Development of a detailed chemical mechanism including nighttime chemistry , 2001 .

[27]  B. Cabañas,et al.  Night-time Atmospheric Loss Process for Unsaturated Aldehydes: Reaction with NO3 Radicals , 2001 .

[28]  John H. Seinfeld,et al.  Modeling the formation of secondary organic aerosol. 1. Application of theoretical principles to measurements obtained in the α-pinene/, β-pinene/, sabinene/, Δ3-carene/, and cyclohexene/ozone systems , 2001 .

[29]  R. Lesclaux,et al.  Reactions of the HO2 Radical with CH3CHO and CH3C(O)O2 in the Gas Phase , 2001 .

[30]  John J. Orlando,et al.  The atmospheric chemistry of the HC(O)CO radical , 2001 .

[31]  B. d'Anna,et al.  Kinetic study of OH and NO3 radical reactions with 14 aliphatic aldehydes , 2001 .

[32]  D. W. Price,et al.  Aspects of the kinetics and mechanism of the gas-phase reactions of ozone with conjugated dienes , 2001 .

[33]  J. Seinfeld,et al.  Modeling the formation of secondary organic aerosol. 1. Application of theoretical principles to measurements obtained in the alpha-pinene/, beta-pinene/, sabinene/, delta3-carene/, and cyclohexane/ozone systems. , 2001, Environmental science & technology.

[34]  K. Houk,et al.  The Pressure Dependence of the OH Radical Yield from Ozone-Alkene Reactions , 2000 .

[35]  K. Houk,et al.  OH Radical Yields from the Ozone Reaction with Cycloalkenes , 2000 .

[36]  A. Mellouki,et al.  The near-UV absorption cross sections for several ketones , 2000 .

[37]  Paul J. Crutzen,et al.  Impact of Non-Methane Hydrocarbons on Tropospheric Chemistry and the Oxidizing Power of the Global Troposphere: 3-Dimensional Modelling Results , 2000 .

[38]  William P L Carter,et al.  Documentation of the SAPRC-99 chemical mechanism for VOC reactivity assessment. Volume 2. , 2000 .

[39]  S. Madronich,et al.  Contribution of Secondary VOC to the Composition of Aqueous Atmospheric Particles: A Modeling Approach , 2000 .

[40]  Barbara J. Turpin,et al.  Secondary organic aerosol formation in cloud and fog droplets: a literature evaluation of plausibility , 2000 .

[41]  F. Deutsch,et al.  The Influence of Oxalate on Fe-Catalyzed S(IV) Oxidation by Oxygen in Aqueous Solution , 2000 .

[42]  B. Finlayson‐Pitts,et al.  Chemistry of the Upper and Lower Atmosphere , 2000 .

[43]  M. Facchini,et al.  Surface tension of atmospheric wet aerosol and cloud/fog droplets in relation to their organic carbon content and chemical composition , 2000 .

[44]  R. Atkinson.  Atmospheric chemistry of VOCs and NOx , 2000 .

[45]  K. Sexton,et al.  Atmospheric photochemical degradation of 1,4-unsaturated dicarbonyls , 1999 .

[46]  Anne Monod,et al.  Impact of clouds on the tropospheric ozone budget: Direct effect of multiphase photochemistry of soluble organic compounds , 1999 .

[47]  S. Paulson,et al.  OH Radical Formation from the Gas-Phase Reaction of Ozone with Terminal Alkenes and the Relationship between Structure and Mechanism , 1999 .

[48]  G. Marston,et al.  OH Yields in the Gas-Phase Reactions of Ozone with Alkenes , 1999 .

[49]  M. Facchini,et al.  Cloud albedo enhancement by surface-active organic solutes in growing droplets , 1999, Nature.

[50]  Lei Zhu,et al.  Wavelength-Dependent Photolysis of i-Pentanal and t-Pentanal from 280 to 330 nm , 1999 .

[51]  R. A. Cox,et al.  Evaluated Kinetic and Photochemical Data for Atmospheric Chemistry, Organic Species: Supplement VII , 1999 .

[52]  J. Orlando,et al.  The rate and mechanism of the gas-phase oxidation of hydroxyacetone , 1999 .

[53]  M. Jacobson.  Isolating nitrated and aromatic aerosols and nitrated aromatic gases as sources of ultraviolet light absorption , 1999 .

[54]  A. A. Boyd,et al.  Structure–reactivity relationships for the self‐ reactions of linear secondary alkylperoxy radicals: An experimental investigation , 1999 .

[55]  A. Mellouki,et al.  Trends in atmospheric photodissociation rates of selected carbonyl compounds , 1999 .

[56]  J. Tadić,et al.  Photolytic studies on glyoxal, crotonaldehyde, acrolein and glycolaldehyde , 1999 .

[57]  Sasha Madronich,et al.  The Role of Solar Radiation in Atmospheric Chemistry , 1999 .

[58]  Philip J. Rasch,et al.  MOZART, a global chemical transport model for ozone and related chemical tracers: 1. Model description , 1998 .

[59]  S. Koch,et al.  Photochemistry of Methylglyoxal in the Vapor Phase , 1998 .

[60]  W. Stockwell,et al.  Kinetics and atmospheric implications of peroxy radical cross reactions involving the CH3C(O)O2 radical , 1998 .

[61]  Thorsten Hoffmann,et al.  Molecular composition of organic aerosols formed in the α‐pinene/O3 reaction: Implications for new particle formation processes , 1998 .

[62]  Combination of Peroxyl Radicals in the Gas Phase , 1998 .

[63]  E. Grosjean,et al.  RATE CONSTANTS FOR THE GAS-PHASE REACTION OF OZONE WITH UNSATURATED OXYGENATES , 1998 .

[64]  S. M. Aschmann,et al.  Kinetics of the gas-phase reactions of NO3 radicals with a series of alcohols, glycol ethers, ethers and chloroalkenes , 1998 .

[65]  S. Koch,et al.  Rate constants for the reactions of methylvinyl ketone, methacrolein, methacrylic acid, and acrylic acid with ozone , 1998 .

[66]  J. Seinfeld,et al.  Mathematical model for gas-particle partitioning of secondary organic aerosols , 1997 .

[67]  F. Kirchner,et al.  A new mechanism for regional atmospheric chemistry modeling , 1997 .

[68]  Lei Zhu,et al.  Temperature dependence of the UV absorption cross sections and photodissociation products of C3C5 nitrates , 1997 .

[69]  Samuel H. Yalkowsky,et al.  Estimating Pure Component Vapor Pressures of Complex Organic Molecules , 1997 .

[70]  R. A. Cox,et al.  Evaluated Kinetic, Photochemical and Heterogeneous Data for Atmospheric Chemistry: Supplement V. IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry , 1997 .

[71]  J. H. Seinfeld,et al.  The Atmospheric Aerosol-Forming Potential of Whole Gasoline Vapor , 1997, Science.

[72]  Frank M. Bowman,et al.  Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons , 1997 .

[73]  M. Jenkin,et al.  The tropospheric degradation of volatile organic compounds: a protocol for mechanism development , 1997 .

[74]  W. Boullart,et al.  Kinetic Studies of Reactions of Alkylperoxy and Haloalkylperoxy Radicals with NO. A Structure-Activity Relationship for Reactions of OH with Alkenes and Polyalkenes , 1997 .

[75]  R. A. Cox,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement V , 1996 .

[76]  Roger Atkinson,et al.  Development and evaluation of a detailed mechanism for the atmospheric reactions of isoprene and NOx , 1996 .

[77]  A. Ravishankara,et al.  Rate Coefficients for Reactions of NO3 with a Few Olefins and Oxygenated Olefins , 1996 .

[78]  J. Pyle,et al.  Is the reaction between CH3C(O)O2 and NO3 important in the night-time troposphere? , 1996 .

[79]  G. Moortgat,et al.  PHOTOOXIDATION OF SELECTED CARBONYL COMPOUNDS IN AIR: METHYL ETHYL KETONE, METHYL VINYL KETONE, METHACROLEIN AND METHYLGLYOXAL , 1995 .

[80]  J. Barker.  Progress and Problems in Atmospheric Chemistry , 1995 .

[81]  J. Seinfeld,et al.  Organics alter hygroscopic behavior of atmospheric particles , 1995 .

[82]  I. Barnes,et al.  Kinetic and mechanistic study of the atmospheric chemistry of muconaldehydes. , 1995, Environmental science & technology.

[83]  R. Atkinson,et al.  Estimation of hydroxyl radical reaction rate constants for gas-phase organic compounds using a structure-reactivity relationship : an update , 1995 .

[84]  Joke Blom,et al.  A comparison of stiff ode solvers for atmospheric chemistry problems , 1995 .

[85]  Jan G. Verwer,et al.  Gauss-Seidel Iteration for Stiff ODES from Chemical Kinetics , 1994, SIAM J. Sci. Comput..

[86]  B. Faust.  Photοcheμistry of clouds, fogs, and aerosols. , 1994, Environmental science & technology.

[87]  I. Barnes,et al.  Atmospheric Chemistry of Unsaturated Carbonyls: Butenedial, 4-Oxo-2-pentenal, 3-Hexene-2,5-dione, Maleic Anhydride, 3H-Furan-2-one, and 5-Methyl-3H-furan-2-one. , 1994, Environmental science & technology.

[88]  R. Sempéré,et al.  Comparative distributions of dicarboxylic acids and related polar compounds in snow, rain and aerosols from urban atmosphere , 1994 .

[89]  R. Atkinson.  Gas-Phase Tropospheric Chemistry of Organic Compounds , 1994 .

[90]  J. Joens,et al.  The near U.V. absorption spectra of several aliphatic aldehydes and ketones at 300 K , 1992 .

[91]  R. A. Cox,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement IV: IUPAC subcommittee on gas kinetic data evaluation for atmospheric chemistry , 1992 .

[92]  R. Atkinson.  Kinetics and Mechanisms of the Gas‐Phase Reactions of the NO3 Radical with Organic Compounds , 1991 .

[93]  W. Stockwell,et al.  The second generation regional acid deposition model chemical mechanism for regional air quality modeling , 1990 .

[94]  R. Atkinson,et al.  A product study of the gas-phase reaction of methacrolein with the OH radical in the presence of NOx , 1990 .

[95]  Jack G. Calvert,et al.  Permutation reactions of organic peroxy radicals in the troposphere , 1990 .

[96]  R. Atkinson,et al.  A Product Study of the Gas Phase Reaction of Methyl Vinyl Ketone with the OH Radical in the Presence of NOx. , 1990 .

[97]  R. Atkinson.  Gas-phase tropospheric chemistry of organic compounds: a review , 1990 .

[98]  R. Atkinson,et al.  A product study of the gas‐phase reaction of methyl vinyl ketone with the OH radical in the presence of NOx , 1989 .

[99]  M. C. Dodge,et al.  A photochemical kinetics mechanism for urban and regional scale computer modeling , 1989 .

[100]  J. Roberts,et al.  UV absorption cross sections of organic nitrates of potential atmospheric importance and estimation of atmospheric lifetimes , 1989 .

[101]  J. Heicklen,et al.  The photo-oxidation of i-C3H7CHO vapour , 1986 .

[102]  M. Molina,et al.  Chemical kinetics and photochemical data for use in stratospheric modeling , 1985 .

[103]  W. Carter,et al.  Hydroxyl radical rate constants and photolysis rates of .alpha.-dicarbonyls. , 1983, Environmental science & technology.