Atmospheric Chemistry and Physics Protocol for the Development of the Master Chemical Mechanism, Mcm V3 (part B): Tropospheric Degradation of Aromatic Volatile Organic Compounds

Kinetic and mechanistic data relevant to the tropospheric degradation of aromatic volatile organic compounds (VOC) have been used to define a mechanism development protocol, which has been used to construct degradation schemes for 18 aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). This is complementary to the treatment of 107 non-aromatic VOC, presented in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the degradation chemistry to first generation products via a number of competitive routes, and the further degradation of first and subsequent generation products. Emphasis is placed on describing where the treatment differs from that applied to the non-aromatic VOC. The protocol is based on work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Photochemical Ozone Creation Potentials (POCP) have been calculated for the 18 aromatic VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. These show distinct differences from POCP values calculated previously for the aromatics, using earlier versions of the MCM, and reasons for these differences are discussed.

[1]  M. Jenkin.  Master Chemical Mechanisms: Comparison with the Real World , 2001 .

[2]  Cornelius Zetzsch,et al.  Gas-phase reaction of the OH–benzene adduct with O2: reversibility and secondary formation of HO2 , 1999 .

[3]  R. A. Cox,et al.  Organic peroxy radicals: Kinetics, spectroscopy and tropospheric chemistry , 1992 .

[4]  F. Berho,et al.  Kinetics and Thermochemistry of the Reversible Combination Reaction of the Phenoxy Radical with NO , 1998 .

[5]  D. Shallcross,et al.  Investigation into the Kinetics and Mechanism of the Reaction of NO3 with CH3O2 at 298 K and 2.5 Torr: A Potential Source of OH in the Night-Time Troposphere? , 1994 .

[6]  R. Atkinson,et al.  A Product Study of the Gas-Phase Reaction of Isoprene with the OH Radical in the Presence of NOx. , 1991 .

[7]  Dimitrios Kotzias,et al.  Carboxylic Acids in Secondary Aerosols from Oxidation of Cyclic Monoterpenes by Ozone , 2000 .

[8]  Glen R. Cass,et al.  Quantification of urban organic aerosols at a molecular level: Identification, abundance and seasonal variation , 1993 .

[9]  H. Jeffries,et al.  Identifying Airborne Carbonyl Compounds in Isoprene Atmospheric Photooxidation Products by Their PFBHA Oximes Using Gas Chromatography/Ion Trap Mass Spectrometry. , 1995, Environmental science & technology.

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

[11]  David R. Cocker,et al.  The effect of water on gas–particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system , 2001 .

[12]  D. M. Rowley,et al.  Kinetic and mechanistic studies of the reactions of cyclopentylperoxy and cyclohexylperoxy radicals with hydroperoxy radical , 1992 .

[13]  Ulrich Platt,et al.  Primary and Secondary Glyoxal Formation from Aromatics: Experimental Evidence for the Bicycloalkyl−Radical Pathway from Benzene, Toluene, and p-Xylene , 2001 .

[14]  A. Duarte,et al.  Identification, abundance and origin of atmospheric organic particulate matter in a Portuguese rural area , 2001 .

[15]  V. Daële,et al.  Kinetic Study of the Reactions of C2H5O and C2H5O2 with NO3 at 298 K , 1996 .

[16]  J. Crowley,et al.  Kinetic Investigations of the Reactions of CD 3 O 2 with NO and NO 3 at 298 K , 1996 .

[17]  A. Mellouki,et al.  Kinetic Studies on the Reactions of Hydroxyl Radicals with Diethers and Hydroxyethers , 1997 .

[18]  T. Wallington,et al.  Kinetic Measurements of the Gas-Phase Reactions of OH Radicals with Hydroxy Ethers, Hydroxy Ketones, and Keto Ethers. , 1990 .

[19]  Garry D. Hayman,et al.  Photochemical ozone creation potentials for oxygenated volatile organic compounds: sensitivity to variations in kinetic and mechanistic parameters , 1999 .

[20]  R. Derwent,et al.  Photochemical ozone creation potentials for a large number of reactive hydrocarbons under European conditions , 1996 .

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

[22]  John H. Seinfeld,et al.  Gas-Phase Ozone Oxidation of Monoterpenes: Gaseous and Particulate Products , 1999 .

[23]  Giovanni Ghigo,et al.  BENZENE OXIDATION IN THE TROPOSPHERE. THEORETICAL INVESTIGATION ON THE POSSIBLE COMPETITION OF THREE POSTULATED REACTION CHANNELS , 1998 .

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

[25]  J. Arey,et al.  Observation of Hydroxycarbonyls from the OH Radical-Initiated Reaction of Isoprene. , 1995, Environmental science & technology.

[26]  S. M. Aschmann,et al.  Products of the gas phase reactions of the OH radical with α‐ and β‐pinene in the presence of NO , 1998 .

[27]  P. Warneck,et al.  Oxidation of toluene in NO? free air: Product distribution and mechanism , 1996 .

[28]  Giovanni Ghigo,et al.  From benzene to muconaldehyde: Theoretical mechanistic investigation on some tropospheric oxidation channels , 1999 .

[29]  S. M. Aschmann,et al.  Products of the gas-phase reactions of o-,m- and p-xylene with the OH radical in thepresence and absence ofNOx , 1997 .

[30]  A. Bouwman,et al.  Description of EDGAR Version 2.0: A set of global emission inventories of greenhouse gases and ozone-depleting substances for all anthropogenic and most natural sources on a per country basis and on 1 degree x 1 degree grid , 1996 .

[31]  Yin‐Nan Lee,et al.  Atmospheric carbonyl compounds at a rural southeastern United States site , 1995 .

[32]  M. Jenkin,et al.  Kinetics of Reactions of Primary, Secondary and Tertiary β- Hydroxy Peroxyl Radicals. Application to Isoprene Degradation , 1995 .

[33]  B. Bohn.  Formation of Peroxy Radicals from OH-Toluene Adducts and O2 , 2001 .

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

[35]  John H. Seinfeld,et al.  Estimating the vapor pressures of multi-functional oxygen-containing organic compounds using group contribution methods , 2002 .

[36]  R. Atkinson.  Kinetics and mechanisms of the gas-phase reactions of the hydroxyl radical with organic compounds , 1989 .

[37]  R. Kamens,et al.  Newly characterized products and composition of secondary aerosols from the reaction of α-pinene with ozone , 1999 .

[38]  J. Seinfeld,et al.  Atmospheric photooxidation of isoprene part I: The hydroxyl radical and ground state atomic oxygen reactions , 1992 .

[39]  R. Derwent,et al.  Photochemical ozone creation potentials for organic compounds in northwest Europe calculated with a master chemical mechanism , 1998 .

[40]  J. Williams,et al.  Regional ozone from biogenic hydrocarbons deduced from airborne measurements of PAN, PPN, and MPAN , 1997 .

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

[42]  R. Atkinson.  A Structure‐Activity Relationship for the Estimation of Rate Constants for the Gas‐Phase Reactions of OH Radicals with Organic Compounds. , 1987 .

[43]  M. Holdren,et al.  Atmospheric chemistry and distribution of formaldehyde and several multioxygenated carbonyl compounds during the 1995 Nashville/Middle Tennessee Ozone Study , 1998 .

[44]  D. Swackhamer.  Rethinking the Ozone Problem in Urban and Regional Air Pollution , 1993 .

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

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

[47]  D. Shallcross,et al.  Investigation into the kinetics and mechanism of the reaction of NO3 with CH3O2 at 298 K and 2.5 Torr: a potential source of OH in the night-time troposphere? , 1994 .

[48]  I. Barnes,et al.  FT–IR study of the ring-retaining products from the reaction of OH radicals with phenol, o-, m-, and p-cresol , 2002 .

[49]  M. Jenkin,et al.  The origin and day-of-week dependence of photochemical ozone episodes in the UK , 2002 .

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

[51]  C. J. Howard,et al.  Temperature-dependent kinetics studies of the reactions of C2H5O2 and n-C3H7O2 radicals with NO , 1996 .

[52]  M. Jenkin,et al.  Hydrocarbons and the long-range transport of ozone and pan across Europe , 1991 .

[53]  J. Arey,et al.  Products of the Gas-Phase Reactions of OH Radicals with p-Xylene and 1,2,3- and 1,2,4-Trimethylbenzene: Effect of NO2 Concentration , 2000 .

[54]  M. Katz,et al.  PHOTOCHEMISTRY OF AIR POLLUTION , 1962 .

[55]  Jack G. Calvert,et al.  The mechanisms of atmospheric oxidation of aromatic hydrocarbons , 2002 .

[56]  E. Grosjean,et al.  Atmospheric chemistry of isoprene and of its carbonyl products , 1993 .

[57]  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.

[58]  M. Kurylo,et al.  UV absorption cross sections and reaction kinetics and mechanisms for peroxy radicals in the gas phase , 1992 .

[59]  O. Nielsen,et al.  Atmospheric Chemistry of the Phenoxy Radical, C6H5O(•): UV Spectrum and Kinetics of Its Reaction with NO, NO2, and O2 , 1998 .

[60]  T. Wallington,et al.  Atmospheric chemistry of benzaldehyde: UV absorption spectrum and reaction kinetics and mechanisms of the C6H5C(O)O2 radical , 1999 .

[61]  R. Atkinson.  Atmospheric reactions of alkoxy and ?-hydroxyalkoxy radicals , 1997 .

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

[63]  G. Poulet,et al.  KINETICS OF THE REACTIONS CH3O + NO, CH3O + NO3, AND CH3O2 + NO3 , 1995 .

[64]  M. Jenkin,et al.  Modelling of the photooxidation of toluene: conceptual ideas for validating detailed mechanisms , 2002 .

[65]  John H. Seinfeld,et al.  Atmospheric Photochemical Oxidation of Benzene: Benzene + OH and the Benzene−OH Adduct (Hydroxyl-2,4-cyclohexadienyl) + O2 , 1996 .

[66]  K. Clemitshaw,et al.  Ozone and other secondary photochemical pollutants: chemical processes governing their formation in the planetary boundary layer , 2000 .

[67]  Roger Atkinson,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III - gas phase reactions of inorganic halogens , 2006 .

[68]  M. Jenkin,et al.  Kinetics and product study of the self-reactions of allyl and allyl peroxy radicals at 296 K , 1993 .

[69]  D. Shallcross,et al.  Development and application of a possible mechanism for the generation of cis-pinic acid from the ozonolysis of α- and β-pinene , 2000 .

[70]  K. Becker,et al.  A product study of the OH radical-initiated oxidation of isoprene: formation of C5-unsaturated diols , 2000 .

[71]  C. J. Howard,et al.  Rate Coefficients for the Reactions of Some C3 to C5 Hydrocarbon Peroxy Radicals with NO , 1997 .

[72]  Y. Rudich,et al.  Product studies of the OH‐ and ozone‐initiated oxidation of some monoterpenes , 2000 .

[73]  S. M. Aschmann,et al.  Formation yields of methyl vinyl ketone and methacrolein from the gas-phase reaction of o3 with isoprene. , 1994, Environmental Science and Technology.

[74]  J. Peeters,et al.  Theoretical Study of the Formation of Acetone in the OH-Initiated Atmospheric Oxidation of α-Pinene , 2000 .

[75]  B. Turpin,et al.  Identification of secondary organic aerosol episodes and quantitation of primary and secondary organic aerosol concentrations during SCAQS , 1995 .

[76]  P. Saxena,et al.  Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds , 1996 .

[77]  J. Roberts,et al.  The atmospheric chemistry of organic nitrates , 1990 .

[78]  Takashi Imamura,et al.  OH-initiated oxidation of benzene Part I . Phenol formation under atmospheric conditions , 2002 .

[79]  J. Burrows,et al.  The nitrate radical: Physics, chemistry, and the atmosphere , 1991 .

[80]  A. Miyoshi,et al.  OH radical‐ initiated photooxidation of isoprene: An estimate of global CO production , 1994 .

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

[82]  J. Roberts,et al.  A PAN analog from isoprene photooxidation , 1991 .

[83]  H. Herrmann,et al.  On the formation of benzene oxide/oxepin in the gas-phase reaction of OH radicals with benzene , 1999 .

[84]  P. Villalta,et al.  REACTION OF ISOPROPYL PEROXY RADICALS WITH NO OVER THE TEMPERATURE RANGE 201-401 K , 1996 .

[85]  P. Maker,et al.  FTIR spectroscopic study of the mechanism for the gas-phase reaction between ozone and tetramethylethylene , 1987 .

[86]  John H. Seinfeld,et al.  Secondary Organic Aerosol from the Photooxidation of Aromatic Hydrocarbons: Molecular Composition , 1997 .

[87]  Reactions of Organic Peroxy Radicals in the Gas Phase , 1998 .

[88]  R. Atkinson.  A structure-activity relationship for the estimation of rate constants for the gas-phase reactions of OH radicals with organic compounds , 1987 .

[89]  Evaluation of the condensed carbon bond (CB-IV) mechanism against smog chamber data at low VOC and NOx concentrations , 1997 .

[90]  Dimitrios Kotzias,et al.  cis-Pinic acid, a possible precursor for organic aerosol formation from ozonolysis of α-pinene , 1998 .

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

[92]  P. Villalta,et al.  Reaction of Isopropyl Peroxy Radicals with NO over the Temperature Range 201‐401 K , 1996 .

[93]  J. Yu,et al.  Atmospheric photooxidation of alkylbenzenes—II. Evidence of formation of epoxide intermediates , 1997 .

[94]  C. N. Hewitt,et al.  A global model of natural volatile organic compound emissions , 1995 .

[95]  Roger Atkinson,et al.  Gas-Phase Tropospheric Chemistry of Volatile Organic Compounds: 1. Alkanes and Alkenes , 1997 .

[96]  P. Villalta,et al.  Direct kinetics study of the CH3C(O)O2 + NO reaction using chemical ionization mass spectrometry , 1996 .

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

[98]  W. Carter,et al.  Atmospheric chemistry of cis- and trans-3-hexene-2,5-dione. , 1985, Environmental science & technology.

[99]  S. Langer,et al.  Reactions of acrolein, crotonaldehyde and pivalaldehyde with Cl atoms: structure–activity relationship and comparison with OH and NO3 reactions , 2001 .

[100]  R. Derwent,et al.  World wide web site of a master chemical mechanism (MCM) for use in tropospheric chemistry models , 1997 .

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

[102]  T. Wallington,et al.  Kinetic measurements of the gas-phase reactions of OH radicals with hydroxy ethers, hydroxy ketones, and keto ethers , 1989 .

[103]  J. Arey,et al.  Rate constants for the gas‐phase reactions of a series of C3C6 aldehydes with OH and NO3 radicals , 2000 .

[104]  D. Shallcross,et al.  Rate constants for the reactions of C2H5, C2H5O and C2H5O2 radicals with NO3 at 298 K and 2.2 torr , 1995 .

[105]  James N. Pitts,et al.  Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications , 1999 .

[106]  A. A. Boyd,et al.  Peroxy Radical Kinetics Resulting from the OH-Initiated Oxidation of 1,3-Butadiene, 2,3-Dimethyl-1,3-Butadiene and Isoprene , 1998 .

[107]  W. Goddard,et al.  Mechanism of atmospheric photooxidation of aromatics: A theoretical study , 1996 .

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

[109]  W. Carter,et al.  An experimental study of incremental hydrocarbon reactivity. , 1987, Environmental science & technology.

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