Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review

Large quantities of non-methane organic compounds are emitted into the atmosphere from biogenic sources, mainly from vegetation. These organic compounds include isoprene, C10H16 monoterpenes, C15H24 sesquiterpenes, and a number of oxygenated compounds including methanol, hexene derivatives, 2-methyl-3-buten-2-ol, and 6-methyl-5-hepten-2-one. In the troposphere these organic compounds react with hydroxyl (OH) radicals, nitrate (NO3) radicals and ozone (O3), and play an important role in the chemistry of the lower troposphere. In this article the kinetics, products and mechanisms of the tropospheric reactions of biogenic organic compounds are presented and briefly discussed.

[1]  R. N. Schindler,et al.  Epoxide formation in the reactions of the nitrate radical with 2,3-dimethyl-2-butene, cis- and trans-2-butene and isoprene , 1994 .

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

[3]  Renyi Zhang,et al.  Mechanism of OH formation from ozonolysis of isoprene: kinetics and product yields , 2002 .

[4]  S. M. Aschmann,et al.  Atmospheric chemistry of the monoterpene reaction products nopinone, camphenilone, and 4-acetyl-1-methylcyclohexene , 1993 .

[5]  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.

[6]  B. Lamb,et al.  Biogenic Hydrocarbons in the Atmospheric Boundary Layer: A Review , 2000 .

[7]  R. Kamens,et al.  Aerosol formation from the reaction of α-pinene and ozone using a gas- phase kinetics-aerosol partitioning model , 1999 .

[8]  J. Lelieveld,et al.  Model study of the influence of cross-tropopause O3 transports on tropospheric O3 levels , 1997 .

[9]  D. Allen,et al.  Measurement and analysis of atmospheric concentrations of isoprene and its reaction products in central Texas , 2001 .

[10]  P. Shepson,et al.  Sequential oxidation products from tropospheric isoprene chemistry : MACR and MPAN at a NOx-rich forest environment in the southeastern United States , 1998 .

[11]  J. Arey,et al.  Rate constants for the gas‐phase reactions of OH radicals with a series of unsaturated alcohols , 2001 .

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

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

[14]  A. Ravishankara,et al.  Atmospheric fate of methyl vinyl ketone and methacrolein , 1997 .

[15]  A. Reissell,et al.  Biogenic volatile organic compounds at Azusa and elevated sites during the 1997 Southern California Ozone Study , 2001 .

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

[17]  E. Grosjean,et al.  Atmospheric chemistry of unsaturated alcohols , 1993 .

[18]  R. Fall Biogenic Emissions of Volatile Organic Compounds from Higher Plants , 1999 .

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

[20]  U. Platt,et al.  Nitrate Radicals in Tropospheric Chemistry , 1994 .

[21]  D. M. Cunnold,et al.  Atmospheric Trends and Lifetime of CH3CCI3 and Global OH Concentrations , 1995, Science.

[22]  B. Lamb,et al.  Natural emissions of non-methane volatile organic compounds, carbon monoxide, and oxides of nitrogen from North America , 2000 .

[23]  F. Comes,et al.  Tropospheric OH formation by ozonolysis of terpenes , 1998 .

[24]  R. Atkinson,et al.  OH radical formation yields from the gas‐phase reactions of O3 with alkenes and monoterpenes , 1996 .

[25]  Donald Dabdub,et al.  Estimate of global atmospheric organic aerosol from oxidation of biogenic hydrocarbons , 1999 .

[26]  John H. Seinfeld,et al.  Aerosol formation in the photooxidation of isoprene and β-pinene , 1991 .

[27]  D. Kotzias,et al.  Gas Phase Terpene Oxidation Products. A Review. , 1999 .

[28]  S. M. Aschmann,et al.  Formation of O(3P) atoms and epoxides from the gas- phase reaction of O3 with isoprene , 1994 .

[29]  S. M. Aschmann,et al.  Product study of the gas-phase reactions of monoterpenes with the OH radical in the presence of NO x , 1990 .

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

[31]  D. M. Cunnold,et al.  Evidence for Substantial Variations of Atmospheric Hydroxyl Radicals in the Past Two Decades , 2001, Science.

[32]  John H. Seinfeld,et al.  Organic aerosol formation from the oxidation of biogenic hydrocarbons , 1999 .

[33]  Hal Westberg,et al.  A national inventory of biogenic hydrocarbon emissions , 1987 .

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

[35]  J. Orlando,et al.  Mechanism of the OH‐initiated oxidation of methacrolein , 1999 .

[36]  John H. Seinfeld,et al.  Identification of Products Containing −COOH, −OH, and −C=O in Atmospheric Oxidation of Hydrocarbons , 1998 .

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

[38]  S. M. Aschmann,et al.  Product formation from the reaction of the NO3 radical with isoprene and rate constants for the reactions of methacrolein and methyl vinyl ketone with the NO3 radical , 1996 .

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

[40]  J. Logan Tropospheric ozone: Seasonal behavior, trends, and anthropogenic influence , 1985 .

[41]  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 .

[42]  E. Grosjean,et al.  The Gas Phase Reaction of Unsaturated Oxygenates with Ozone: Carbonyl Products and Comparison with the Alkene-Ozone Reaction , 1997 .

[43]  A. Wisthaler,et al.  Measurements of acetone and other gas phase product yields from the OH-initiated oxidation of terpenes by proton-transfer-reaction mass spectrometry (PTR-MS) , 2001 .

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

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

[46]  S. M. Aschmann,et al.  Products of the gas‐phase reactions of O(3 P) atoms and O3 with α‐pinene and 1,2‐dimethyl‐1‐cyclohexene , 1998 .

[47]  J. Seinfeld,et al.  Gas-phase reaction of ozone with trans-2-hexenal, trans-2-hexenyl acetate, ethylvinyl ketone, and 6-methyl-5-hepten-2-one , 1996 .

[48]  E. Grosjean,et al.  A biogenic precursor of peroxypropionyl nitrate : atmospheric oxidation of cis-3-hexen-1-ol , 1993 .

[49]  James G. Anderson,et al.  Mechanism of HOx Formation in the Gas-Phase Ozone-Alkene Reaction. 1. Direct, Pressure-Dependent Measurements of Prompt OH Yields†. , 2001, The journal of physical chemistry. A.

[50]  A. Reissell,et al.  Products of the OH radical‐ and O3‐initiated reactions of myrcene and ocimene , 2002 .

[51]  James G. Anderson,et al.  Accurate, direct measurements of oh yields from gas‐phase ozone‐alkene reactions using an in situ LIF Instrument , 2001 .

[52]  W. Schneider,et al.  Quantum yields for the photodissociation of acetone in air and an estimate for the life time of acetone in the lower troposphere , 1986 .

[53]  T. Berndt,et al.  PRODUCTS AND MECHANISM OF THE GAS-PHASE REACTION OF NO3 RADICALS WITH ALPHA -PINENE , 1997 .

[54]  S. M. Aschmann,et al.  Rate constants for the gas‐phase reactions of O3 with a series of monoterpenes and related compounds at 296 ± 2 K , 1990 .

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

[56]  R. Atkinson,et al.  Kinetics of the gas-phase reactions of hydroxyl and nitrogen oxide (NO3) radicals with 2-carene, 1,8-cineole, p-cymene, and terpinolene , 1990 .

[57]  P. Midgley,et al.  Transport and Chemical Transformation in the Troposphere , 2001 .

[58]  I. Barnes,et al.  Product study and mechanisms of the reactions of α‐pinene and of pinonaldehyde with OH radicals , 1999 .

[59]  C. Vinckier,et al.  Identification of the oxidation products of the reaction between alpha-pinene and hydroxyl radicals by gas and high-performance liquid chromatography with mass spectrometric detection. , 2000, Journal of chromatography. A.

[60]  N. Jensen,et al.  Mechanistic studies of the atmospheric oxidation of methyl butenol by OH radicals, ozone and NO3 radicals , 1998 .

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

[62]  J. Seinfeld,et al.  Photochemical aerosol formation from α‐pinene‐ and β‐pinene , 1992 .

[63]  Hal Westberg,et al.  A biogenic hydrocarbon emission inventory for the U.S.A. using a simple forest canopy model , 1993 .

[64]  Claus J. Nielsen,et al.  Gas-Phase Reactions of Nopinone, 3-Isopropenyl-6-oxo-heptanal, and 5-Methyl-5-vinyltetrahydrofuran-2-ol with OH, NO3, and Ozone , 1999 .

[65]  S. M. Aschmann,et al.  OH radical formation from the gas-phase reactions of O3 with methacrolein and methyl vinyl ketone , 1996 .

[66]  C. Geron,et al.  A review and synthesis of monoterpene speciation from forests in the United States. , 2000 .

[67]  S. M. Aschmann,et al.  Formation of OH radicals in the gas phase reactions of O3 with a series of terpenes , 1992 .

[68]  A. Winer,et al.  Estimation of night-time N2O5 concentrations from ambient NO2 and NO3 radical concentrations and the role of N2O5 in night-time chemistry , 1986 .

[69]  T. Berndt,et al.  GAS-PHASE REACTION OF NO3 RADICALS WITH ISOPRENE : A KINETIC AND MECHANISTIC STUDY , 1997 .

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

[71]  I. Barnes,et al.  Evidence for formation of a PAN analogue of pinonic structure and investigation of its thermal stability , 1998 .

[72]  R. Atkinson,et al.  Rate constants for the gas‐phase reactions of O3 with a series of Terpenes and OH radical formation from the O3 reactions with Sesquiterpenes at 296 ± 2 K , 1994 .

[73]  S. Montzka,et al.  Isoprene and its oxidation products, methyl vinyl ketone and methacrolein, in the rural troposphere , 1993 .

[74]  J. Seinfeld RETHINKING THE OZONE PROBLEM IN URBAN AND REGIONAL AIR POLLUTION , 1991 .

[75]  H. Hakola,et al.  Product formation from the gas-phase reactions of hydroxyl radicals and ozone with .beta.-phellandrene , 1993 .

[76]  P. Warneck,et al.  Product distributions from the OH radical-induced oxidation of but-1-ene, methyl-substituted but-1-enes and isoprene in NOx-free air , 2000 .

[77]  H. Hakola,et al.  Product formation from the gas-phase reactions of OH radicals and O3 with a series of monoterpenes , 1994 .

[78]  Arthur M. Winer,et al.  A spatially and temporally resolved biogenic hydrocarbon emissions inventory for the California South Coast Air Basin , 1997 .

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

[80]  Formation of 3-Methylfuran from the gas-phase reaction of OH radicals with isoprene and the rate constant for its reaction with the OH radical , 1989 .

[81]  S. M. Aschmann,et al.  Reactions of stabilized criegee intermediates from the gas‐phase reactions of O3 with selected alkenes , 2002 .

[82]  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 .

[83]  D. Kotzias,et al.  Product analysis of the gas-phase reaction of β-caryophyllene with ozone , 1997 .

[84]  A. Reissell,et al.  Formation of acetone from the OH radical‐ and O3‐initiated reactions of a series of monoterpenes , 1999 .

[85]  J. Arey,et al.  Products of the Gas-Phase Reactions of Linalool with OH Radicals, NO3 Radicals, and O3 , 1997 .

[86]  J. Orlando,et al.  The reactions of ozone with alkenes: An important source of HOx in the boundary layer , 1996 .

[87]  J. Arey,et al.  Kinetics of the Gas-Phase Reactions of OH and NO3 Radicals and O3 with the Monoterpene Reaction Products Pinonaldehyde, Caronaldehyde, and Sabinaketone , 1998 .

[88]  S. Paulson,et al.  Evidence for formation of OH radicals from the reaction of O3 with alkenes in the gas phase , 1997 .

[89]  Atmospheric oxidation of linalool , 1995, Naturwissenschaften.

[90]  R. Atkinson,et al.  Kinetics and Products of the Gas-Phase Reactions of 6-Methyl-5-hepten-2-one and trans-Cinnamaldehyde with OH and NO3 Radicals and O3 at 296 ± 2 K , 1996 .

[91]  H. Akimoto,et al.  Reactions of ozone with α‐pinene and β‐pinene in air: Yields of gaseous and particulate products , 1989 .

[92]  S. M. Aschmann,et al.  OH radical formation from the gas-phase reactions of O3 with a series of terpenes , 2002 .

[93]  P. Shepson,et al.  Observations of isoprene chemistry and its role in ozone production at a semirural site during the 1995 Southern Oxidants Study , 1998 .

[94]  Ian Barnes,et al.  Aerosol and Product Yields from NO3 Radical-Initiated Oxidation of Selected Monoterpenes , 1999 .

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

[96]  H. Skov,et al.  Products and mechanisms of the reactions of the nitrate radical (NO3) with isoprene, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene in air , 1992 .

[97]  V. L. Orkin,et al.  Scientific Assessment of Ozone Depletion: 2010 , 2003 .

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

[99]  Paul J. Crutzen,et al.  An inverse modeling approach to investigate the global atmospheric methane cycle , 1997 .

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

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

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

[103]  G. Moortgat,et al.  Formation of hydrogen peroxide in the ozonolysis of isoprene and simple alkenes under humid conditions , 1999 .

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

[105]  G. Moortgat,et al.  Formation of OH radicals in the gas-phase reaction of propene, isobutene and isoprene with O3: Yields and mechanistic implications , 1999 .

[106]  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 .

[107]  J. Seinfeld,et al.  Fourier transform infrared analysis of aerosol formed in the photo-oxidation of isoprene and β-pinene , 1992 .

[108]  M. Spittler,et al.  Development Of Monoterpene Oxidation Mechanisms: Results From Laboratory And Smog Chamber Studies , 1970 .

[109]  I. Barnes,et al.  Kinetics of the reactions of pinonaldehyde with OH radicals and with Cl atoms , 1999 .

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

[111]  R. N. Schindler,et al.  Formation of OH radicals in the gas phase ozonolysis of alkenes: the unexpected role of carbonyl oxides , 1996 .

[112]  John H. Seinfeld,et al.  Atmospheric oxidation of biogenic hydrocarbons : Reaction of ozone with β-pinene, d-limonene and trans-caryophyllene , 1993 .

[113]  I. Wängberg,et al.  Product and Mechanistic Study of the Reaction of NO3 Radicals with α-Pinene , 1997 .

[114]  K. Becker,et al.  Studies on the formation of H2O2 in the ozonolysis of alkenes , 1993 .

[115]  S. M. Aschmann,et al.  Products of the gas-phase reactions of cis-3-hexen-1-ol with OH radicals and O3 , 1997 .

[116]  S. M. Aschmann,et al.  Kinetics of the gas‐phase reactions of OH radicals with a series of α,β‐unsaturated carbonyls at 299 ± 2 K , 1983 .

[117]  G. Moortgat,et al.  Products and Mechanism of the Gas Phase Reaction of Ozone with β-Pinene , 2000 .

[118]  Robert J. O'Brien,et al.  Measurement of free radicals OH and HO2 in Los Angeles smog , 1999 .

[119]  S. Montzka,et al.  Measurements of 3‐methyl furan, methyl vinyl ketone, and methacrolein at a rural forested site in the southeastern United States , 1995 .

[120]  H. Akimoto,et al.  Reactions of OH with α‐pinene and β‐pinene in air: Estimate of global CO production from the atmospheric oxidation of terpenes , 1991 .

[121]  R. N. Schindler,et al.  On the use of CO as scavenger for OH radicals in the ozonolysis of simple alkenes and isoprene , 1997 .

[122]  S. M. Aschmann,et al.  Products and mechanisms of the gas-phase reactions of OH radicals and O3 with 2-methyl-3-buten-2-ol , 1999 .

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

[124]  S. Paulson,et al.  Measurement of Absolute Unimolecular and Bimolecular Rate Constants for CH3CHOO Generated by thetrans-2-Butene Reaction with Ozone in the Gas Phase , 2000 .

[125]  K. Becker,et al.  Production of hydrogen peroxide in forest air by reaction of ozone with terpenes , 1990, Nature.

[126]  P. Shepson,et al.  Measurement of the organic nitrate yield from OH reaction with isoprene , 1998 .

[127]  B. Finlayson‐Pitts,et al.  Formation of molecular chlorine from the photolysis of ozone and aqueous sea-salt particles , 1998, Science.

[128]  James G. Anderson,et al.  Mechanism of HOx Formation in the Gas-Phase Ozone-Alkene Reaction. 2. Prompt versus Thermal Dissociation of Carbonyl Oxides to Form OH , 2001 .

[129]  A. Reissell,et al.  Atmospheric Chemistry of Camphor , 2001 .

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

[131]  S. M. Aschmann,et al.  Rate constants for the gas‐phase reactions of cis‐3‐Hexen‐1‐ol, cis‐3‐Hexenylacetate, trans‐2‐Hexenal, and Linalool with OH and NO3 radicals and O3 at 296 ± 2 K, and OH radical formation yields from the O3 reactions , 1995 .

[132]  I. Barnes,et al.  Kinetics and products of the reactions of nitrate radical with monoalkenes, dialkenes, and monoterpenes , 1990 .

[133]  W. Rolle†,et al.  Reaction of NO3 Radicals with 1,3‐Cyclohexadiene, α‐Terpinene, and α‐Phellandrene: Kinetics and Products , 1996 .

[134]  S. Koch,et al.  Formation of new particles in the gas phase ozonolysis of monoterpenes , 2000 .

[135]  A. Volz-Thomas,et al.  Simultaneous measurements of peroxy and nitrate radicals at Schauinsland , 1993 .

[136]  C. N. Hewitt,et al.  Reactive hydrocarbons in the atmosphere. , 1999 .

[137]  S. M. Aschmann,et al.  Products of reaction of OH radicals with α‐pinene , 2002 .

[138]  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.

[139]  S. Madronich,et al.  The Mechanisms of Atmospheric Oxidation of the Alkenes , 2000 .

[140]  E. Grosjean,et al.  The Reaction of Unsaturated Aliphatic Oxygenates with Ozone , 1999 .

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

[142]  J. Orlando,et al.  Rate and mechanism of the reactions of OH and Cl with 2-methyl-3-buten-2-ol , 1998 .

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

[144]  P. Shepson,et al.  Nighttime isoprene chemistry at an urban‐impacted forest site , 1998 .

[145]  S. Paulson,et al.  Measurement of OH radical formation from the reaction of ozone with several biogenic alkenes , 1998 .

[146]  G. Marston,et al.  The Effect of Criegee-Intermediate Scavengers on the OH Yield from the Reaction of Ozone with 2-methylbut-2-ene , 2001 .

[147]  Y. Yokouchi Seasonal and diurnal variation of isoprene and its reaction products in a semi-rural area , 1994 .

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

[149]  E. Grosjean,et al.  Rate constants for the gas-phase reactions of Ozone with unsaturated Aliphatic Alcohols , 1994 .

[150]  J. Seinfeld,et al.  Atmospheric photooxidation of isoprene part II: The ozone‐isoprene reaction , 1992 .

[151]  S. Oltmans,et al.  Surface ozone measurements from a global network , 1994 .

[152]  E. Grosjean,et al.  Carbonyl products of the ozone-unsaturated alcohol reaction , 1995 .