Product study of the gas-phase reactions of monoterpenes with the OH radical in the presence of NO x

Hydroxyl radical reactions play an important role in the removal of monoterpenes from the troposphere during daytime hours, but there are few data available to date concerning the products of these reactions. From the gas-phase reactions of β-pinene and d-limonene with the OH radical in the presence of NOx, the predicted products, 6,6-dimethylbicyclo[3.1.1]-heptan-2-one and 4-acetyl-1-methylcyclohexene, respectively, were observed with formation yields of 30.0±4.5% and 17.4±2.8%. On the basis of mass spectral data a number of ketone and keto-aldehyde products were tentatively identified in irradiated CH3ONO–NO–air–monoterpene mixtures of d-limonene, α-pinene, Δ3-carene, sabinene, and terpinolene. The estimated formation yields of the observed products range from a low of ∼29% for α-pinene to a high of ∼45% for d-limonene. No significant products were observed from the OH radical-initiated reaction of myrcene. Certain of these monoterpene reaction products, such as the 6,6-dimethylbicyclo[3.1.1]heptan-2-one observed from β-pinene, are less reactive than the parent monoterpene and are formed in sufficient yield that they may serve as markers for the monoterpene emissions. These gas-phase products should be amenable to analysis by the techniques used for ambient air sampling of monoterpenes.

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

[2]  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 .

[3]  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 .

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

[5]  J. Arey,et al.  Monoterpene emission rate measurements from a Monterey pine , 1990 .

[6]  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 .

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

[8]  E. Dlugokencky,et al.  Studies of nitrate radical reactions with some atmospheric organic compounds at low pressures , 1989 .

[9]  M. Mizuochi,et al.  Aerosol formation by the photooxidation of cyclohexene in the presence of nitrogen oxides. , 1988, Environmental science & technology.

[10]  S. M. Aschmann,et al.  Rate constants for the gas-phase reactions of the nitrate radical with a series of organic compounds at 296 .+-. 2 K , 1988 .

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

[12]  S. M. Aschmann,et al.  Rate constants for the gas‐phase reactions of the OH radical with a series of monoterpenes at 294 ± 1 K , 1986 .

[13]  W. Carter,et al.  Extent of H‐atom abstraction from the reaction of the OH radical with 1‐butene under atmospheric conditions , 1985 .

[14]  C. J. Hahn,et al.  Monoterpene hydrocarbons in the nighttime troposphere. , 1985, Environmental science & technology.

[15]  B. Lamb,et al.  Biogenic hydrocarbon emissions from deciduous and coniferous trees in the United States , 1985 .

[16]  W. Carter,et al.  Kinetics and mechanisms of the gas-phase reactions of ozone with organic compounds under atmospheric conditions , 1984 .

[17]  Alan C. Lloyd,et al.  Evaluation of Kinetic and Mechanistic Data for Modeling of Photochemical Smog , 1984 .

[18]  Ø. Hov,et al.  Measurement and modeling of the concentrations of terpenes in coniferous forest air , 1983 .

[19]  D. Albritton,et al.  Measurement of monoterpene hydrocarbons at Niwot Ridge, Colorado , 1983 .

[20]  W. Carter,et al.  Alkyl nitrate formation from the NO/sub x/-air photooxidations of C/sub 2/-C/sub 8/ n-alkanes , 1982 .

[21]  D. Tingey,et al.  Estimates of Isoprene and Monoterpene Emission Rates in Plants , 1982, Botanical Gazette.

[22]  L. Grothaus,et al.  Influence of light and temperature on monoterpene emission rates from slash pine. , 1980, Plant physiology.

[23]  G. Takacs,et al.  Atmospheric photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate , 1980 .

[24]  T. Graedel.  Terpenoids in the atmosphere , 1979 .

[25]  R. Rasmussen.  What do the hydrocarbons from trees contribute to air pollution? , 1972, Journal of the Air Pollution Control Association.

[26]  S. M. Aschmann,et al.  Rate constants for the gas-phase reactions of OH and NO3 radicals and O3 with sabinene and camphene at 296±2 K , 1990 .

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

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

[29]  C. Zetzsch,et al.  A smog chamber for studies of the reactions of terpenes and alkanes with ozone and OH , 1988 .

[30]  G. Petersson.  High ambient concentrations of monoterpenes in a Scandinavian pine forest , 1988 .

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

[32]  Y. Yokouchi,et al.  AEROSOLS FORMED FROM THE CHEMICAL REACTION OF MONOTERPENES AND OZONE , 1985 .

[33]  I. Zenkevich,et al.  Volatile organic compounds in the atmosphere of forests , 1985 .

[34]  P. Maker,et al.  Mechanism for hydroxyl radical initiated oxidation of olefin-nitric oxide mixtures in parts per million concentrations , 1978 .