Pinene, atmosphere

Grosjean D, EL Williams, E Grosjean, JM Andino, JH Seinfeld (1993c) Atmospheric oxidation of biogenic hydrocarbons reaction of ozone with 3-pinene, D-limonene, and rra -caryophyllene. Environ Sci Technol 27 2754-2758. 

Organic aerosols formed by gas-phase photochemical reactions of hydrocarbons, ozone, and nitrogen oxides have been identified recently in both urban and rural atmospheres. Aliphatic organic nitrates, such dicarboxylic acids as adipic and glutaric acids, carboxylic acids derived from aromatic hydrocarbons (benzoic and phenylacetic acids) and from terpenes emitted by vegetation, such as pinonic acid from a pinene, have been identified. The most important contribution in this held has been that of Schuetzle et al., who used computer-controlled... 

Vereecken and Peelers (2000) reported that acetone is formed from the reaction of a-pinene and OH radicals in the atmosphere. This reaction resulted in an acetone yield of 8.5% which is consistent with available experimental data. 

Vereecken, L. and Peelers, J. Theoretical study of the formation of acetone in the OH-initiated atmospheric oxidation of a-pinene, / PAjs. Chem. A, 104(47) 11140-11146, 2000. 

Figure 26. A kinetic plot on air oxidation of a-pinene using Co(III)-HMS as the catalyst rmder atmospheric pressure at 100 °C [ 15].

Arnts, R. R., Peterson, W. B., Seila, R. L., and Gay, B. W., Jr. (1982). Estimates of alpha-pinene emissions from a loblolly pine forest using an atmospheric diffusion model. 

Grosjean, D., E. L. Williams, II, E. Grosjean, J. M. Andino, and J. H. Seinfeld, Atmospheric Oxidation of Biogenic Hydrocarbons Reaction of Ozone with /J-Pinene, d-Limonene, and trans-Caryophyllene, Em iron. Sci. Techriol., 27, 2754-2758 (1993a). 

Hallquist, M I. Wangberg, and E. Ljungstrom, Atmospheric Fate of Carbonyl Oxidation Products Originating from a-Pinene and A3-Carene Determination of Rate of Reaction with OH and N03 Radicals, UV Absorption Cross Sections, and Vapor Pressures, Environ. Sci. TechnoL, 31, 3166-3172 (1997). 

Hatakeyama, S., K. Izumi, T. Fukuyama, H. Akimoto, and N. Washida, Reactions of OH with a-Pinene and /3-Pinene in Air Estimate of Global CO Production from the Atmospheric Oxidation of Terpenes, J. Geophys. Res., 96, 947-958 (1991). 

Balsam turpentine oil is obtained from the resins of living trees of suitable Pinus species by distillation at atmospheric pressure and temperatures up to 180°C, or by other fractionation methods, which do not change the terpene composition of the resins. Wood turpentine oils, on the other hand, are generally obtained by steam distillation of chopped tree trunks, dead wood, or of resin extracted from this wood. Sulfate turpentine oil is produced as waste in the manufacture of cellulose by the sulfate process and is also a wood turpentine. Pine oil is another wood turpentine oil that is obtained by dry distillation of suitable pine and fir trees, followed by fractionation. However, the term pine oil is nowadays used for a product which is manufactured by hydration of turpentine oil (a-pinene). The resulting product is a mixture of monoterpenes containing o-terpineol as the main component. In addition to many other technical purposes, it is used to a large extent in cheap perfumes for technical applications. 

In addition to being oxidized by the hydroxyl radical, alkenes may react with the N03 radical as has been described by several investigators (52, 56, 66). Listed in Table I are some of the organic nitrates that have been predicted to be produced via reaction of OH and N03 with isoprene and pro-pene. Analogous compounds would be expected from other simple alkenes and from terpenes such as a- and (3-pinene. Other possible organic nitrates may be produced via the oxidation of aromatic compounds (53, 54) and the oxidation of carbonaceous aerosols (67). Quantitative determination of these species has not been made in the ambient atmosphere. 

Capouet, M., Peeters, J., Noziere, B. and Muller, J.F. (2004) Alpha-pinene oxidation by OH simulations of laboratory experiments. Atmospheric Chemistry and Physics, 4, 2285-311. 

Product study and mechanisms of the reactions of alpha-pinene and of pinonaldehyde with OH radicals. Journal of Geophysical Research-Atmospheres, 104 (D19), 23645-56. 

Warscheid, B. and Hoffmann, T. (2001) On-line measurements of alpha-pinene ozonolysis products using an atmospheric pressure chemical ionization ion-trap mass spectrometer. Atmospheric Environment, 35, 2927-40. 

Wolkoff, P., Clausen, P.A., Wilkins, C.K., Hougaard, K.S. and Nielsen, G.D. (1999) Formation of strong airway irritants in a model mixture of (+)-alpha-pinene/ozone. Atmospheric Environment, 33, 693-8. 

Barr et al. (2003) performed an analysis of the impact of phytogenic aerosol (PhA) which is defined as forming mainly due to monoterpene oxidation (primarily, a- and /3-pinenes), on the radiative regime of the ABL over the forest in the eastern part of Canada. In the forest ecosystem the level of emissions to the atmosphere of biogenic hydrocarbons is moderate, with the concentration of a- and /3-pinenes constituting about 1.6 ppb. NMHC oxidation resulted in the formation of PhA at a number density of particles of about 5 108 cm 3. For a given concentration and size distribution of aerosol, its impact on the short-wave radiation transfer in the ABL was assessed. 

The mechanism of the hydroxyl radical-initiated oxidation of /i-pincnc in the presence of NO has been investigated using a discharge-flow system. Propagation of hydroxyl radicals was observed after the addition of O2 and NO, and the measured concentration profiles were compared with simulations based on both the master chemical mechanism and the regional atmospheric chemistry mechanism for /i-pinene oxidation.228... 

In a 2-L, three-necked flask fitted with a condenser, mechanical stirrer, and a gas inlet tube Is placed 90.0 g (0.66 mol) of (-)-a-pinene (Note 15), The flask 1s cooled to 0°C and under an inert atmosphere a total of 300 mL (0,30 mol) of 1 M borane in tetrahydrofuran (Note 16) Is added dropwise over a 1-hr period. The solution is stirred for 18 hr at 0°C during which time a white precipitate of (+)-di-3-pinanylborane forms. This, solution is then cooled to -78°C. The ca. 0.30 mol solution of methyl 2,4-cyclopentadiene-l-acetate (Part B) 1s transferred at -78°C to a 500-mL pressure-equalizlng dropping funnel through a U-tube in an Inert atmosphere, and is added rapidly, In one portion, to the stirring solution of di-3-pinanylborane at -78°C. After this mixture is stirred for 6 hr at -78°C, the bath temperature is allowed to rise to 0°C and the mixture is stirred for 16 hr at 0°C to complete the hydroboratlon reaction. 

Oxidation of hydrocarbons has long been considered as a fundamental problem to atmospheric chemists, both from experimental and theoretical points of view, because of the inherent complexity. The reaction kinetics and mechanism of atmospheric hydrocarbons have been the focuses of numerous researches in both experimental and theoretical aspects. Although advances have been made in elucidation of the VOC oxidation mechanisms, large uncertainty and tremendous numbers of unexplored reactions still remain. Several review articles on the atmospheric degeneration of VOCs have been published [4,11-14]. In this review, recent advances in the application of theoretical methods to the atmospheric oxidation of biogenic hydrocarbons are discussed. We will introduce the backgrounds on the quantum chemical calculations and kinetic rate theories, recent progress on theoretical studies of isoprene and a-, y3-pinenes, and studies on other monoter-penes and sesquiterpenes. 

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