Gas-phase reaction of ozone withtrans-2-hexenal,trans-2-hexenyl acetate, ethylvinyl ketone, and 6-methyl-5-hepten-2-one

Grosjean, Eric; Grosjean, Daniel; Seinfeld, John H.

doi:10.1002/(sici)1097-4601(1996)28:5<373::aid-kin6>3.0.co;2-s

Cited by 62 publications

(79 citation statements)

References 23 publications

(47 reference statements)

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“…For this reason, the aldehydes lifetime is in the order of 200-400 h, which is comparable to the lifetimes due to O 3 with trans-2-hexenal (only the trans-2-hexenal has been studied (Grosjean et al, 1996). Nevertheless, the contribution of Cl atoms may be significant in those areas with higher concentrations.…”

Section: Resultsmentioning

confidence: 82%

Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

Rodrı́guez

Rodrı́guez²,

Notario

et al. 2005

Atmos. Chem. Phys.

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Abstract. The reactions of Cl atoms with a series of unsaturated aldehydes have been investigated for the first time using a relative method. In order to obtain additional information for a qualitative structure versus reactivity discussion, we have also determined the rate coefficients for the reactions of atomic chlorine with their respective saturated aldehydes. These relative measurements were performed at room temperature and atmospheric pressure of air and N 2 , by using ethane, propene and 1-butene as reference compounds. The weighted average relative rate constants obtained, k Cl ±2σ (in units of cm 3 molecule −1 s −1 ) were: trans-2-pentenal (1.31±0.19)×10 −10 ; trans-2-hexenal (1.92±0.22)×10 −10

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Section: Resultsmentioning

confidence: 82%

Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

Rodrı́guez

Rodrı́guez²,

Notario

et al. 2005

Atmos. Chem. Phys.

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“…This value is typical for the variety of methyl‐substituted internal olefins that have been studied [cf. Grosjean et al , 1996; Grosjean and Grosjean , 1999; Atkinson et al , 1995]. We note that for these species, O 3 reaction alone (at 40 ppb O 3 ) leads to a lifetime of ∼40 min.…”

Section: Methodsmentioning

confidence: 84%

Comparison of the measured and simulated isoprene nitrate distributions above a forest canopy

et al. 2005

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[1] It is known that isoprene nitrate production can represent a significant sink for atmospheric NO x and free radicals, and therefore this chemistry is important to understanding tropospheric O 3 and the fate of NO x in forest-impacted environments. Although six structural isoprene nitrate isomers can be produced from OH reaction with isoprene in the presence of NO, these have not been separately quantified in the atmosphere. A zero-dimensional isoprene photochemistry model was developed based on the known gas-phase isoprene oxidation chemistry for comparison with isoprene nitrate ambient concentration data obtained from field and laboratory measurements. The model incorporates calculated individual branching ratios for each isomer as well as rate constants for the reaction of each isomeric nitrate with the OH radical and O 3 and losses from the boundary layer by dry deposition and vertical mixing. The model indicates that under atmospheric conditions, there should be three nitrate isomers that represent 86% of the total, while our ambient measurements indicate only two dominant nitrate isomers. This contrasts significantly with what is observed in the laboratory because of atmospheric conversion to other nitrogen-containing products. These secondary nitrates are likely to be a significant fraction of NO y in forest environments.Citation: Giacopelli, P., K. Ford, C. Espada, and P. B. Shepson (2005), Comparison of the measured and simulated isoprene nitrate distributions above a forest canopy,

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“…However, kinetic calculations using the reported second order rate constants for the reactions of ozone with 6-MHO and geranyl acetone (34,20), indicate that ≈90% of the 4-OPA found in the gas phase during these experiments was derived from surface reactions (see SI Text).…”

Section: Resultsmentioning

confidence: 99%

Reactions of ozone with human skin lipids: Sources of carbonyls, dicarbonyls, and hydroxycarbonyls in indoor air

Wisthaler

Weschler

2010

Proc. Natl. Acad. Sci. U.S.A.

371

544

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This study has used proton transfer reaction-mass spectrometry (PTR-MS) for direct air analyses of volatile products resulting from the reactions of ozone with human skin lipids. An initial series of small-scale in vitro and in vivo experiments were followed by experiments conducted with human subjects in a simulated office. The latter were conducted using realistic ozone mixing ratios (≈15 ppb with occupants present). Detected products included mono- and bifunctional compounds that contain carbonyl, carboxyl, or α -hydroxy ketone groups. Among these, three previously unreported dicarbonyls have been identified, and two previously unreported α -hydroxy ketones have been tentatively identified. The compounds detected in this study (excepting acetone) have been overlooked in surveys of indoor pollutants, reflecting the limitations of the analytical methods routinely used to monitor indoor air. The results are fully consistent with the Criegee mechanism for ozone reacting with squalene, the single most abundant unsaturated constituent of skin lipids, and several unsaturated fatty acid moieties in their free or esterified forms. Quantitative product analysis confirms that squalene is the major scavenger of ozone at the interface between room air and the human envelope. Reactions between ozone and human skin lipids reduce the mixing ratio of ozone in indoor air, but concomitantly increase the mixing ratios of volatile products and, presumably, skin surface concentrations of less volatile products. Some of the volatile products, especially the dicarbonyls, may be respiratory irritants. Some of the less volatile products may be skin irritants.

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Gas-phase reaction of ozone withtrans-2-hexenal,trans-2-hexenyl acetate, ethylvinyl ketone, and 6-methyl-5-hepten-2-one

Cited by 62 publications

References 23 publications

Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

Comparison of the measured and simulated isoprene nitrate distributions above a forest canopy

Reactions of ozone with human skin lipids: Sources of carbonyls, dicarbonyls, and hydroxycarbonyls in indoor air

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