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PRODUCTS OF THE GAS-PHASE REACTIONS OF 1,3-BUTADIENE WITH OH AND NO3 RADICALS. (R825252)
Citation:
Tuazon, E. C., S. M. Alvarado, S. M. Aschmann, R. Atkinson, AND J. Arey. PRODUCTS OF THE GAS-PHASE REACTIONS OF 1,3-BUTADIENE WITH OH AND NO3 RADICALS. (R825252). ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, 33:3586-3595, (1999).
Description:
1,3-Butadiene is emitted into the atmosphere from a number of sources
including combustion sources and is listed in the United States as a hazardous
air pollutant. In the atmosphere, 1,3-butadiene reacts with OH radicals,
NO3 radicals, and O3 with the dominant tropospheric
removal processes being daytime reaction with the OH radical and nighttime
reaction with the NO3 radical. We have used gas chromatography, in
situ Fourier transform infrared (FT-IR) absorption spectroscopy, and in situ
atmospheric pressure ionization tandem mass spectrometry (API-MS) to identify
and quantify the products formed from the reactions of 1,3-butadiene with OH
radicals (in the presence of NO) and NO3 radicals. Acrolein,
formaldehyde, and furan were identified and quantified from the OH
radical-initiated reaction, with formation yields of 0.58 ? 0.04, 0.62 ? 0.05,
and 0.03-0.04, respectively. Organic nitrates were observed by FT-IR
spectroscopy with an estimated yield of 0.07 ? 0.03, and the API-MS analyses
indicated that these organic nitrates are mainly the hydroxynitrate
HOCH2CH=CHCH2ONO2 and/or its isomers. API-MS
analyses showed the formation of a hydroxycarbonyl with the formula
C4H6O2, attributed to HOCH2CH=CHCHO
and/or its isomers. The major products of the NO3 radical-initiated
reaction were organic nitrates; the API-MS analyses indicated the formation of
acrolein, 1,2-epoxy-3-butene, and unsaturated C4-hydroxycarbonyls,
hydroxynitrates, carbonyl nitrates, and nitrooxyhydroperoxides. Acrolein, HCHO,
and furan were again quantified by gas chromatographic and FT-IR analyses. Our
data are compared with previous literature studies, and detailed reaction
mechanisms are presented and discussed.