Studies of the Atmospheric Chemsitry of Energy-Related Volatile Organic Compounds and of their Atmospheric Reaction Products
The focus of this contract was to investigate selected aspects of the atmospheric chemistry of volatile organic compounds (VOCs) emitted into the atmosphere from energy-related sources as well as from biogenic sources. The classes of VOCs studied were polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs, the biogenic VOCs isoprene, 2-methyl-3-buten-2-ol and cis-3-hexen-1-ol, alkenes (including alkenes emitted from vegetation) and their oxygenated atmospheric reaction products, and a series of oxygenated carbonyl and hydroxycarbonyl compounds formed as atmospheric reaction products of aromatic hydrocarbons and other VOCs. Large volume reaction chambers were used to investigate the kinetics and/or products of photolysis and of the gas-phase reactions of these organic compounds with hydroxyl (OH) radicals, nitrate (NO3) radicals, and ozone (O3), using an array of analytical instrumentation to analyze the reactants and products (including gas chromatography, in situ Fourier transform infrared spectroscopy, and direct air sampling atmospheric pressure ionization tandem mass spectrometry). The following studies were carried out. The photolysis rates of 1- and 2-nitronaphthalene and of eleven isomeric methylnitronaphthalenes were measured indoors using blacklamp irradiation and outdoors using natural sunlight. Rate constants were measured for the gas-phase reactions of OH radicals, Cl atoms and NO3 radicals with naphthalene, 1- and 2-methylnaphthalene, 1- and 2-ethylnaphthalene and the ten dimethylnaphthalene isomers. Rate constants were measured for the gas-phase reactions of OH radicals with four unsaturated carbonyls and with a series of hydroxyaldehydes formed as atmospheric reaction products of other VOCs, and for the gas-phase reactions of O3 with a series of cycloalkenes. Products of the gas-phase reactions of OH radicals and O3 with a series of biogenically emitted VOCs were identified and quantified. Ambient atmospheric measurements of the concentrations of a number of PAHs, nitro-PAHs, nitrated polycyclic aromatic compounds and biogenic VOCs were carried out in the Los Angeles air basin. In addition to these laboratory and ambient field studies, two literature reviews of VOC atmospheric chemistry and of the kinetics of the reactions of OH radicals with alkanes were also carried out. This research has been reported in 15 peer-reviewed publications.
- Research Organization:
- University of California, Riverside, CA
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- FG02-01ER63095
- OSTI ID:
- 902099
- Report Number(s):
- DOE/ER/63095-1; TRN: US200722%%318
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ATMOSPHERIC CHEMISTRY
ATMOSPHERIC PRESSURE
GAS CHROMATOGRAPHY
LIGHT BULBS
LOS ANGELES
ORGANIC COMPOUNDS
POLYCYCLIC AROMATIC HYDROCARBONS
RADICALS
VOLATILE MATTER
HYDROXYL RADICALS
NITRATES
Atmospheric chrmistry
volatile organic compound
hydroxyl radical
nitrate radical
ozone
reaction kinetics
reaction mechanisms