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Title: Studies of the Atmospheric Chemsitry of Energy-Related Volatile Organic Compounds and of their Atmospheric Reaction Products

Abstract

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-ethylnaphthalenemore » 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.« less

Authors:
;
Publication Date:
Research Org.:
University of California, Riverside, CA
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
902099
Report Number(s):
DOE/ER/63095-1
TRN: US200722%%318
DOE Contract Number:
FG02-01ER63095
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 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

Citation Formats

Roger Atkinson, and Janet Arey. Studies of the Atmospheric Chemsitry of Energy-Related Volatile Organic Compounds and of their Atmospheric Reaction Products. United States: N. p., 2007. Web. doi:10.2172/902099.
Roger Atkinson, & Janet Arey. Studies of the Atmospheric Chemsitry of Energy-Related Volatile Organic Compounds and of their Atmospheric Reaction Products. United States. doi:10.2172/902099.
Roger Atkinson, and Janet Arey. Sat . "Studies of the Atmospheric Chemsitry of Energy-Related Volatile Organic Compounds and of their Atmospheric Reaction Products". United States. doi:10.2172/902099. https://www.osti.gov/servlets/purl/902099.
@article{osti_902099,
title = {Studies of the Atmospheric Chemsitry of Energy-Related Volatile Organic Compounds and of their Atmospheric Reaction Products},
author = {Roger Atkinson and Janet Arey},
abstractNote = {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.},
doi = {10.2172/902099},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sat Apr 14 00:00:00 EDT 2007},
month = {Sat Apr 14 00:00:00 EDT 2007}
}

Technical Report:

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  • In the second year of an overall two-year contract for the Coordinating Research Council and the National Renewable Energy Laboratory, the Statewide Air Pollution Research Center (SAPRC), University of California, Riverside, has carried out product studies of the gas-phase reactions of the OH radical (in the presence of NO) and O3 with a series of alkenes to (1) determine the yields of O((3)P) atoms, OH radicals and those carbonyls expected from cleavage of the >C=C< bond from the O3 reactions with a series of alkenes in the presence of an OH radical scavenger, and (2) determine the yields of themore » carbonyls expected from cleavage of the >C=C< bond from the reactions of the OH radical with a series of alkenes, including the 1-alkenes 1-pentene through 1-octene.« less
  • Photochemical oxidant models are essential tools for assessing effects of emissions changes on ground-level ozone formation. Such models are needed for predicting the ozone impacts of increased alternative fuel use. The gas-phase photochemical mechanism is an important component of these models because ozone is not emitted directly, but is formed from the gas-phase photochemical reactions of the emitted volatile organic compounds (VOCs) and oxides of nitrogen (NO{sub x}) in air. The chemistry of ground level ozone formation is complex; hundreds of types of VOCs being emitted into the atmosphere, and most of their atmospheric reactions are not completely understood. Becausemore » of this, no chemical model can be relied upon to give even approximately accurate predictions unless it has been evaluated by comparing its predictions with experimental data. Therefore an experimental and modeling study was conducted to assess how chemical mechanism evaluations using environmental chamber data are affected by the light source and other chamber characteristics. Xenon arc lights appear to give the best artificial representation of sunlight currently available, and experiments were conducted in a new Teflon chamber constructed using such a light source. Experiments were also conducted in an outdoor Teflon Chamber using new procedures to improve the light characterization, and in Teflon chambers using blacklights. These results, and results of previous runs other chambers, were compared with model predictions using an updated detailed chemical mechanism. The magnitude of the chamber radical source assumed when modeling the previous runs were found to be too high; this has implications in previous mechanism evaluations. Temperature dependencies of chamber effects can explain temperature dependencies in chamber experiments when Ta-300{degree}K, but not at temperatures below that.« less
  • Environmental chamber experiments were conducted to measure reactivities of 12 representative alkanes, alkenes, aromatics, and oxygenates in irradiations of various reactive organic gas (ROG) surrogate - NOx - air mixtures designed to approximate photochemical smog. The results show that VOCs have a greater range of reactivities with a simpler surrogate than when the more realistic surrogate is used. Reducing NOx reduced reactivities by differing amounts for different VOCs. These results are consistent with model predictions, though the model performed better simulating experiments with the more complex surrogate than the simpler systems, because the latter are more sensitive to differrences amongmore » the VOCs. The model predicted that experimental and atmospheric reactivities may correlate under high NOx conditions, but not when NOx is low. Thus the best use of reactivity experiments is evaluating the models which predict atmospheric reactivities.« less
  • An experimental and modeling study was conducted to assess how chemical mechanism evaluations using environmental chamber data are affected by the light source and other chamber characteristics. Xenon arc light lights appear to give best artificial representation of sunlight currently available, and experiments were conducted in a new Teflon chamber constructed using such a light source. Experiments were also conducted in an Outdoor Teflon Chamber using new procedures to improve the light characterization, and in Teflon chambers using blacklights. These results and results of previous runs other chambers, were compared with model predictions using an updated detailed chemical mechanism.
  • In 1980, Lawrence Livermore National Laboratory (LLNL) initiated a preliminary ground water study beneath and in the vicinity of the LLNL site in Livermore, California. Findings from that study indicated that volatile organic compounds (VOCs), primarily tetrachloroethylene (PCE) and trichloroethylene (TCE), were present in local ground water. Subsequent sampling results showed several locations with VOCs in the parts-per-billion range, and three areas where parts-per-million concentrations were detected. Subsequently, more than 200 wells were drilled and tested during investigations to assess the lateral and stratigraphic extent of ground water contamination and to understand the hydrogeologic characteristics under the Laboratory and adjacentmore » affected areas. Although PCE and TCE predominate, dichloroethanes, dichloroethylenes, and carbon tetrachloride have been detected in ground water at concentrations exceeding California Department of Health Services recommended action levels. In order to predict the rate and extent of movement of the VOCs in ground water, it is essential to understand the sorptive properties of these compounds in relation to the subsurface soils that exist in this area. TCE and PCE were selected for study initially because of their predominance in the contaminant plume. Additional tests were performed using 1,2-dichloroethane (DCA), 1,2-dichloroethene (DCE), and chloroform (CF). 28 refs., 4 figs., 7 tabs.« less