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Title: The Role of Heterogeneous Chemistry of Volatile ORganic Compounds: A Modeling and Laboratory Study

Abstract

Overview The outputs of this research have been reported annually via the RIMS system. This report serves as an update and final report. The focus of our DOE BES funded project is on the importance of heterogeneous reactions in the troposphere. The primary objectives of our study were to: (i) Evaluate the extent to which heterogeneous chemistry affects the photochemical oxidant cycle, particularly, sources and sinks of tropospheric ozone; and (ii) Conduct laboratory studies on heterogeneous reactions involving NOy, O3 and VOCs on aerosol surfaces. These objectives were pursued through a multidisciplinary approach that combines modeling and laboratory components as discussed in more detail below. In addition, in response to the reconfiguring of the Atmospheric Science Program to focus on aerosol radiative forcing of climate, we also began to investigate the radiative properties of atmospheric aerosol.

Authors:
;
Publication Date:
Research Org.:
The University of Iowa
Sponsoring Org.:
USDOE
OSTI Identifier:
900190
Report Number(s):
DOE/FG62580-1
TRN: US200821%%245
DOE Contract Number:
FG02-98ER62580
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; AEROSOLS; ORGANIC COMPOUNDS; OZONE; PHOTOCHEMICAL OXIDANTS; TROPOSPHERE; ATMOSPHERIC CHEMISTRY; NITROGEN OXIDES; VOLATILE MATTER

Citation Formats

Gregory R. Carmichael, and Vicki H. Grassian. The Role of Heterogeneous Chemistry of Volatile ORganic Compounds: A Modeling and Laboratory Study. United States: N. p., 2007. Web. doi:10.2172/900190.
Gregory R. Carmichael, & Vicki H. Grassian. The Role of Heterogeneous Chemistry of Volatile ORganic Compounds: A Modeling and Laboratory Study. United States. doi:10.2172/900190.
Gregory R. Carmichael, and Vicki H. Grassian. Thu . "The Role of Heterogeneous Chemistry of Volatile ORganic Compounds: A Modeling and Laboratory Study". United States. doi:10.2172/900190. https://www.osti.gov/servlets/purl/900190.
@article{osti_900190,
title = {The Role of Heterogeneous Chemistry of Volatile ORganic Compounds: A Modeling and Laboratory Study},
author = {Gregory R. Carmichael and Vicki H. Grassian},
abstractNote = {Overview The outputs of this research have been reported annually via the RIMS system. This report serves as an update and final report. The focus of our DOE BES funded project is on the importance of heterogeneous reactions in the troposphere. The primary objectives of our study were to: (i) Evaluate the extent to which heterogeneous chemistry affects the photochemical oxidant cycle, particularly, sources and sinks of tropospheric ozone; and (ii) Conduct laboratory studies on heterogeneous reactions involving NOy, O3 and VOCs on aerosol surfaces. These objectives were pursued through a multidisciplinary approach that combines modeling and laboratory components as discussed in more detail below. In addition, in response to the reconfiguring of the Atmospheric Science Program to focus on aerosol radiative forcing of climate, we also began to investigate the radiative properties of atmospheric aerosol.},
doi = {10.2172/900190},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu Mar 01 00:00:00 EST 2007},
month = {Thu Mar 01 00:00:00 EST 2007}
}

Technical Report:

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  • The purpose of this phase of the study was to develop models of VOC emissions that can be used to determine the importance of individual stages in the preliminary and primary operations sequence. Included in the study was selection of candidate operations for design or operational modification to minimize emission rates. Overall emissions predicted during preliminary and primary treatment were approximately 25% of influent VOC load and varied from 0.02 to 0.03 g-VOCs/cu m of wastewater treated, depending on the method of plant operation selected. Major losses occurred in aerated grit chambers and at the weirs. Losses from non-aerated tanksmore » and conveyance channels were negligible relative to other units. Emissions predicted for headworks steps were small, but not negligible. Options to covering treatment units and collection of off-gases are clearly available in many cases. Submerged weirs, launder depth controls, and elimination of aeration are examples of modifications that can be used to effectively decrease VOC emissions.« less
  • In October 1988, the federal and provincial environment ministers requested that a comprehensive national plan be developed to further manage nitrogen oxides (NOx) and volatile organic compound (VOC) emissions in Canada. This technical annex considers the state of the environment, including the effects of nitrogen-related compounds on the environment, existing environmental targets developed to protect human health and vegetation, and observed concentrations and deposition levels in Canada; describes the state of knowledge of atmospheric chemistry and implications for the control of ozone; and discusses the transboundary contribution to the NOx and VOC problem in Canada.
  • 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
  • The relative hydroxyl (OH) reaction rates from the simulated atmospheric oxidation of several acetates and other oxygenated organic compounds have been measured. The OH radical was from the photolysis of methyl nitrite in air. The reaction products of 2-ethoxyethyl acetate with OH identified and quantified and a reaction mechanism is proposed. The measured rate constants (x10(-11)cm(3)molecule(-1)s(-1)) are: 6.77+/-0.50 for trans-4-octene, 1.40+/-0.07 for 4-methyl-2-pentanone, 6.70+/-0.23 for trans-2-heptene, .342+/-0.087 for n-propyl acetate, .571+/-0.094 for n-butyl acetate, 0.753+/-0.048 for n-pentyl acetate, 1.056+/-0.131 for 2-ethoxyethyl acetate, 1.356+/-0.232 for 2-ethoxyethyl isobutyrate, 2.722+/-.206 for 2-ethoxyethyl methacrylate, 4.34+/-.385 4-penten-1-yl acetate, and 3.33+/-0.122 for 3-ethoxyacrylic acid ethyl ester.
  • The gas-phase transfer of hexachlorobenzene (HCB) from the solid to the chambers used for sediment-water bioaccumulation tests was investigated. The physical properties of HCB found in the literature are summarized. Significant discrepencies were found among different methods. The chief sources in uncertainty in these data were due to variations in temperature, and the possible incomplete equilibration of the solid with the gas. These items are discussed in detail. The theory for transfer from gas to a liquid is developed. The effects of association of HCB with humate and other competing processes (head space losses, adsorption to food, organisms, sediment) aremore » included. Experimental data from the use of the apparatus in actual bioaccumulation experiments are discussed.« less