A Computational Approach to Understanding Aerosol Formation and Oxidant Chemistry in the Troposphere

PDF Version Also Available for Download.

Description

An understanding of the mechanisms and kinetics of aerosol formation and ozone production in the troposphere is currently a high priority because these phenomena are recognized as two major effects of energy-related air pollution. Atmospheric aerosols are of concern because of their effect on visibility, climate, and human health. Equally important, aerosols can change the chemistry of the atmosphere, in dramatic fashion, by providing new chemical pathways (in the condensed phase) unavailable in the gas phase. The oxidation of volatile organic compounds (VOCs) and inorganic compounds (e.g., sulfuric acid, ammonia, nitric acid, ions, and mineral) can produce precursor molecules that ... continued below

Physical Description

PDFN

Creation Information

Francisco, Joseph S.; Kathmann, Shawn M.; Schenter, Gregory K.; Dang, Liem X.; Xantheas, Sotiris S.; Garrett, Bruce C. et al. April 18, 2006.

Context

This report is part of the collection entitled: Office of Scientific & Technical Information Technical Reports and was provided by UNT Libraries Government Documents Department to Digital Library, a digital repository hosted by the UNT Libraries. More information about this report can be viewed below.

Who

People and organizations associated with either the creation of this report or its content.

Publisher

  • Pacific Northwest National Laboratory (U.S.)
    Publisher Info: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States), Environmental Molecular Sciences Laboratory (EMSL)
    Place of Publication: Richland, Washington

Provided By

UNT Libraries Government Documents Department

Serving as both a federal and a state depository library, the UNT Libraries Government Documents Department maintains millions of items in a variety of formats. The department is a member of the FDLP Content Partnerships Program and an Affiliated Archive of the National Archives.

Contact Us

What

Descriptive information to help identify this report. Follow the links below to find similar items on the Digital Library.

Description

An understanding of the mechanisms and kinetics of aerosol formation and ozone production in the troposphere is currently a high priority because these phenomena are recognized as two major effects of energy-related air pollution. Atmospheric aerosols are of concern because of their effect on visibility, climate, and human health. Equally important, aerosols can change the chemistry of the atmosphere, in dramatic fashion, by providing new chemical pathways (in the condensed phase) unavailable in the gas phase. The oxidation of volatile organic compounds (VOCs) and inorganic compounds (e.g., sulfuric acid, ammonia, nitric acid, ions, and mineral) can produce precursor molecules that act as nucleation seeds. The U.S. Department of Energy (DOE) Atmospheric Chemistry Program (ACP) has identified the need to evaluate the causes of variations in tropospheric aerosol chemical composition and concentrations, including determining the sources of aerosol particles and the fraction of such that are of primary and secondary origin. In particular, the ACP has called for a deeper understanding into aerosol formation because nucleation creates substantial concentrations of fresh particles that, via growth and coagulation, influence the Earth's radiation budget. Tropospheric ozone is also of concern primarily because of its impact on human health. Ozone levels are controlled by NOx and by VOCs in the lower troposphere. The VOCs can be either from natural emissions from such sources as vegetation and phytoplankton or from anthropogenic sources such as automobiles and oil-fueled power production plants. The major oxidant for VOCs in the atmosphere is the OH radical. With the increase in VOC emissions, there is rising concern regarding the available abundance of HOx species needed to initiate oxidation. Over the last five years, there have been four field studies aimed at initial measurements of HOx species (OH and HO? radicals). These measurements revealed HOx levels that are two to four times higher than expected from the commonly assumed primary sources. Such elevated abundances of HOx imply a more photochemically active troposphere than previously thought. This implies that rates of ozone formation in the lower region of the atmosphere and the oxidation of SO? can be enhanced, thus promoting the formation of new aerosol properties. Central to unraveling this chemistry is the ability to assess the photochemical product distributions resulting from the photodissociation of by-products of VOC oxidation. We propose to use state-of-the-art theoretical techniques to develop a detailed understanding of the mechanisms of aerosol formation in multicomponent (mixed chemical) systems and the photochemistry of atmospheric organic species. The aerosol studies involve an approach that determines homogeneous gas-particle nucleation rates from knowledge of the molecular interactions that are used to define properties of molecular clusters. Over the past several years we developed Dynamical Nucleation Theory (DNT), a novel advance in the theoretical description of homogeneous gas-liquid nucleation, and applied it to gas-liquid nucleation of a single component system (e.g., water). The goal of the present research is to build upon these advances by extending the theory to multicomponent systems important in the atmosphere (such as clusters containing sulfuric acid, water, ions, ammonia, and organics). In addition, high-level ab initio electronic structure calculations will be used to unravel the chemical reactivity of the OH radical and water clusters.

Physical Description

PDFN

Language

Item Type

Identifier

Unique identifying numbers for this report in the Digital Library or other systems.

  • Report No.: PNNL-15772
  • Grant Number: AC05-76RL01830
  • DOI: 10.2172/881691 | External Link
  • Office of Scientific & Technical Information Report Number: 881691
  • Archival Resource Key: ark:/67531/metadc875031

Collections

This report is part of the following collection of related materials.

Office of Scientific & Technical Information Technical Reports

What responsibilities do I have when using this report?

When

Dates and time periods associated with this report.

Creation Date

  • April 18, 2006

Added to The UNT Digital Library

  • Sept. 21, 2016, 2:29 a.m.

Description Last Updated

  • Dec. 6, 2016, 7:54 p.m.

Usage Statistics

When was this report last used?

Yesterday: 0
Past 30 days: 0
Total Uses: 2

Interact With This Report

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

Francisco, Joseph S.; Kathmann, Shawn M.; Schenter, Gregory K.; Dang, Liem X.; Xantheas, Sotiris S.; Garrett, Bruce C. et al. A Computational Approach to Understanding Aerosol Formation and Oxidant Chemistry in the Troposphere, report, April 18, 2006; Richland, Washington. (digital.library.unt.edu/ark:/67531/metadc875031/: accessed August 18, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.