Photochemistry of Hazardous Chemicals in Natural Water

Abstract

The aquatic photo chemistry of two high-energy compounds was investigated as a part of a larger study of their environmental fate. Ammonium dinitramide (ADN) absorbs light < 4OOnm and degrades rapidly upon exposure to sunlight. Half-lives for the photolysis of ADN at the surface of a body of water were calculated as six minutes for a location in Syracuse, NY. However, much of the light that degrades ADN directly is absorbed in the top layer of water; the half-life at a depth of 2m was calculated as 15 years. A model of the absorption of light passing through the water column in combination with quantum yields was used in order to compare predicted and observed rates in Onondaga Lake, with good agreement. Dark solutions of ADN were stable indefinitely and indirect photolysis did not provide a significant decay mechanism. Although quadricyclane did not photolyze in distilled water, it degraded if natural dissolved organic matter (DOM) was also present. This phenomenon was ascribed to the reaction of quadricyclane with hydroperoxy (HOe) and its conjugate base, superoxide (02 degrees). The kinetics of this reaction were tested through the use of an alternative Hoe/e2- generator, xanthine-xanthine oxidase and a probe, ferricytochrome C. Using quadricyclan9 as a probe, the pH dependence of the production rate of Hoe/e2' was determined for a commercial humic solution. Results indicated that the predominant mechanism of formation of Hoe/e2' was electron transfer from an excited DOM moiety to oxygen and not the reaction of oxygen with hydrated electrons, photejected by excited DOM.

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Document Details

Document Type
Technical Report
Publication Date
Jul 31, 2000
Accession Number
ADA383559

Entities

People

  • John P. Hassett

Organizations

  • State University of New York at Albany

Tags

Communities of Interest

  • Energy and Power Technologies
  • Weapons Technologies

DTIC Thesaurus Topics

  • Air Force
  • Buffers (Chemistry)
  • Chemical Reaction Properties
  • Chemical Reactions
  • Chemical Synthesis
  • Chemistry
  • Electromagnetic Radiation
  • Electron Transfer
  • Ionization
  • Liquid Chromatography
  • Measurement
  • Oxygen
  • Photochemical Reactions
  • Quantum Yields
  • Rocket Oxidizers
  • Solar Radiation
  • Solid Rocket Oxidizers

Readers

  • Mathematics or Statistics
  • Organic Chemistry
  • Systems Analysis and Design

Technology Areas

  • Microelectronics
  • Quantum Computing