Date of Award:

12-2008

Document Type:

Dissertation

Degree Name:

Doctor of Philosophy (PhD)

Department:

Chemistry and Biochemistry

Committee Chair(s)

Philip J. Silva

Committee

Philip J. Silva

Committee

Robert S. Brown

Committee

Stephen E. Bialkowski

Committee

Cheng-Wei T. Chang

Committee

Randal S. Martin

Abstract

The research in this dissertation explored the sources and chemistry of organic nitrogen aerosols in the atmosphere. Two approaches were employed: field measurements and laboratory experiments. In order to characterize atmospheric aerosol, two ambient studies were conducted in Cache Valley in Northern Utah during strong winter inversions of 2004 and 2005. The economy of this region is heavily dependent on agriculture. There is also a fast growing urban population. Urban and agricultural emissions, aided by the valley geography and meteorology, led to high concentrations of fine particles that often exceeded the national ambient air quality standards. Aerosol composition was dominated by ammonium nitrate and organic species. Mass spectra from an aerosol mass spectrometer revealed that the organic ion peaks were consistent with reduced organic nitrogen compounds, typically associated with animal husbandry practices. Although no direct source characterization studies have been undertaken in Cache Valley with an aerosol mass spectrometer, spectra from a study at a swine facility in Ames, Iowa, did not show any evidence of reduced organic nitrogen species. This, combined with temporal and diurnal characteristics of organic aerosol peaks, was a pointer that the organic nitrogen species in Cache Valley likely formed from secondary chemistry. Application of multivariate statistical analyses to the organic aerosol spectra further supported this hypothesis. To quantify organic nitrogen signals observed in ambient studies as well as understand formation chemistry, three categories of laboratory experiments were performed. These were calibration experiments, smog chamber studies, and an analytical method development. Laboratory calibration experiments using standard calibrants indicated that quantifying the signals from organic nitrogen species was dependent on whether they formed through acid-base chemistry or via secondary organic aerosol pathway. Results from smog chamber reactions of amines with ozone, nitrogen oxides, nitrate radical, and nitric acid showed that the secondary organic aerosol pathway was more plausible than acid-base chemistry, thus making the contribution of the organic nitrogen species to the total aerosol mass in Cache Valley significant. Gas phase and aerosol products formed from the smog chamber reactions were identified and used to devise reaction mechanisms. Finally, an ion chromatographic method for detecting and quantifying some key organic nitrogen species in aerosol was developed and tested.

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Comments

This work was revised and made publicly available electronically on July 19, 2011

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