Date of Award

2008

Degree Type

Dissertation

Abstract

Formaldehyde (CH2O) is a central component of photooxidation chemistry. The atmospheric sources of CH2O involve a complex mixture of biogenic and anthropogenic volatile organic compounds (VOCs). This study explores the geographical and altitudinal variations of CH2O production from its precursors over the Eastern U.S. and assesses the contributions from biogenic and anthropogenic VOC emissions to atmospheric CH2O. Measurements of airborne CH2O and hydrocarbons over North America and model results were used to evaluate CH2O production from its precursors. Source attribution results from a photochemical box model indicate 95% of the CH2O arose in various proportions from a mixture of methane, isoprene, methyl hydroperoxide, methanol, and a peroxyacetyl group. Methane on average contributed 32% at altitudes below 2 km to CH2O production, 43% in 2-6 km, and 52% in 6-12 km. It was the predominant CH 2O source in 1-12 km. Isoprene served as a major source of CH2 O (range 0-72%, average 17%) over the southeastern U.S. region within 0-1-km layer. Methyl hydroperoxide was one of the predominant contributors over the ocean and averaged from 6 to 33% in all layers. Production from the peroxyacetyl group and methanol were 7-17% and 10-14% on average in the layers in 0-12 km, respectively. A compound specific radiocarbon analysis technique was developed for atmospheric CH2O to examine its biogenic and anthropogenic carbon fraction. The method used filter collection, a preparative capillary gas chromatography isolation technique, and AMS detection. Ambient samples were collected on the roof of the CACS building at the Bay Campus of the University of RI, Narragansett, RI. The 14CH2O data, 48-hour back trajectories, and VOC observations from the RI Department of Environmental Management were used to assess the relative contributions of biogenic and fossil precursors to CH2O. The results show a large fraction of fossil/industrial carbon in collected CH2O samples and imply the precursors of CH 2O were dominated by fossil/industrial sources even during summer when biogenic sources are expected at their highest. It is suggested that pollutants from upwind coastal cities carried by the southwest sea breeze strongly influenced the site during our limited summer sample collection.

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