Laboratory studies on the production of alpha-pinene-derived organic nitrates and their atmospheric fate

<p>Currently, the formation yields of organic nitrates from the oxidation of biogenic volatile organic compounds, such as α-pinene, is highly uncertain, negatively impacting our knowledge on tropospheric ozone production and the fate of atmospheric NO_x. To lower this uncertainty, we quantified the organic nitrate yield from the OH radical oxidation of α-pinene under high NO_x conditions. The α-pinene- derived nitrates created in chamber experiments readily partitioned to the aerosol phase and underwent particle phase hydrolysis, indicating that these processes are likely a sink for atmospheric NO_x. The hydrolysis of organic nitrates was found to be specific acid-catalyzed and proceeded via unimolecular mechanisms under acidic conditions. The hydrolysis lifetime of a synthesized α-pinene nitrate standard was well within the lifetime of an atmospheric particle. Previously unreported α-pinene oxidation products from chamber studies were identified using mass spectrometry, and, for the first time, individual α-pinene-derived nitrates were identified in a complex mixture. In addition, paper spray ionization was adapted for the direct detection of organosulfates from filter samples and a Raman technique was developed to directly measure the pH of single aerosol particles, for the first time.</p>

Name thesis:degree_name

Doctor of Philosophy (PhD)

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Year

2015

Author dc:creator

• Rindelaub, Joel David

Contributors dc:contributor

• Paul B. Shepson
• Garth J. Simpson
• David R. McMillin
• Peter Kissinger

• Analytical Chemistry
• Atmospheric Sciences

Repository record dc:identifier

https://docs.lib.purdue.edu/open_access_dissertations/548

OAI identifier oai:identifier

oai:docs.lib.purdue.edu:open_access_dissertations-1490