Date of Award

Summer 8-13-2014

Degree Type

Dissertation

Degree Name

Ph.D.

Degree Program

Chemistry

Department

Chemistry

Major Professor

Dr. Matthew Tarr

Second Advisor

Dr. John Wiley

Third Advisor

Dr. Yang Cai

Fourth Advisor

Dr. Mark Trudell

Abstract

The behavior of Deepwater Horizon crude oil and other sources of oil were investigated when exposed to sunlight in aquatic systems under environmentally relevant conditions. This research decoupled the abiotic and biotic weathering modifications of oil by focusing solely on the photochemical transformations of oil in aquatic systems. Photochemical rates and mechanisms were measured through the determination of reactive transients. Total hydroxyl radical formation was studied using high benzoic acid concentrations and varying exposure time. Titanium dioxide (TiO2) nanomaterials were added to the system in an effort to determine if the photocatalyst would enhance oil photodegradation. Photochemical production of singlet oxygen from thin oil films over seawater and pure water was measured with furfuryl alcohol as a selective chemical probe. The loss of furfuryl alcohol and the formation of 6-hydroxy(2H)pyran-3(6H)-one were monitored. Photochemical production of organic triplets from 6 different compositions of petroleum was measured through the cis-trans isomerization of 1,3 pentadiene in Gulf water. The data correlate very well with previously measured singlet oxygen concentrations. The energies were measured in the range of 280-300 kJ/mol. Macondo Well Oil from the Deepwater Horizon (DWH) rig was mixed with pure water and seawater and irradiated with simulated sunlight. After irradiation, the water-soluble organics (WSO) from the dark and irradiated samples were extracted and characterized by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Liquid-liquid extraction yielded two fractions from dark and irradiated water/oil mixtures: acidic WSOs (negative-ion electrospray (ESI)), and base/neutral WSOs (positive-ion ESI). These fractions were analyzed by FT-ICR MS to catalogue molecular-level transformations that occurred to oil-derived WSOs after solar irradiation. The increased abundance of higher-order oxygen classes in the irradiated samples relative to the dark samples indicates that photooxidized components of the Macondo crude oil become water-soluble after irradiation. Time series studies were performed to observe the changes in WSO composition. The predominance of higher-order oxygen classes indicates that multiple photochemical pathways exist that result in oxidation of petroleum compounds. More oxygenated compounds were observed in the WSO acid fraction of oils with higher API gravity.

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The University of New Orleans and its agents retain the non-exclusive license to archive and make accessible this dissertation or thesis in whole or in part in all forms of media, now or hereafter known. The author retains all other ownership rights to the copyright of the thesis or dissertation.

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