title: Sunlight creates oxygenated species in water-soluble fractions of Deepwater Horizon oil.
abstract: In order to assess the impact of sunlight on oil fate, Macondo well oil from the Deepwater Horizon (DWH) rig was mixed with pure water 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) coupled to FT-ICR MS to catalog molecular-level transformations that occur to Macondo-derived WSOs after solar irradiation. Such direct measure of oil phototransformation has not been previously reported. The most abundant heteroatom class detected in the irradiated WSO acid fractions correspond to molecules that contain five oxygens (O5), while the most abundant acids in the dark samples contain two oxygen atoms per molecule (O2). Higher-order oxygen classes (O5-O9) were abundant in the irradiated samples, but <1.5% relative abundance in the dark sample. 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. The base/neutral fraction showed decreased abundance of pyridinic nitrogen (N1) concurrent with an increased abundance of N1Ox classes after irradiation. The predominance of higher-order oxygen classes indicates that multiple photochemical pathways exist that result in oxidation of petroleum compounds.
authors.affiliation: Department of Chemistry, University of New Orleans, New Orleans, LA 70148, United States.
authors.forename: Phoebe
authors.initials: P
authors.lastname: Zito
authors.affiliation: National High Magnetic Field Laboratory, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005, United States.
authors.forename: Huan
authors.initials: H
authors.lastname: Chen
authors.affiliation: National High Magnetic Field Laboratory, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005, United States; Future Fuels Institute, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005, United States.
authors.forename: David C
authors.initials: DC
authors.lastname: Podgorski
authors.affiliation: National High Magnetic Field Laboratory, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, FL 32310-4005, United States.
authors.forename: Amy M
authors.initials: AM
authors.lastname: McKenna
authors.affiliation: Department of Chemistry, University of New Orleans, New Orleans, LA 70148, United States. Electronic address: mtarr@uno.edu.
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Tarr
mesh_terms: D010084:Oxidation-Reduction; D010578:Petroleum / Q000528:radiation effects*; D059392:Petroleum Pollution; D013472:Sunlight; D014874:Water Pollutants, Chemical / Q000737:chemistry / Q000528:radiation effects*
chemical_list: D010578:Petroleum; D014874:Water Pollutants, Chemical
keywords: Deep water horizon; Oil spill; Petroleum; Photochemistry; Photodegradation; Water soluble organics