Evaluations of Weathering of Polar and Nonpolar Petroleum Components in a Simulated Freshwater-Oil Spill by Orbitrap and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Chukwuemeka Ajaero; Ian Vander Meulen; Nicole E Heshka; Qin Xin; Dena W McMartin; Kerry M Peru; Huan Chen; Amy M McKenna; Kiaura Reed; John V Headley

doi:10.1021/acs.energyfuels.3c04994

Evaluations of Weathering of Polar and Nonpolar Petroleum Components in a Simulated Freshwater-Oil Spill by Orbitrap and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Energy Fuels. 2024 Apr 8;38(8):6753-6763. doi: 10.1021/acs.energyfuels.3c04994. eCollection 2024 Apr 18.

Authors

Chukwuemeka Ajaero^{1

2}, Ian Vander Meulen^{1

3}, Nicole E Heshka⁴, Qin Xin⁴, Dena W McMartin^{2

3}, Kerry M Peru¹, Huan Chen⁵, Amy M McKenna^{5

6}, Kiaura Reed⁷, John V Headley¹

Affiliations

¹ Environment and Climate Change Canada, Watershed Hydrology and Ecology Research Division, National Hydrology Research Center, 11 Innovation Boulevard, Saskatoon, Saskatchewan S7N 3H5, Canada.
² Department of Geography and Environment, University of Lethbridge, 4401 University Drive, Lethbridge, Alberta T1K 3M4, Canada.
³ Department of Civil, Geological and Environmental Engineering, 57 Campus Drive, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5A9, Canada.
⁴ CanmetENERGY Devon, Natural Resources Canada, 1 Oil Patch Drive, Devon, Alberta T9G 1A8, Canada.
⁵ National High Field Magnet Laboratory, Florida State University, 1800 E. Paul Dirac Dr.,Tallahassee, Florida 32306, United States.
⁶ Soil and Crop Sciences, Colorado State University, 301 University Ave., Fort Collins, Colorado 80523, United States.
⁷ Department of Biology, College of Science and Technology, Florida Agricultural and Mechanical University, 1601 S. Martin Luther King Jr Blvd, Tallahassee, Florida 32307 United States.

PMID: 38654763
PMCID: PMC11034502 (available on 2025-04-08)
DOI: 10.1021/acs.energyfuels.3c04994

Abstract

The comprehensive chemical characterization of crude oil is important for the evaluation of the transformation and fate of components in the environment. Molecular-level speciation of naphthenic acid fraction compounds (NAFCs) was investigated in a mesoscale spill tank using both negative-ion electrospray ionization (ESI) Orbitrap mass spectrometry (MS) and positive-ion atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (APPI-FT-ICR-MS). Both ionization techniques are coupled to high-resolution mass spectrometric detectors (ESI: Orbitrap MS; APPI: FT-ICR-MS at 9.4 T), enabling insight into the behavior and fate of petrogenic compounds during a simulated freshwater crude oil spill. Negative-ion ESI Orbitrap-MS reveals that oxygen-containing (O_x) classes are detected early in the spill, whereby species with more oxygen per molecule evolve later in the simulated spill. The O₂-containing species gradually decreased in relative abundance, while O₃ and O₄ species increased in relative abundance throughout the simulated spill, which could correspond to a relative degree of oxygen incorporation. Nonpolar speciation by positive-ion APPI 9.4 T FT-ICR-MS allowed for the identification of water-soluble nonpolar and less polar acidic species. Molecular-level graphical representation of elemental compositions derived from simulated spill water-soluble and oil-soluble species suggest that biological activity is the primary degradation mechanism and that biodegradation was the dominant mechanism based on the negative-ion ESI Orbitrap-MS results.