4.7 Article

Discovery of Oxygenated Hydrocarbon Biodegradation Products at a Late-Stage Petroleum Release Site

Journal

ENERGY & FUELS
Volume 35, Issue 20, Pages 16713-16723

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.energyfuels.1c02642

Keywords

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Funding

  1. University Consortium for Field-Focused Groundwater Research and the Ion Cyclotron Resonance User facility at the National High Magnetic Field Laboratory - National Science Foundation Division of Chemistry and Division of Materials Research [DMR 16-44779]
  2. State of Florida

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The late stage of petroleum hydrocarbon releases to the subsurface is a concept that is still largely unexplored. This study found differences in the biodegradation processes between transmissive aquifer zones with little remaining petroleum liquids and low-permeability zones, with unexpected findings of higher oxygenation in the metabolites from the anoxic low-k zone.
The late stage of petroleum hydrocarbon releases to the subsurface is an evolving but largely unexplored concept. Herein, transmissive aquifer zones with little remaining petroleum liquids become attenuation zones for dissolved organic species released from low-permeability (low-k) zones via back diffusion. To address the knowledge gaps surrounding these subsurface zones, we explored a 40-year-old depleted petroleum body at a former refinery through high-resolution chemical and biomolecular analyses of a cryogenically collected soil core. 16S rRNA gene transcript-based analyses of active microbial communities uncovered predominately aerobic bacteria in the transmissive zone in contrast to anaerobic fermenting bacteria and methanogenic archaea in the low-k zone. Unexpectedly, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analyses revealed a substantially higher degree of oxygenation in the petroleum biodegradation metabolites from the anoxic low-k zone compared to species in the oxic transmissive zone. Likely, a small diffusive influx of molecular oxygen enables limited aerobic metabolism in the low-k zone, while more abundant O-2 in the transmissive zone promotes rapid aerobic biodegradation of petroleum hydrocarbons without the accumulation of highly oxygenated intermediates. While much remains to be uncovered, our work is a critical first step toward enabling better-informed decision making regarding best management practices for late-stage petroleum hydrocarbonimpacted sites.

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