Environmental Petroleum Pollution Analysis Using Ramped Pyrolysis-gas Chromatography–mass Spectrometry

In response to the Deepwater Horizon oil spill, critical research has tracked the changes in petroleum hydrocarbons with environmental weathering. There are limitations, however, whereby single analytical techniques cannot always identify the wide breadth of petroleum and petroleum-derived compounds. We explore the analytical capabilities of ramped pyrolysis-gas chromatography–mass spectrometry (Py-GC–MS) to evaluate environmental samples of petroleum hydrocarbons from the Deepwater Horizon oil spill. We show that bulk flow Py-GC–MS can quantify the overall degree of petroleum hydrocarbon weathering. Furthermore, thermal slicing Py-GC–MS can quantify specific compounds in the “thermal desorption zone” (50–370 °C), as well as characterize pyrolyzed fragments from non-GC-amenable petroleum hydrocarbons (including oxygenated hydrocarbons) in the “cracking zone” (370–650 °C). Our data also suggest an increase in thermochemical stability, concentration of oxygenated products and complexity of high molecular weight and/or polar components with advanced weathering. This analysis not only elucidates weathering trends in Deepwater Horizon oil over several years, but also illustrates the analytical capacity of this method for future petroleum hydrocarbon investigations, filling a void in research connecting Py-GC–MS and environmentally weathered oil samples.