Orbitrap ESI-MS evaluation of solvent extractable organics from a crude oil release site

The concentrations of oxygen-containing organic compounds (OCOC), measured as dissolved organic carbon (DOC), in groundwater exceeds those of dissolved hydrocarbons, measured as total petroleum hydrocarbons (TPH), at a crude oil release site. Orbitrap mass spectrometry was used to characterize OCOC in samples of the oil, water from upgradient of the release, source area, and downgradient wells, and a local lake. Chemical characterization factors included carbon number, oxygen number, formulae similarity, double bond equivalents (DBE) and radiocarbon dating. Oil samples were dominated by formulae with less than 30 carbons, four or fewer oxygens, and a DBE of less than four. In water samples, formulae were identified with more than 30 carbons, more than 10 oxygens, and a DBE exceeding 30. These characteristics are consistent with DOC found in unimpacted water. Between 65% and 92% of the formulae found in samples collected within the elevated OCOC plume were also found in the upgradient or surface water samples. Evidence suggests that many of the OCOC are not petroleum degradation intermediates, but microbial products generated as a result of de novo synthesis by organisms growing on carbon supplied by the oil. Implications of these results for understanding the fate and managing the risk of hydrocarbons in the subsurface are discussed.