Characterization of the partial oxidation products of crude oil contaminating groundwater at the U.S. Geological Survey Bemidji research site in Minnesota by elemental analysis, radiocarbon dating, nuclear magnetic resonance spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry

Abstract

In oil spill research, a topic of increasing attention during the last decade has been the environmental impact of the partial oxidation products that result from transformation of the petroleum in freshwater, marine, and terrestrial ecosystems. This report describes the isolation and characterization of the partial oxidation products from crude oil contaminating groundwater at the long-term U.S. Geological Survey Bemidji research site in Minnesota. As the result of a pipeline burst in August 1979, a body of light aliphatic crude oil is present from the land surface to 2 meters below the water table in a shallow sand and gravel aquifer in a remote area outside Bemidji, Minnesota, United States. Biodegradation has resulted in the formation of a plume of dissolved organic carbon (DOC) downgradient from the oil body. Groundwater has also been contaminated in an area known as the spray zone, from vertical infiltration of DOC resulting from biodegradation of oil in the soil column, and possibly from photooxidation of oil at the soil surface. The majority of DOC in the contaminated groundwater is in the form of nonvolatile organic acids (NVOAs) which represent the partial oxidation products of the crude oil constituents. The NVOAs have been classified into three fractions according to their isolation on XAD resins: hydrophobic neutrals (HPON), hydrophobic acids (HPOA), and hydrophilic acids (HPIA). These fractions of NVOAs were isolated from wells downgradient from the oil body (sampling well numbers 533, 532, 530, 515), in the spray zone (603), and from an uncontaminated well upgradient of the oil body (310) between the years 1986 and 1989, and again from wells 530 and 603 in 1998. The samples have been characterized by elemental analysis, radiocarbon dating, carbon-13 nuclear magnetic resonance spectroscopy ( 13 C NMR), and negative-mode (-) electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS), with a particular focus on fractions from wells 310, 530, and 603. All the characterization data indicate that the NVOAs from contaminated wells are distinguishable from the background DOC. Carbon-14 ( 14 C) ages of NVOAs from contaminated wells ranged from 3,615 to 18,985 years before the present, whereas the background DOC from the aquifer was post-bomb (post 1950). By elemental analysis, NVOAs from contaminated wells had higher sulfur but lower nitrogen contents than the background. By electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, number average molecular weights determined from assigned molecular formulas ranged from 416 to 486 daltons for the HPOA and HPIA fractions from both background and contaminant wells. NVOAs from contaminated wells had significantly greater numbers of assigned molecular formulas containing sulfur, with elevated concentrations of the S 1 O 4-10 species in particular. Compared to the background, HPOA and HPIA fractions from contaminant wells had a broader range of double bond equivalents (DBEs) within O n compound classes (n is number of atoms). Additionally, within O n compound classes, contaminant well HPOA fractions had a greater abundance of lower n (less than eight) than the background. Contaminant well double bond equivalents versus carbon number (C # ) plots of oxygen compound classes suggest oil-derived aliphatic compounds in the range from C 12 to C 22 in HPOA and HPIA fractions and oil-derived compounds containing aromatic or saturated rings in the approximate range from C 20 to C 30 are present in HPOA fractions. The data suggest the NVOAs originate from biodegradation of several classes of C 12 and greater crude oil constituents: sulfur-containing constituents, including possibly the resins and asphaltenes; constituents containing aromatic rings substituted with methyl groups, including alkylaromatic and naph- thenoaromatic compounds, and C 12 to C 22 alkyl constituents. The overall similarities of the carbon-13 nuclear magnetic resonance spectra for the well 603 and 530 samples from the two sampling dates suggest that a steady state in the composition of the partial oxidation products in each of the two wells had been reached between 1986–1989 and 1998.