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Barbara Bekins

Publications and source records attributed to Barbara Bekins.

2 recordsLinked to original sources

Natural source zone depletion of crude oil in the subsurface: Processes controlling mass losses of individual compounds

At many petroleum hydrocarbon spill sites, residual spilled product forms a long-term source of groundwater contamination. The phrase source zone natural depletion is used to refer to the mass loss rates. Overall mass lost under environmental conditions was analyzed using conservative biomarker concentrations for a 1979 oil spill in northern Minnesota, USA. After 40–41 years, an average of 50% of the mass was lost with values ranging from 22% to 57% depending on location. It is also important to understand the composition changes in the source. To understand controls on the losses of individual compounds, concentrations of volatile hydrocarbons in oil samples were compared with aqueous solubilities, and pore-space oil saturations. The results of the comparison show that losses of the oil compounds were controlled by pore-space oil saturations, solubility, and susceptibility to degradation under methanogenic conditions. Compounds that degrade under methanogenic conditions, including toluene, o -xylene, and n -alkanes are more depleted compared to benzene, ethylbenzene, and m - and p -xylene for which losses are dominated by dissolution. These rates and compound-specific behaviors form a foundation for improved modeling approaches and risk analyses.

Minnesota

Examining the compositional selectivity of hydrocarbon oxidation products using liquid–liquid extraction and solid-phase extraction techniques

The effect of extraction methods on detecting hydrocarbon oxidation products (HOPs) in groundwater remains unclear. HOPs are polar, water-soluble byproducts of petroleum biodegradation. Our previous work showed that liquid–liquid extraction (LLE), a method commonly used in regulatory monitoring, has a significantly lower extraction efficiency for HOPs compared to solid-phase extraction (SPE). In this study, we evaluate the analytical limitations and compositional selectivity of LLE and SPE using groundwater samples from the Bemidji, MN, crude oil spill site. Optical properties were characterized using excitation–emission matrix spectroscopy (EEMs), and a three-component PARAFAC model was validated, showing consistent trends across both extracts and whole water samples. Ultrahigh-resolution mass spectrometry (UHR-MS) revealed that LLE selectively recovered aliphatic-like compounds but underrepresented more polar oxygenated HOPs. In contrast, SPE methods were more effective at isolating highly oxidized compound classes. These differences were consistent across a gradient of contamination. Overall, the LLE was less precise and less representative of polar HOPs, introducing bias in the characterization of HOPs. This study is the first to quantitatively demonstrate the compositional selectivity and analytical bias of LLE versus SPE for HOPs using combined EEM-PARAFAC and UHR-MS techniques, with implications for long-term monitoring and site assessment protocols.

Environmental Science and Technology