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Nonvolatile dissolved organic carbon (NVDOC), total petroleum hydrocarbons at the USGS crude oil study site near Bemidji, Minnesota, USA (2018)
This data set describes dissolved concentrations in groundwater of nonvolatile dissolved organic carbon (NVDOC), total petroleum hydrocarbons (TPH) in the gasoline (C6-C10), diesel range (C10-C28) with and without silica gel cleanup, and oil range (>C28-C40) with and without silica gel cleanup. Groundwater samples were collected in June 2018 from the USGS crude oil study site located near Bemidji, MN. A background (reference) well located 200 m upgradient from the source and five wells along a flowline in the plume at 39, 68, 102, 125, and 254 m downgradient from the source.
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Nonvolatile dissolved organic carbon and diesel range organics concentrations measured in 2016 at the USGS crude oil study site near Bemidji, Minnesota, USA
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The Bemidji crude oil spill site is a long-term USGS study site to understand the fate of crude oil in the shallow subsurface. A description of the site can be found at https://mn.water.usgs.gov/projects/bemidji. In 2014 concentrations of non-volatile dissolved organic carbon (NVDOC) were three times higher than diesel range organics (DRO) in the contaminant plume*. This is important because most of the NVDOC in the plume is composed of partial transformation products of compounds from the crude oil that are not reflected in a DRO analysis. In 2016 we conducted a campaign to determine if DRO values continue to reflect only a fraction of the NVDOC. These data are the results of that campaign. A total of 25 wells were sampled for DRO and NVDOC in August, 2016. Three wells with long term records were included in the sampling: 530B, 515B, and 9316D. Wells sampled in 2016 but not in 2014 include two wells located 14 m from a down gradient lake (1217B and 1217C) and one well in the zone sprayed by oil (956). *Bekins, B. A., Cozzarelli, I. M., Erickson, M. L., Steenson, R. A., and Thorn, K. A., 2016, Crude Oil Metabolites in Groundwater at Two Spill Sites: Groundwater, v. 54, no. 5, p. 681-691.
Dissolved organic carbon, total petroleum hydrocarbons and and toxicity assay results for Bemidji, MN (2018) (ver. 2.0, June 2023)
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In crude-oil-contaminant plumes the dissolved organic carbon (DOC) is mainly hydrocarbon degradation intermediates only partly quantified by the diesel range total petroleum hydrocarbon (TPHd) method. To understand potential biological effects of degradation intermediates we tested three fractions of DOC: (1) solid phase extract (HLB); (2) dichloromethane (DCM-total) extract used in TPHd; and (3) DCM extract with hydrocarbons isolated by silica gel cleanup (DCM-SGC). Bioactivity of extracts from five wells spanning a range of DOC was tested using an in vitro multiplex reporter system that evaluates modulation of activity of 46 transcription factors; extracts were evaluated at concentrations equivalent to the well water samples. The aryl hydrocarbon (AhR) and pregnane X (PXR) transcription factors showed the greatest upregulation; with HLB exceeding DCM-total, and no upregulation in the hydrocarbon fraction (DCM-SGC). The HLB extracts were further studied with HepG2 CALUX in vitro assays at nine concentrations ranging from 40 to 0.01 times the well water concentrations. Reponses decreased with distance from the source but were still present at two wells without detectable hydrocarbons. Thus, our in vitro assay results indicate that risks associated with degradation intermediates of hydrocarbons in groundwater will be under estimated when protocols that remove these chemicals are employed.
Inorganic and organic chemical composition of groundwater collected from monitoring wells located at the National Crude Oil Spill Fate and Natural Attenuation Research Site, Bemidji, Minnesota, USA 2009-2023
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This dataset contains information from groundwater monitoring wells at the National Crude Oil Spill Fate and Natural Attenuation Research Site near Bemidji, Minnesota, USA. The information includes field and laboratory methods, site locations, and inorganic and organic chemistry data. Samples were collected between 2009 and 2023, and analyzed for inorganic anions: F (fluoride), Cl (chloride), Br (bromide), NO3 (nitrate), PO4 (phosphate), SO4 (sulfate), and cations: Ca (calcium), Na, (sodium), Mg (magnesium), K (potassium), Si (silicon), Sr (strontium), Al (aluminum), Fe (iron), Mn (manganese), Ba (barium), B (boron), Li (lithium), Ag (silver), As (arsenic), Be (beryllium), Bi (bismuth), Cd (cadmium), Ce (cerium), Co (cobalt), Cs (cesium), Cr (chromium), Cu (copper), La (lanthanum), Mo (molybdenum), Ni (nickel), Pb (lead), Rb (rubidium), Sb (antimony), Se (selenium), Sn (tin), Th (thorium), Tl (thallium), U (uranium), V (vanadium), W (tungsten), and Zn (zinc). Additionally, samples were analyzed for benzene, toluene, ethylbenzene, o, m, p-xylene, total VHC (30 volatile hydrocarbons), NVDOC (non-volatile dissolved organic carbon), methane, ammonia as nitrogen, alkalinity as HCO3 (bicarbonate), and LMWOA (low molecular weight organic acids; lactate, acetate, propionate, formate, butyrate, pyruvate, and benzoate). The following analyses were performed during a select number of years: delta 13C of DIC (dissolved inorganic carbon) delta 13C of DOC, (dissolved organic carbon) and delta 2H in H2O, delta 18O in H2O. Field measurements for specific conductance, pH, and dissolved oxygen were measured daily. Water levels were measured during the sampling events. The supporting metadata files contain site information, field and laboratory methods, water chemistry, and quality-control results. There are three tables.
Analyses of Select Organic and Inorganic Data Collected from Lysimeters Installed at the Bemidji Crude Oil Spill Site, Minnesota, 2018, 2019, 2021
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The U.S. Geological Survey (USGS) collected porewater samples from nine suction lysimeters in 2018, 2019, and 2021 for analysis of organic and inorganic constituents from the National Crude Oil Spill Fate and Natural Attenuation Research Site near Bemidji, MN. In August of 1979, approximately 1,700,000 L (liters), or 10,700 barrels, of crude oil spilled onto a glacial outwash aquifer. Sampled lysimeters included L310-1.5, L310-4.5, L1802-1.8, L9014-1.5, L9014-3.0, L9014-4.5, L9017-1.3, L9017-2.5, and L9017-3.7. This data release presents data on analytes that are important indicators of biodegradation processes. Some of these analytes, if present in elevated concentrations, can be a concern regarding potential effects on human health and the environment. There is one tabulated data set containing concentrations of non-volatile dissolved organic carbon (NVDOC), ammonium (NH3-N), orthophosphate, alkalinity as bicarbonate (HCO3-), major inorganic anions, cations, and trace elements. The supporting metadata file contains site information, field and laboratory methods, water chemistry, and quality-control results. Samples were analyzed in the Reston Biogeochemical Processes in Groundwater Laboratory (RBPGL) in Reston, VA, and by a contract lab, Meadowlands Environmental Research Institute (MERI) in Lyndhurst, NJ.
Analyses of Select Organic and Inorganic Data Collected from Lysimeters Installed at the Bemidji Crude Oil Spill Site, Minnesota, 2018, 2019, 2021
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The U.S. Geological Survey (USGS) collected porewater samples from nine suction lysimeters in 2018, 2019, and 2021 for analysis of organic and inorganic constituents from the National Crude Oil Spill Fate and Natural Attenuation Research Site near Bemidji, MN. In August of 1979, approximately 1,700,000 L (liters), or 10,700 barrels, of crude oil spilled onto a glacial outwash aquifer. Sampled lysimeters included L310-1.5, L310-4.5, L1802-1.8, L9014-1.5, L9014-3.0, L9014-4.5, L9017-1.3, L9017-2.5, and L9017-3.7. This data release presents data on analytes that are important indicators of biodegradation processes. Some of these analytes, if present in elevated concentrations, can be a concern regarding potential effects on human health and the environment. There is one tabulated data set containing concentrations of non-volatile dissolved organic carbon (NVDOC), ammonium (NH3-N), orthophosphate, alkalinity as bicarbonate (HCO3-), major inorganic anions, cations, and trace elements. The supporting metadata file contains site information, field and laboratory methods, water chemistry, and quality-control results. Samples were analyzed in the Reston Biogeochemical Processes in Groundwater Laboratory (RBPGL) in Reston, VA, and by a contract lab, Meadowlands Environmental Research Institute (MERI) in Lyndhurst, NJ.
Organic Analysis of Oilfield Produced Water from the Williston Basin, North Dakota
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The organic composition of produced waters (flowback and formation waters) from the Bakken Formation and the Three Forks Formation in the Williston Basin, North Dakota were examined in this study in order to aid in the remediation of surface contamination due to spills during transport and help develop treatment methods for recycling. Twelve produced water samples were collected from wells in the Bakken and Three Forks Formations at the well head and analyzed for non-purgable dissolved organic carbon (NPDOC), acetate, and extractable hydrocarbons. NPDOC and acetate concentrations from sampled wells from ranged from 33-190 milligrams per liter (mg/L) and 16-40 mg/L, respectively. Concentrations of individual extractable hydrocarbon compounds ranged from less than 1 to greater than 450 micrograms per liter (µg/L), and included polycyclic aromatic hydrocarbons (PAHs), phenolic compounds, glycol ethers, and cyclic ketones.
Weathering of Oil in a Surficial Aquifer, Bemidji, MN
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The dataset consists of 30-year percentage depletion calculations, hydrocarbon group compositions, organic carbon mass fractions and hydrocarbon concentrations for 16 locations sampled at the Bemidji (MN) oil spill study site. Also included in the dataset are concentrations for 33 individual volatile hydrocarbons from the aforementioned sampling locations.
Weathering of Oil in a Surficial Aquifer, Bemidji, MN
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The dataset consists of 30-year percentage depletion calculations, hydrocarbon group compositions, organic carbon mass fractions and hydrocarbon concentrations for 16 locations sampled at the Bemidji (MN) oil spill study site. Also included in the dataset are concentrations for 33 individual volatile hydrocarbons from the aforementioned sampling locations.
Dataset of C1-C6 Dissolved Trace Hydrocarbon Measurements in the Western "Wet Gas" Part of the Marcellus Shale Oil and Gas Play in West Virginia, U.S.A. Collected between June and August 2018
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This dataset contains measurements of dissolved hydrocarbons in from groundwater samples collected in the shale gas producing regions of West Virginia, USA, between June and August of 2018. The target analytes in this study were: methane (CH4), ethane (C2H6), ethene (C2H4), ethyne (C2H2), propane (C3H8), propene (C3H6), i-butane (C4H10), n-butane (C4H10), 1-butene (C4H8), propyne (C3H4), i-pentane (C5H12), n-pentane (C5H12), 2-methyl-pentane (C6H14), 3-methyl-pentane (C6H14), hexane (C6H14), and benzene (C6H6). This dataset also contains corresponding measurements of chlorofluorocarbons (CFCs), Sulfurhexafluoride (SF6), dissolved permanent gases (N2/Ar), tritium, the isotope ratio of helium dissolved in water, the concentration of neon dissolved in water, the isotope ratios of hydrogen-2 and oxygen-18 in water, and the isotope ratio of carbon-13 in dissolved inorganic carbon (DIC).
Data release for Organic geochemistry and petrology of Devonian shale in eastern Ohio: implications for petroleum systems assessment (2018)
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Recent production of light sweet oil from shallow (~2,000 ft) horizontal wells in the Upper Devonian Berea Sandstone of eastern Kentucky and historical oil production from conventional wells in the Berea of adjoining southern Ohio has prompted re-evaluation of Devonian petroleum systems in the central Appalachian Basin. Herein, we examined Upper Devonian Ohio Shale (lower Huron Member) and Middle Devonian Marcellus Shale organic-rich source rocks from eastern Ohio and nearby areas using organic petrography and geochemical analyses of solvent extracts. The data indicate the organic matter in the Ohio and Marcellus Shales was primarily derived from marine algae and its degradation products including bacterial biomass. Absence of odd-over-even n-alkane distributions in gas chromatograms and low gammacerane index values in Devonian source rocks are similar to properties reported for Devonian-reservoired oils in eastern Ohio, suggesting a strong oil-source rock correlation. However, petrographic and geochemical parameters presented here were unable to discriminate specific shale source rocks (e.g., Ohio Shale vs. Marcellus Shale) for the Devonian oils. Lower Paleozoic oils from eastern Ohio, in contrast, are characterized by the presence of odd-over-even n-alkane distributions and higher gammacerane values which clearly discriminate them from Devonian shale-derived oils. Measurements of solid bitumen reflectance (BRo) at the thermal maturity range of the samples (immature to peak oil conditions) tend to underestimate ‘true’ thermal maturity because solid bitumen has lower reflectance than co-occurring vitrinite. Because solid bitumen dominates the organic matter in Devonian shale and vitrinite is sparse, the value of reflectance as a thermal proxy is questionable and its use may lead to reports of ‘vitrinite reflectance suppression’ in early mature to oil window mature areas. For example, thermal maturity estimates from equilibrium(?) biomarker isomerization ratios may suggest some of the Devonian source rock samples are at middle to peak oil window conditions e.g., approximate vitrinite reflectance values of 0.8-0.9%, whereas solid bitumen reflectance is approximately 0.52-0.54% in the same samples. If correct, this observation may require that the predicted onset of oil generation from Devonian shale source rocks in eastern Ohio is moved farther westward. As a consequence, only local to short-distance (30-50 mi) migration would be necessary for emplacement of Devonian-sourced oils into Devonian reservoirs of eastern Ohio, rather than long-distance migration (>50 mi) from ‘deep in the Appalachian basin’, as suggested by previous workers, potentially impacting exploration and future assessments of undiscovered petroleum resources in the Berea Sandstone. However, biomarker isomerization ratios do not show consistent relationships to other thermal maturity parameters (BRo, Tmax), thereby preventing development of robust empirical calibrations for these thermal proxies in the Devonian of eastern Ohio.