Geology topics

Isabelle M. Cozzarelli

Publications and source records attributed to Isabelle M. Cozzarelli.

At least 37 records · Page 2Linked to original sources

USGS2021

Arsenic in petroleum-contaminated groundwater near Bemidji, Minnesota is predicted to persist for centuries

We used a reactive transport model to investigate the cycling of geogenic arsenic (As) in a petroleum-contaminated aquifer. We simulated As mobilization and sequestration using surface complexation reactions with Fe(OH) 3 during petroleum biodegradation coupled with Fe-reduction. Model results predict that dissolved As in the plume will exceed the U.S. and EU 10 µg/L drinking water standard for ~400 years. Non-volatile dissolved organic carbon (NVDOC) in the model promotes As mobilization by exerting oxygen demand, which maintains anoxic conditions in the aquifer. After NVDOC degrades, As re-associates with Fe(OH) 3 as oxygenated conditions are re-established. Over the 400-year simulation, As transport resembles a “roll front” in which: (1) arsenic sorbed to Fe(OH) 3 is released during Fe-reduction coupled to petroleum biodegradation; (2) dissolved As resorbs to Fe(OH) 3 at the plume’s leading edge; and (3) over time, the plume expands, and resorbed As is re-released into groundwater. This “roll front” behavior underscores the transience of sorption as an As attenuation mechanism. Over the plume’s lifespan, simulations suggest that As will contaminate more groundwater than benzene from the oil spill. At its maximum, the model simulates that ~5.7× more groundwater will be contaminated by As than benzene, suggesting that As could pose a greater long-term water quality threat than benzene in this petroleum-contaminated aquifer.

Minnesota↗

USGS2021

Hydrocarbons to carboxyl-rich alicyclic molecules: A continuum model to describe biodegradation of petroleum-derived dissolved organic matter in contaminated groundwater plumes

Relationships between dissolved organic matter (DOM) reactivity and chemical composition in a groundwater plume containing petroleum-derived DOM (DOM HC ) were examined by quantitative and qualitative measurements to determine the source and chemical composition of the compounds that persist downgradient. Samples were collected from a transect down the core of the plume in the direction of groundwater flow. An exponential decrease in dissolved organic carbon concentration resulting from biodegradation along the transect correlated with a continuous shift in fluorescent DOM HC from shorter to longer wavelengths. Moreover, ultrahigh resolution mass spectrometry showed a shift from low molecular weight (MW) aliphatic, reduced compounds to high MW, unsaturated (alicyclic/aromatic), high oxygen compounds that are consistent with carboxyl-rich alicyclic molecules. The degree of condensed aromaticity increased downgradient, indicating that compounds with larger, conjugated aromatic core structures were less susceptible to biodegradation. Nuclear magnetic resonance spectroscopy showed a decrease in alkyl (particularly methyl) and an increase in aromatic/olefinic structural motifs. Collectively, data obtained from the combination of these complementary analytical techniques indicated that changes in the DOM HC composition of a groundwater plume are gradual, as relatively low molecular weight (MW), reduced, aliphatic compounds from the oil source were selectively degraded and high MW, alicyclic/aromatic, oxidized compounds persisted.

Minnesota↗

USGS2021

Arsenic release to the environment from hydrocarbon production, storage, transportation, use and waste management

Arsenic (As) is a toxic trace element with many sources, including hydrocarbons such as oil, natural gas, oil sands, and oil- and gas-bearing shales. Arsenic from these hydrocarbon sources can be released to the environment through human activities of hydrocarbon production, storage, transportation and use. In addition, accidental release of hydrocarbons to aquifers with naturally occurring (geogenic) As can induce mobilization of As to groundwater through biogeochemical reactions triggered by hydrocarbon biodegradation. In this paper, we review the occurrence of As in different hydrocarbons and the release of As from these sources into the environment. We also examine the occurrence of As in wastes from hydrocarbon production, including produced water and sludge. Last, we discuss the potential for As release related to waste management, including accidental or intentional releases, and recycling and reuse of these wastes.

Journal of Hazardous Materials↗

USGS2021

Geochemical and geophysical indicators of oil and gas wastewater can trace potential exposure pathways following releases to surface waters

Releases of oil and gas (OG) wastewaters can have complex effects on stream-water quality and downstream organisms, due to sediment-water interactions and groundwater/surface water exchange. Previously, elevated concentrations of sodium (Na), chloride (Cl), barium (Ba), strontium (Sr), and lithium (Li), and trace hydrocarbons were determined to be key markers of OG wastewater releases when combined with Sr and radium (Ra) isotopic compositions. Here, we assessed the persistence of an OG wastewater spill in a creek in North Dakota using a combination of geochemical measurements and modeling, hydrologic analysis, and geophysical investigations. OG wastewater comprised 0.1 to 0.3% of the stream-water compositions at downstream sites in February and June 2015 but could not be quantified in 2016 and 2017. However, OG-wastewater markers persisted in sediments and pore water for 2.5 years after the spill and up to 7.2-km downstream from the spill site. Concentrations of OG wastewater constituents were highly variable depending on the hydrologic conditions. Electromagnetic measurements indicated substantially higher electrical conductivity under the bank adjacent to a seep 7.2 km downstream from the spill site. Geomorphic investigations revealed mobilization of sediment is an important contaminant transport process. Labile Ba, Ra, Sr, and ammonium (NH 4 ) concentrations extracted from sediments indicated sediments are a long-term reservoir of these constituents, both in the creek and on the floodplain. Using the drivers of ecological effects identified at this intensively studied site we identified 41 watersheds across the North Dakota landscape that may be subject to similar episodic inputs from OG wastewater spills. Effects of contaminants released to the environment during OG waste management activities remain poorly understood; however, analyses of Ra and Sr isotopic compositions, as well as trace inorganic and organic compound concentrations at these sites in pore-water provide insights into potentials for animal and human exposures well outside source-remediation zones.

North Dakota↗

USGS2020

Biological effects of hydrocarbon degradation intermediates: Is the total petroleum hydrocarbon analytical method adequate for risk assessment?

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 the activity of 46 transcription factors; extracts were evaluated at concentrations equivalent to the well water samples. The aryl hydrocarbon receptor (AhR) and pregnane X receptor (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 chemically activated luciferase expression (CALUX) in vitro assays at nine concentrations ranging from 40 to 0.01 times the well water concentrations. Responses 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 underestimated when protocols that remove these chemicals are employed.

Minnesota↗

USGS2020

Shale gas development has limited effects on stream biology and geochemistry in a gradient-based, multiparameter study in Pennsylvania

The number of horizontally drilled shale oil and gas wells in the United States has increased from nearly 28,000 in 2007 to nearly 127,000 in 2017, and research has suggested the potential for the development of shale resources to affect nearby stream ecosystems. However, the ability to generalize current studies is limited by the small geographic scope as well as limited breadth and integration of measured chemical and biological indicators parameters. This study tested the hypothesis that a quantifiable, significant relationship exists between the density of oil and gas (OG) development, increasing streamwater concentrations of known geochemical tracers of OG extraction, and the composition of benthic macroinvertebrate and microbial communities. 25 headwater streams that drain lands across a gradient of shale gas development intensity were sampled. Our strategy included comprehensive measurements across multiple seasons of sampling to account for temporal variability of geochemical parameters, including known shale OG geochemical tracers, and microbial and benthic macroinvertebrate communities. No significant relationships were found between the intensity of OG development, shale OG geochemical tracers, or benthic macroinvertebrate or microbial community composition, whereas significant seasonal differences in stream chemistry were observed. These results highlight the importance of considering spatial and temporal variability in stream chemistry and biota and not only the presence of anthropogenic activities in a watershed. This comprehensive, integrated study of geochemical and biological variability of headwater streams in watersheds undergoing OG development provides a robust framework for examining the effects of energy development at a regional scale.

Pennsylvania↗

USGS2020

Landfill leachate contributes per-/poly-fluoroalkyl substances (PFAS) and pharmaceuticals to municipal wastewater

Widespread disposal of landfill leachate to municipal sewer infrastructure in the United States calls for an improved understanding of the relative organic-chemical contributions to the wastewater treatment plant (WWTP) waste stream and associated surface-water discharge to receptors in the environment. Landfill leachate, WWTP influent, and WWTP effluent samples were collected from three landfill-WWTP systems and compared with analogous influent and effluent samples from two WWTPs that did not receive leachate. Samples were analyzed for 73 per-/poly-fluoroalkyl substances (PFAS), 109 pharmaceuticals, and 21 hormones and related compounds. PFAS were detected more frequently in leachate (92%) than in influent (55%). Total PFAS concentrations in leachate (93,100 ng/L) were more than ten times higher than in influent (6,950 ng/L), and effluent samples (3,730 ng/L). Concentrations of bisphenol A; the nonprescription pharmaceuticals cotinine, lidocaine, nicotine; and the prescription pharmaceuticals amphetamine, carisoprodol, pentoxifylline, and thiabendazole were an order of magnitude higher in landfill leachate than WWTP influent. Leachate load contributions for PFAS (0.78 to 31 g/d), bisphenol A (0.97 to 8.3 g/d), and nonprescription (2.0 to 3.1 g/d) and prescription (0.48 to 2.5 g/d) pharmaceuticals to WWTP influent were generally low (<10 g/d) for most compounds because of high influent-to-leachate volumetric ratios (0.983). No clear differences in concentrations were apparent between effluents from WWTPs receiving landfill leachate and those that did not receive landfill leachate.

Environmental Science: Water Research & Technology↗

USGS2019

Urban stormwater: An overlooked pathway of extensive mixed contaminants to surface and groundwaters in the United States

Increasing global reliance on stormwater control measures to reduce discharge to surface water, increase groundwater recharge, and minimize contaminant delivery to receiving waterbodies necessitates improved understanding of stormwater-contaminant profiles. A multi-agency study of organic and inorganic chemicals in urban stormwater from 50 runoff events at 21 sites across the United States demonstrated that stormwater transports substantial mixtures of polycyclic aromatic hydrocarbons, bioactive contaminants (pesticides and pharmaceuticals), and other organic chemicals known or suspected to pose environmental health concern. Numerous organic-chemical detections per site (median number of chemicals detected = 73), individual concentrations exceeding 10,000 ng/L, and cumulative concentrations up to 263,000 ng/L suggested concern for potential environmental effects during runoff events. Organic concentrations, loads, and yields were positively correlated with impervious surfaces and highly developed urban catchments. Episodic storm-event organic concentrations and loads were comparable to and often exceeded those of daily wastewater plant discharges. Inorganic chemical concentrations were generally dilute in concentration and did not exceed chronic aquatic life criteria. Methylmercury was measured in 90% of samples with concentrations that ranged from 0.05 to 1.0 ng/L.

Environmental Science & Technology↗

USGS2019

Biological effects of elevated major ions in surface water contaminated by a produced water from oil production

Produced water (PW) from oil and gas extraction processes has been shown to contain elevated concentrations of major ions. The objective of this study was to determine the potential effects of elevated major ions in PW-contaminated surface water on a fish (fathead minnow, Pimephales promelas ) and a unionid mussel (fatmucket, Lampsilis siliquoidea ) in short-term (7-day) exposures. The test organisms were exposed in 3 reconstituted waters formulated with 1, 2, and 4 times the major ions measured at a PW-contaminated stream site 1 month after a PW spill from an oil production wastewater pipeline in the Williston Basin, North Dakota. A reconstituted water mimicking the ionic composition of an upstream site from the spill was used as a reference water. Significant reductions in survival and growth of the fish were observed in the 4× treatment compared with the reference. The mussels were more sensitive than the fish, with significant reductions in survival in the 2× and 4× treatments, and significant reductions in length in the 1× and 2× treatments. Overall, these results indicate that elevated concentrations of major ions in PW-contaminated surface waters could adversely affect the fish and mussels tested and potentially other aquatic organisms.

Archives of Environmental Contamination and Toxico↗

USGS2019

Organic geochemistry and toxicology of a stream impacted by unconventional oil and gas wastewater disposal operations

Water and sediment extracts samples were analyzed for extractable hydrocarbons by gas chromatography/mass spectrometry (GC/MS) using an Agilent (Agilent Technologies, Palo Alto, CA, USA) 7890 series GC and 5975 electron ionization (EI) mass selective detector (MSD) operated in scan mode. Agilent ChemStation software was used for data acquisition and analysis (version E.02.00.493 on GC/MS computer and version F.01.03.2357 on laptop for data workup). A 30 m x 250 m x 0.25 m HP-5MS column (95% dimethyl 5% diphenyl polydimethylsiloxane) was used for GC/MS under the following conditions: 1.0 L splitless injection, constant flow of 0.7 mL/min, solvent delay of 7.5 min, injector temperature of 280C, interface at 300C, temperature program of 50-150C at 7C/min, 150-230C at 6C/min, and 230-300C at 3C/min with mass scanned from 35-500 Da.

West Virginia↗

USGS2019

Associations between environmental pollutants and larval amphibians in wetlands contaminated by energy-related brines are potentially mediated by feeding traits

Energy production in the Williston Basin, located in the Prairie Pothole Region of central North America, has increased rapidly over the last several decades. Advances in recycling and disposal practices of saline wastewaters (brines) co-produced during energy production have reduced ecological risks, but spills still occur often and legacy practices of releasing brines into the environment caused persistent salinization in many areas. Aside from sodium and chloride, these brines contain elevated concentrations of metals and metalloids (lead, selenium, strontium, antimony and vanadium), ammonium, volatile organic compounds, hydrocarbons, and radionuclides. Amphibians are especially sensitive to chloride and some metals, increasing potential effects in wetlands contaminated by brines. We collected bed sediment and larval amphibians ( Ambystoma mavortium , Lithobates pipiens and Pseudacris maculata ) from wetlands in Montana and North Dakota representing a range of brine contamination history and severity to determine if contamination was associated with metal concentrations in sediments and if metal accumulation in tissues varied by species. In wetland sediments, brine contamination was positively associated with the concentrations of sodium and strontium, both known to occur in oil and gas wastewater, but negatively correlated with mercury. In amphibian tissues, selenium and vanadium were associated with brine contamination. Metal tissue concentrations were higher in tadpoles that graze compared to predatory salamanders; this suggests frequent contact with the sediments could lead to greater ingestion of metal-laden materials. Although many of these metals may not be directly linked with energy development, the potential additive or synergistic effects of exposure along with elevated chloride from brines could have important consequences for aquatic organisms. To effectively manage amphibian populations in wetlands contaminated by saline wastewaters we need a better understanding of how life history traits, species-specific susceptibilities and the physical-chemical properties of metals co-occurring in wetland sediments interact with other stressors like chloride and wetland drying.

Williston Basin↗

USGS2019

Predicting attenuation of salinized surface- and groundwater-resources from legacy energy development in the Prairie Pothole Region

Oil and gas (energy) development in the Williston Basin, which partly underlies the Prairie Pothole Region in central North America, has helped meet U.S. energy demand for decades. Historical handling and disposal practices of saline wastewater co-produced during energy development resulted in salinization of surface and groundwater at numerous legacy energy sites. Thirty years of monitoring (1988–2018) at Goose Lake, which has been producing since the 1960s, documents long-term spatial and temporal changes in water quality from legacy energy development. Surface water quality was highly variable and decoupled from changes in groundwater quality, likely due to annual and regional climatic fluctuations. Therefore, changes in surface water-quality were not considered a reliable indicator of subsurface chloride migration. However, chloride concentrations in monitoring wells near wastewater sources exhibited systematic temporal reductions allowing for estimates of the time required for natural attenuation of groundwater to U.S. Environmental Protection Agency acute and chronic chloride toxicity benchmarks and a local background level. Point attenuation rates differed based on sediment type (outwash vs till) and yielded a range of predicted years when water-quality targets will be reached: acute – 2045 to 2113; chronic – 2069 to 2160; background – 2126 to 2275. Bulk attenuation rates from four separate years of data were used to calculate the distances chloride could migrate downgradient from the largest wastewater source. Potential distances of downgradient migration before dilution to water-quality targets decreased from 1989 to 2018: acute – 949 to 673 m; chronic – 1220 to 922 m; background – 1878 to 1525 m. Several downgradient wetlands are within these distances and will continue to receive saline contaminated groundwater for years. While these results demonstrate chloride attenuation at a legacy energy site, they also highlight the persistence of saline wastewater contamination and the need to mitigate future spills to prevent long-term salinization from energy development.

Montana↗

USGS2018

Toxicity assessment of groundwater contaminated by petroleum hydrocarbons at a well-characterized, aged, crude oil release site

Management of petroleum-impacted waters by monitored natural attenuation requires an understanding of the toxicology of both the original compounds released and the transformation products formed during natural breakdown. Here, we report data from a groundwater plume consisting of a mixture of crude oil compounds and transformation products in an effort to bridge the gap between groundwater quality information and potential biological effects of human exposures. Groundwater samples were characterized for redox processes, concentrations of nonvolatile dissolved organic carbon (NVDOC) and total petroleum hydrocarbons in the diesel range, as well as for activation of human nuclear receptors (hNR) and toxicologically relevant transcriptional pathways. Results show upregulation of several biological pathways, including peroxisome proliferator-activated receptor gamma and alpha, estrogen receptor alpha, and pregnane X receptor (PXR) with higher levels of hNR activity observed in more contaminated samples. Our study of affected groundwater contaminated by a crude-oil release 39 years ago shows these types of waters may have the potential to cause adverse impacts on development, endocrine, and liver functioning in exposed populations. Additionally, positive trends in activation of some of the molecular targets (e.g., PXR) with increasing NVDOC concentrations (including polar transformation products) demonstrate the importance of improving our understanding of the toxicity associated with the unknown transformation products present in hydrocarbon-impacted waters. Our results begin to provide insight into the potential toxicity of petroleum-impacted waters, which is particularly timely given the ubiquitous nature of waters impacted by petroleum contamination not only recently but also in the past and the need to protect drinking-water quality.

Environmental Science & Technology↗

USGS2018

Examining natural attenuation and acute toxicity of petroleum-derived dissolved organic matter with optical spectroscopy

Groundwater samples containing petroleum-derived dissolved organic matter (DOM HC ) originating from the north oil body within the National Crude Oil Spill Fate and Natural Attenuation Research Site near Bemidji, MN, USA were analyzed by optical spectroscopic techniques (i.e., absorbance and fluorescence) to assess relationships that can be used to examine natural attenuation and toxicity of DOM HC in contaminated groundwater. A strong correlation between the concentration of dissolved organic carbon (DOC) and absorbance at 254 nm ( a 254 ) along a transect of the DOM HC plume indicates that a 254 can be used to quantitatively assess natural attenuation of DOM HC . Fluorescence components, identified by parallel factor (PARAFAC) analysis, show that the composition of the DOM HC beneath and adjacent to the oil body is dominated by aliphatic, low O/C compounds (“protein-like” fluorescence) and that the composition gradually evolves to aromatic, high O/C compounds (“humic-/fulvic-like” fluorescence) as a function of distance downgradient from the oil body. Finally, a direct, positive correlation between optical properties and Microtox acute toxicity assays demonstrates the utility of these combined techniques in assessing the spatial and temporal natural attenuation and toxicity of the DOM HC in petroleum-impacted groundwater systems.

Environmental Science & Technology↗

USGS2018

Regional patterns in the geochemistry of oil-field water, southern San Joaquin Valley, California, USA

Chemical and isotopic data for water co-extracted with hydrocarbons in oil and gas fields are commonly used to examine the source of the formation water and possible impacts on groundwater in areas of oil and gas development. Understanding the geochemical variability of oil-field water could help to evaluate its origin and delineate possible contamination of shallow aquifers in cases where oil-field water is released to the environment. Here we report geochemical and multiple isotope (H, C, O, Sr, Ra) data from 22 oil wells, three sources of produced water that are disposed of in injection wells, and two surface disposal ponds in four oil fields in the southern San Joaquin Valley, California (Fruitvale, Lost Hills, North and South Belridge). Correlations between Cl and δ 18 O, as well as other ions, and gradual increases in salinity with depth, indicate dilution of one or more saline end-members by meteoric water. The saline end-members, represented by deep samples (610 m–2621 m) in three oil-bearing zones, are characterized by Na Cl composition, near-seawater Cl concentrations (median 20,000 mg/L), enriched δ 18 O H 2 O (median 3.4‰), high ammonium(up to 460 mg-N/L), and relatively high radium activity ( 226 Ra+ 228 Ra = 12.3 Bq/L). The deepest sample has low Na/Cl (0.74), high Ca/Mg (5.0), and low 87 Sr/ 86 Sr (0.7063), whereas the shallower samples have higher Na/Cl (0.86–1.2), Ca/Mg near 1, and higher 87 Sr/ 86 Sr (∼0.7083). The data are consistent with an original seawater source being modified by various depth and lithology dependent diagenetic processes. Dilution by meteoric water occurs naturally on the east side of the valley, and in association with water-injectionactivities on the west side. Meteoric-water flushing, particularly on the east side, results in lower solute concentrations (minimum total dissolved solids 2730 mg/L) and total radium (minimum 0.27 Bq/L) in oil-field water, and promotes biodegradation of dissolved organic carbon and hydrocarbon gases like propane. Acetate concentrations and δ 13 C of dissolved inorganic carbon indicate biogenic methane production occurs in some shallow oil zones. Natural and human processes produce substantial variability in the geochemistry of oil-field water that should be considered when evaluating mixing between oil-field waters and groundwater. The variability could result in uncertainty as to detecting the potential source and impact of oil-field water on groundwater.

California↗

USGS2018

Effects of persistent energy-related brine contamination on amphibian abundance in national wildlife refuge wetlands

To inform sustainable energy development, it is important to understand the ecological effects of historical and current production practices and the persistence of those effects. The Williston Basin is one of North America's largest oil production areas and overlaps the Prairie Pothole Region, an area densely populated with wetlands that provide important wildlife habitat. Although historical disposal practices that released chloride-rich waters (brines) produced during oil extraction into the environment are no longer used, brine spills still occur frequently. We sampled 33 wetlands for three amphibian species in Montana and North Dakota during 2015–2017, primarily on National Wildlife Refuges, and used N-mixture models to determine how abundance varied with evidence of brine contamination. To provide insight into effects of historical versus contemporary contamination, we also estimated the association of well density and age with water quality and amphibian abundance. Abundance of boreal chorus frog ( Pseudacris maculata ) larvae declined most rapidly in response to increased chloride (range: 0.04–17,500 mg/L), followed by the northern leopard frog ( Lithobates [ Rana ] pipiens ) and barred tiger salamander ( Ambystoma mavortium ). Water quality and population- and community-level abundance of amphibians were more strongly related to nearby wells (≤800 m) installed before 1982 than to wells installed since 1982. These results suggest historical brine management practices were the primary driver of contamination and reduced amphibian abundance in wetlands we sampled, reflecting multi-decadal ecological effects. These persistent effects also underscore the critical need for tools to restore landscapes affected by brine contamination.

Montana, North Dakota, South Dakota↗

USGS2018

Common hydraulic fracturing fluid additives alter the structure and function of anaerobic microbial communities

The development of unconventional oil and gas (UOG) resources results in the production of large volumes of wastewater containing a complex mixture of hydraulic fracturing chemical additives and components from the formation. The release of these wastewaters into the environment poses potential risks that are poorly understood. Microbial communities in stream sediments form the base of the food chain and may serve as sentinels for changes in stream health. Iron-reducing organisms have been shown to play a role in the biodegradation of a wide range of organic compounds, and so to evaluate their response to UOG wastewater, we enriched anaerobic microbial communities from sediments collected upstream (background) and downstream (impacted) of an UOG wastewater injection disposal facility in the presence of hydraulic fracturing fluid (HFF) additives: guar gum, ethylene glycol, and two biocides, 2,2-dibromo-3-nitrilopropionamide (DBNPA) and bronopol (C 3 H 6 BrNO 4 ). Iron reduction was significantly inhibited early in the incubations with the addition of biocides, whereas amendment with guar gum and ethylene glycol stimulated iron reduction relative to levels in the unamended controls. Changes in the microbial community structure were observed across all treatments, indicating the potential for even small amounts of UOG wastewater components to influence natural microbial processes. The microbial community structure differed between enrichments with background and impacted sediments, suggesting that impacted sediments may have been preconditioned by exposure to wastewater. These experiments demonstrated the potential for biocides to significantly decrease iron reduction rates immediately following a spill and demonstrated how microbial communities previously exposed to UOG wastewater may be more resilient to additional spills.

Applied and Environmental Microbiology↗

USGS2017

Weathering of oil in a surficial aquifer

The composition of crude oil in a surficial aquifer was determined in two locations at the Bemidji, MN, spill site. The abundances of 71 individual hydrocarbons varied within 16 locations sampled. Little depletion of these hydrocarbons (relative to the pipeline oil) occurred in the first 10 years after the spill, whereas losses of 25% to 85% of the total measured hydrocarbons occurred after 30 years. The C 6‐30 n ‐alkanes, toluene, and o ‐xylene were the most depleted hydrocarbons. Some hydrocarbons, such as the n‐ C 10–24 cyclohexanes, tri‐ and tetra‐ methylbenzenes, acyclic isoprenoids, and naphthalenes were the least depleted. Benzene was detected at every sampling location 30 years after the spill. Degradation of the oil led to increases in the percent organic carbon and in the δ 13 C of the oil. Another method of determining hydrocarbon loss was by normalizing the total measured hydrocarbon concentrations to that of the most conservative analytes. This method indicated that the total measured hydrocarbons were depleted by 47% to 77% and loss of the oil mass over 30 years was 18% to 31%. Differences in hydrocarbon depletion were related to the depth of the oil in the aquifer, local topography, amount of recharge reaching the oil, availability of electron acceptors, and the presence of less permeable soils above the oil. The results from this study indicate that once crude oil has been in the subsurface for a number of years there is no longer a “starting oil concentration” that can be used to understand processes that affect its fate and the transport of hydrocarbons in groundwater.

Minnesota↗