Illegal dumping of oil and gas wastewater alters arid soil microbial communities.

The Permian Basin, underlying southeast New Mexico and west Texas, is one of the most productive oil and gas (OG) provinces in the United States. Oil and gas production yields large volumes of wastewater with complex chemistries, and the environmental health risks posed by these OG wastewaters on sensitive desert ecosystems are poorly understood. Starting in November 2017, 39 illegal dumps, as defined by federal and state regulations, of OG wastewater were identified in southeastern New Mexico, releasing ~600,000 L of fluid onto dryland soils. To evaluate the impacts of these releases, we analyzed changes in soil geochemistry and microbial community composition by comparing soils from within OG wastewater dump-affected samples to unaffected zones. We observed significant changes in soil geochemistry for all dump-affected compared with control samples, reflecting the residual salts and hydrocarbons from the OG-wastewater release (e.g., enriched in sodium, chloride, and bromide). Microbial community structure significantly (P < 0.01) differed between dump and control zones, with soils from dump areas having significantly (P < 0.01) lower alpha diversity and differences in phylogenetic composition. Dump-affected soil samples showed an increase in halophilic and halotolerant taxa, including members of the Marinobacteraceae, Halomonadaceae, and Halobacteroidaceae, suggesting that the high salinity of the dumped OG wastewater was exerting a strong selective pressure on microbial community structure. Taxa with high similarity to known hydrocarbon-degrading organisms were also detected in the dump-affected soil samples. Overall, this study demonstrates the potential for OG wastewater exposure to change the geochemistry and microbial community dynamics of arid soils.IMPORTANCEThe long-term environmental health impacts resulting from releases of oil and gas (OG) wastewater, typically brines with varying compositions of ions, hydrocarbons, and other constituents, are understudied. This is especially true for sensitive desert ecosystems, where soil microbes are key primary producers and drivers of nutrient cycling. We found that releases of OG wastewater can lead to shifts in microbial community composition and function toward salt- and hydrocarbon-tolerant taxa that are not typically found in desert soils, thus altering the impacted dryland soil ecosystem. Loss of key microbial taxa, such as those that catalyze organic carbon cycling, increase arid soil fertility, promote plant health, and affect soil moisture retention, could result in cascading effects across the sensitive desert ecosystem. By characterizing environmental changes due to releases of OG wastewater to soils overlying the Permian Basin, we gain further insights into how OG wastewater may alter dryland soil microbial functions and ecosystems.

Contaminant Exposure and Transport from Three Potential Reuse Waters within a Single Watershed.

Global demand for safe and sustainable water supplies necessitates a better understanding of contaminant exposures in potential reuse waters. In this study, we compared exposures and load contributions to surface water from the discharge of three reuse waters (wastewater effluent, urban stormwater, and agricultural runoff). Results document substantial and varying organic-chemical contribution to surface water from effluent discharges (e.g., disinfection byproducts [DBP], prescription pharmaceuticals, industrial/household chemicals), urban stormwater (e.g., polycyclic aromatic hydrocarbons, pesticides, nonprescription pharmaceuticals), and agricultural runoff (e.g., pesticides). Excluding DBPs, episodic storm-event organic concentrations and loads from urban stormwater were comparable to and often exceeded those of daily wastewater-effluent discharges. We also assessed if wastewater-effluent irrigation to corn resulted in measurable effects on organic-chemical concentrations in rain-induced agricultural runoff and harvested feedstock. Overall, the target-organic load of 491 g from wastewater-effluent irrigation to the study corn field during the 2019 growing season did not produce substantial dissolved organic-contaminant contributions in subsequent rain-induced runoff events. Out of the 140 detected organics in source wastewater-effluent irrigation, only imidacloprid and estrone had concentrations that resulted in observable differences between rain-induced agricultural runoff from the effluent-irrigated and nonirrigated corn fields. Analyses of pharmaceuticals and per-/polyfluoroalkyl substances in at-harvest corn-plant samples detected two prescription antibiotics, norfloxacin and ciprofloxacin, at concentrations of 36 and 70 ng/g, respectively, in effluent-irrigated corn-plant samples; no contaminants were detected in noneffluent irrigated corn-plant samples.

Using Biological Responses to Monitor Freshwater Post-Spill Conditions over 3 years in Blacktail Creek, North Dakota, USA.

A pipeline carrying unconventional oil and gas (OG) wastewater spilled approximately 11 million liters of wastewater into Blacktail Creek, North Dakota, USA. Flow of the mix of stream water and wastewater down the channel resulted in storage of contaminants in the hyporheic zone and along the banks, providing a long-term source of wastewater constituents to the stream. A multi-level investigation was used to assess the potential effects of oil and brine spills on aquatic life. In this study, we used a combination of experiments using a native fish species, Fathead Minnow (Pimephales promelas), field sampling of the microbial community structure, and measures of estrogenicity. The fish investigation included in situ experiments and experiments with collected site water. Estrogenicity was measured in collected site water samples, and microbial community analyses were conducted on collected sediments. During the initial post-spill investigation, February 2015, performing in situ fish bioassays was impossible because of ice conditions. However, microbial community (e.g., the presence of members of the Halomonadaceae, a family that is indicative of elevated salinity) and estrogenicity differences were compared to reference sites and point to early biological effects of the spill. We noted water column effects on in situ fish survival 6 months post-spill during June 2015. At that time, total dissolved ammonium (sum of ammonium and ammonia, TAN) was 4.41 mg NH4/L with an associated NH3 of 1.09 mg/L, a concentration greater than the water quality criteria established to protect aquatic life. Biological measurements in the sediment defined early and long-lasting effects of the spill on aquatic resources. The microbial community structure was affected during all sampling events. Therefore, sediment may act as a sink for constituents spilled and as such provide an indication of continued and cumulative effects post-spill. However, lack of later water column effects may reflect pulse hyporheic flow of ammonia from shallow ground water. Combining fish toxicological, microbial community structure and estrogenicity information provides a complete ecological investigation that defines potential influences of contaminants at organismal, population, and community levels. In general, in situ bioassays have implications for the individual survival and changes at the population level, microbial community structure defines potential changes at the community level, and estrogenicity measurements define changes at the individual and molecular level. By understanding effects at these various levels of biological organization, natural resource managers can interpret how a course of action, especially for remediation/restoration, might affect a larger group of organisms in the system. The current work also reviews potential effects of additional constituents defined during chemistry investigations on aquatic resources.

Oil and Gas Wastewater Components Alter Streambed Microbial Community Structure and Function.

The widespread application of directional drilling and hydraulic fracturing technologies expanded oil and gas (OG) development to previously inaccessible resources. A single OG well can generate millions of liters of wastewater, which is a mixture of brine produced from the fractured formations and injected hydraulic fracturing fluids (HFFs). With thousands of wells completed each year, safe management of OG wastewaters has become a major challenge to the industry and regulators. OG wastewaters are commonly disposed of by underground injection, and previous research showed that surface activities at an Underground Injection Control (UIC) facility in West Virginia affected stream biogeochemistry and sediment microbial communities immediately downstream from the facility. Because microbially driven processes can control the fate and transport of organic and inorganic components of OG wastewater, we designed a series of aerobic microcosm experiments to assess the influence of high total dissolved solids (TDS) and two common HFF additives-the biocide 2,2-dibromo-3-nitrilopropionamide (DBNPA) and ethylene glycol (an anti-scaling additive)-on microbial community structure and function. Microcosms were constructed with sediment collected upstream (background) or downstream (impacted) from the UIC facility in West Virginia. Exposure to elevated TDS resulted in a significant decrease in aerobic respiration, and microbial community analysis following incubation indicated that elevated TDS could be linked to the majority of change in community structure. Over the course of the incubation, the sediment layer in the microcosms became anoxic, and addition of DBNPA was observed to inhibit iron reduction. In general, disruptions to microbial community structure and function were more pronounced in upstream and background sediment microcosms than in impacted sediment microcosms. These results suggest that the microbial community in impacted sediments had adapted following exposure to OG wastewater releases from the site. Our findings demonstrate the potential for releases from an OG wastewater disposal facility to alter microbial communities and biogeochemical processes. We anticipate that these studies will aid in the development of useful models for the potential impact of UIC disposal facilities on adjoining surface water and shallow groundwater.

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.

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 (DOMHC) 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 DOMHC 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 DOMHC 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.

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 (NH4) 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.

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.

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 stream water concentrations of known geochemical tracers of OG extraction, and the composition of benthic macroinvertebrate and microbial communities. Twenty-five 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.

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 multiagency 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.

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.

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.

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.

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.

Examining Natural Attenuation and Acute Toxicity of Petroleum-Derived Dissolved Organic Matter with Optical Spectroscopy.

Groundwater samples containing petroleum-derived dissolved organic matter (DOMHC) 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 DOMHC in contaminated groundwater. A strong correlation between the concentration of dissolved organic carbon (DOC) and absorbance at 254 nm ( a254) along a transect of the DOMHC plume indicates that a254 can be used to quantitatively assess natural attenuation of DOMHC. Fluorescence components, identified by parallel factor (PARAFAC) analysis, show that the composition of the DOMHC 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 DOMHC in petroleum-impacted groundwater systems.

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 (C3H6BrNO4). 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.IMPORTANCE Organic components of UOG wastewater can alter microbial communities and biogeochemical processes, which could alter the rates of essential natural attenuation processes. These findings provide new insights into microbial responses following a release of UOG wastewaters and are critical for identifying strategies for the remediation and natural attenuation of impacted environments.

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 C6-30 n-alkanes, toluene, and o-xylene were the most depleted hydrocarbons. Some hydrocarbons, such as the n-C10-24 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.

Degradation of Crude 4-MCHM (4-Methylcyclohexanemethanol) in Sediments from Elk River, West Virginia.

In January 2014, approximately 37 800 L of crude 4-methylcyclohexanemethanol (crude MCHM) spilled into the Elk River, West Virginia. To understand the long-term fate of 4-MCHM, we conducted experiments under environmentally relevant conditions to assess the potential for the 2 primary compounds in crude MCHM (1) to undergo biodegradation and (2) for sediments to serve as a long-term source of 4-MCHM. We developed a solid phase microextraction (SPME) method to quantify the cis- and trans-isomers of 4-MCHM. Autoclaved Elk River sediment slurries sorbed 17.5% of cis-4-MCHM and 31% of trans-4-MCHM from water during the 2-week experiment. Sterilized, impacted, spill-site sediment released minor amounts of cis- and up to 35 µg/L of trans-4-MCHM into water, indicating 4-MCHM was present in sediment collected 10 months post spill. In anoxic microcosms, 300 µg/L cis- and 150 µg/L trans-4-MCHM degraded to nondetectable levels in 8-13 days in both impacted and background sediments. Under aerobic conditions, 4-MCHM isomers degraded to nondetectable levels within 4 days. Microbial communities at impacted sites differed in composition compared to background samples, but communities from both sites shifted in response to crude MCHM amendments. Our results indicate that 4-MCHM is readily biodegradable under environmentally relevant conditions.

A mass balance approach to investigate arsenic cycling in a petroleum plume.

Natural attenuation of organic contaminants in groundwater can give rise to a series of complex biogeochemical reactions that release secondary contaminants to groundwater. In a crude oil contaminated aquifer, biodegradation of petroleum hydrocarbons is coupled with the reduction of ferric iron (Fe(III)) hydroxides in aquifer sediments. As a result, naturally occurring arsenic (As) adsorbed to Fe(III) hydroxides in the aquifer sediment is mobilized from sediment into groundwater. However, Fe(III) in sediment of other zones of the aquifer has the capacity to attenuate dissolved As via resorption. In order to better evaluate how long-term biodegradation coupled with Fe-reduction and As mobilization can redistribute As mass in contaminated aquifer, we quantified mass partitioning of Fe and As in the aquifer based on field observation data. Results show that Fe and As are spatially correlated in both groundwater and aquifer sediments. Mass partitioning calculations demonstrate that 99.9% of Fe and 99.5% of As are associated with aquifer sediment. The sediments act as both sources and sinks for As, depending on the redox conditions in the aquifer. Calculations reveal that at least 78% of the original As in sediment near the oil has been mobilized into groundwater over the 35-year lifespan of the plume. However, the calculations also show that only a small percentage of As (∼0.5%) remains in groundwater, due to resorption onto sediment. At the leading edge of the plume, where groundwater is suboxic, sediments sequester Fe and As, causing As to accumulate to concentrations 5.6 times greater than background concentrations. Current As sinks can serve as future sources of As as the plume evolves over time. The mass balance approach used in this study can be applied to As cycling in other aquifers where groundwater As results from biodegradation of an organic carbon point source coupled with Fe reduction.