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USGS2016

The effects of co-contaminants and native wetland sediments on the activity and dominant transformation mechanisms of a 1,1,2,2-tetrachloroethane (TeCA)-degrading enrichment culture

Bioremediation strategies, including bioaugmentation with chlorinated ethene-degrading enrichment cultures, have been successfully applied in the cleanup of subsurface environments contaminated with tetrachloroethene (PCE) and/or trichloroethene (TCE). However, these compounds are frequently found in the environment as components of mixtures that may also contain chlorinated ethanes and methanes. Under these conditions, the implementation of bioremediation may be complicated by inhibition effects, particularly when multiple dehalorespirers are present. We investigated the ability of the 1,1,2,2-tetrachloroethane (TeCA)-dechlorinating culture WBC-2 to biotransform TeCA alone, or a mixture of TeCA plus PCE and carbon tetrachloride (CT), in microcosms. The microcosms contained electron donors provided to biostimulate the added culture and sediment collected from a wetland where numerous “hotspots” of contamination with chlorinated solvent mixtures exist. The dominant TeCA biodegradation mechanism mediated by the WBC-2 culture in the microcosms was different in the presence of these wetland sediments than in the sediment-free enrichment culture or in previous WBC-2 bioaugmented microcosms and column tests conducted with wetland sediment collected at nearby sites. The co-contaminants and their daughter products also inhibited TeCA biodegradation by WBC-2. These results highlight the need to conduct biodegradability assays at new sites, particularly when multiple contaminants and dehalorespiring populations are present.

Chemosphere↗

USGS2015

Enhanced microbial coalbed methane generation: A review of research, commercial activity, and remaining challenges

Coalbed methane (CBM) makes up a significant portion of the world’s natural gas resources. The discovery that approximately 20% of natural gas is microbial in origin has led to interest in microbially enhanced CBM (MECoM), which involves stimulating microorganisms to produce additional CBM from existing production wells. This paper reviews current laboratory and field research on understanding processes and reservoir conditions which are essential for microbial CBM generation, the progress of efforts to stimulate microbial methane generation in coal beds, and key remaining knowledge gaps. Research has been primarily focused on identifying microbial communities present in areas of CBM generation and attempting to determine their function, in-situ reservoir conditions that are most favorable for microbial CBM generation, and geochemical indicators of metabolic pathways of methanogenesis (i.e., acetoclastic or hydrogenotrophic methanogenesis). Meanwhile, researchers at universities, government agencies, and companies have focused on four primary MECoM strategies: 1) microbial stimulation (i.e., addition of nutrients to stimulate native microbes); 2) microbial augmentation (i.e., addition of microbes not native to or abundant in the reservoir of interest); 3) physically increasing microbial access to coal and distribution of amendments; and 4) chemically increasing the bioavailability of coal organics. Most companies interested in MECoM have pursued microbial stimulation: Luca Technologies, Inc., successfully completed a pilot scale field test of their stimulation strategy, while two others, Ciris Energy and Next Fuel, Inc., have undertaken smaller scale field tests. Several key knowledge gaps remain that need to be addressed before MECoM strategies can be implemented commercially. Little is known about the bacterial community responsible for coal biodegradation and how these microorganisms may be stimulated to enhance microbial methanogenesis. In addition, research is needed to understand what fraction of coal is available for biodegradation, and methods need to be developed to determine the extent of in-situ coal biodegradation by MECoM processes for monitoring changes to coal quality. Questions also remain about how well field-scale pilot tests will scale to commercial production, how often amendments will need to be added to maintain new methane generation, and how well MECoM strategies transfer between coal basins with different formation water geochemistries and coal ranks. Addressing these knowledge gaps will be key in determining the feasibility and commercial viability of MECoM technology.

International Journal of Coal Geology↗

USGS2017

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.

Environmental Pollution↗

USGS2019

Changes in microbial communities and associated water and gas geochemistry across a sulfate gradient in coal beds: Powder River Basin, USA

Competition between microbial sulfate reduction and methanogenesis drives cycling of fossil carbon and generation of CH 4 in sedimentary basins. However, little is understood about the fundamental relationship between subsurface aqueous geochemistry and microbiology that drives these processes. Here we relate elemental and isotopic geochemistry of coal-associated water and gas to the microbial community composition from wells in two different coal beds across CH 4 and SO 4 2− gradients (Powder River Basin, Montana, USA). Areas with high CH 4 concentrations generally have higher alkalinity and δ 13 C-DIC values, little to no SO 4 2− , and greater conversion of coal-biodegradable organics to CH 4 (based on δ 13 C-CH 4 and δ 13 C-CO 2 values). Wells with SO 4 2− concentrations from 2 to 10 mM had bacterial populations dominated by several different sulfate-reducing bacteria and archaea that were mostly novel and unclassified. In contrast, in wells with SO 4 2− concentrations <1 mM, the sequences were dominated by presumptive syntrophic bacteria as well as archaeal Methanosarcinales and Methanomicrobiales . The presence of sequences indicative of these bacteria in low SO 4 2− methanogenic wells may suggest a syntrophic role in coal biodegradation and/or the generation of methanogenic substrates from intermediate organic compounds. Archaeal sequences were observed in all sampled zones, with an enrichment of sequences indicative of methanogens in low SO 4 2− zones and unclassified sequences in high SO 4 2− zones. However, sequences indicative of Methanomassiliicoccales were enriched in intermediate SO 4 2− zones and suggest tolerance to SO 4 2− and/or alternative metabolisms in the presence of SO 4 2− . Moreover, sequences indicative of methylotrophic methanogens were more prevalent in an intermediate SO 4 2− and CH 4 well and results suggest an important role for methylotrophic methanogens in critical zone transitions. The presented results demonstrate in situ changes in bacterial and archaeal population distributions along a SO 4 2− gradient associated with recalcitrant, organic carbon that is biodegraded and converted to CO 2 and/or CH 4 .

Powder River Basin↗

USGS2004

Degradation of 1,1,2,2-tetrachloroethane and accumulation of vinyl chloride in wetland sediment microcosms and in situ porewater: Biogeochemical controls and associations with microbial communities

The biodegradation pathways of 1,1,2,2-tetrachloroethane (TeCA) and 1,1,2-trichloroethane (112TCA) and the associated microbial communities in anaerobic wetland sediments were evaluated using concurrent geochemical and genetic analyses over time in laboratory microcosm experiments. Experimental results were compared to in situ porewater data in the wetland to better understand the factors controlling daughter product distributions in a chlorinated solvent plume discharging to a freshwater tidal wetland at Aberdeen Proving Ground, Maryland. Microcosms constructed with wetland sediment from two sites showed little difference in the initial degradation steps of TeCA, which included simultaneous hydrogenolysis to 112TCA and dichloroelimination to 1,2-dichloroethene (12DCE). The microcosms from the two sites showed a substantial difference, however, in the relative dominance of subsequent dichloroelimination of 112TCA. A greater dominance of 112TCA dichloroelimination in microcosms constructed with sediment that was initially iron-reducing and subsequently simultaneously iron-reducing and methanogenic caused approximately twice as much vinyl chloride (VC) production as microcosms constructed with sediment that was methanogenic only throughout the incubation. The microcosms with higher VC production also showed substantially more rapid VC degradation. Field measurements of redox-sensitive constituents, TeCA, and its anaerobic degradation products along flowpaths in the wetland porewater also showed greater production and degradation of VC with concurrent methanogenesis and iron reduction. Molecular fingerprinting indicated that bacterial species [represented by a peak at a fragment size of 198 base pairs (bp) by MnlI digest] are associated with VC production from 112TCA dichloroelimination, whereas methanogens (190 and 307 bp) from the Methanococcales or Methanobacteriales family are associated with VC production from 12DCE hydrogenolysis. Acetate-utilizing methanogens (acetotrophs) appear to be involved in the biodegradation of VC. The relative abundance of Methanosarcinaceae, the only methanogen group with acetotrophic members, doubled in microcosms in which degradation of VC was observed. In addition, molecular analyses using primers specific for known dehalorespiring bacteria in the Dehalococcoides and Desulfuromonas groups showed the presence of these bacteria in microcosm slurry from the site that showed the highest VC production and degradation. Determination of biogeochemical controls and microbial consortia involved in TeCA degradation is leading to a better understanding of the heterogeneity in biodegradation rates and daughter product distribution in the wetland, improving capabilities for developing remediation and monitoring plans.

Journal of Contaminant Hydrology↗

USGS2018

Relative contributions of microbial and infrastructure heat at a crude oil-contaminated site

Biodegradation of contaminants can increase the temperature in the subsurface due to heat generated from exothermic reactions, making temperature observations a potentially low-cost approach for determining microbial activity. For this technique to gain more widespread acceptance, it is necessary to better understand all the factors affecting the measured temperatures. Biodegradation has been occurring at a crude oil-contaminated site near Bemidji, Minnesota for 39 years, creating a quasi-steady-state plume of contaminants and degradation products. A model of subsurface heat generation and transport helps elucidate the contribution of microbial and infrastructure heating to observed temperature increases at this site. We created a steady-state, two-dimensional, heat transport model using previous-published parameter values for physical, chemical and biodegradation properties. Simulated temperature distributions closely match the observed average annual temperatures measured in the contaminated area at the site within less than 0.2 °C in the unsaturated zone and 0.4 °C in the saturated zone. The model results confirm that the observed subsurface heat from microbial activity is due primarily to methane oxidation in the unsaturated zone resulting in a 3.6 °C increase in average annual temperature. Another important source of subsurface heat is from the active, crude-oil pipelines crossing the site. The pipelines impact temperatures for a distance of 200 m and contribute half the heat. Model results show that not accounting for the heat from the pipelines leads to overestimating the degradation rates by a factor of 1.7, demonstrating the importance of identifying and quantifying all heat sources. The model results also highlighted a zone where previously unknown microbial activity is occurring at the site.

Minnesota↗

USGS2008

Selecting remediation goals by assessing the natural attenuation capacity of groundwater systems

Remediation goals for the source areas of a chlorinated ethene‐contaminated groundwater plume were identified by assessing the natural attenuation capacity of the aquifer system. The redox chemistry of the site indicates that sulfate‐reducing (H 2 ∼ 2 nanomoles [nM]) per liter conditions near the contaminant source grade to Fe(III)‐reducing conditions (H 2 ∼ 0.5 nM) downgradient of the source. Sulfate‐reducing conditions facilitate the initial reduction of perchloroethene (PCE) to trichloroethene (TCE), cis ‐dichloroethene ( cis ‐DCE), and vinyl chloride (VC). Subsequently, the Fe(III)‐reducing conditions drive the oxidation of cis ‐DCE and VC to carbon dioxide and chloride. This sequence gives the aquifer a substantial capacity for biodegrading chlorinated ethenes. Natural attenuation capacity (the slope of the steady‐state contaminant concentration profile along a groundwater flowpath) is a function of biodegradation rates, aquifer dispersive characteristics, and groundwater flow velocity. The natural attenuation capacity at the Kings Bay, Georgia site was assessed by estimating groundwater flowrates (∼0.23 ± 0.12 m/d) and aquifer dispersivity (∼1 m) from hydrologic and scale considerations. Apparent biodegradation rate constants (PCE and TCE ∼ 0.01 d −1 ; cis ‐DCE and VC ∼ 0.025 d −1 ) were estimated from observed contaminant concentration changes along aquifer flowpaths. A boundary‐value problem approach was used to estimate levels to which contaminant concentrations in the source areas must be lowered (by engineered removal), or groundwater flow velocities lowered (by pumping) for the natural attenuation capacity to achieve maximum concentration limits (MCLs) prior to reaching a predetermined regulatory point of compliance.

Bioremediation Journal↗

USGS2015

Arsenic cycling in hydrocarbon plumes: secondary effects of natural attenuation

Monitored natural attenuation is widely applied as a remediation strategy at hydrocarbon spill sites. Natural attenuation relies on biodegradation of hydrocarbons coupled with reduction of electron acceptors, including solid phase ferric iron (Fe(III)). Because arsenic (As) adsorbs to Fe-hydroxides, a potential secondary effect of natural attenuation of hydrocarbons coupled with Fe(III) reduction is a release of naturally occurring As to groundwater. At a crude-oil-contaminated aquifer near Bemidji, Minnesota, anaerobic biodegradation of hydrocarbons coupled to Fe(III) reduction has been well documented. We collected groundwater samples at the site annually from 2009 to 2013 to examine if As is released to groundwater and, if so, to document relationships between As and Fe inside and outside of the dissolved hydrocarbon plume. Arsenic concentrations in groundwater in the plume reached 230 µg/L, whereas groundwater outside the plume contained less than 5 µg/L As. Combined with previous data from the Bemidji site, our results suggest that (1) naturally occurring As is associated with Fe-hydroxides present in the glacially derived aquifer sediments; (2) introduction of hydrocarbons results in reduction of Fe-hydroxides, releasing As and Fe to groundwater; (3) at the leading edge of the plume, As and Fe are removed from groundwater and retained on sediments; and (4) downgradient from the plume, patterns of As and Fe in groundwater are similar to background. We develop a conceptual model of secondary As release due to natural attenuation of hydrocarbons that can be applied to other sites where an influx of biodegradable organic carbon promotes Fe(III) reduction.

Minnesota↗

USGS2009

Flowpath independent monitoring of reductive dechlorination potential in a fractured rock aquifer

The flowpath dependent approaches that are typically employed to assess biodegradation of chloroethene contaminants in unconsolidated aquifers are problematic in fractured rock settings, due to difficulties defining discrete groundwater flowpaths in such systems. In this study, the variation in the potential for chloroethene biodegradation with depth was evaluated in a fractured rock aquifer using two flowpath independent lines of field evidence: (1) the presence of the three biochemical prerequisites [electron donor(s), chloroethene electron acceptor(s), and chlororespiring microorganism(s)] for efficient chloroethene chlororespiration and (2) the in situ accumulation of chloroethene reductive dechlorination daughter products. The validity of this approach was assessed by comparing field results with the results of [1, 2‐ 14 C] cis ‐DCE microcosm experiments. Microcosms were prepared with depth‐specific core material, which was crushed and emplaced in discrete packer intervals for 1 year to allow colonization by the indigenous microbial community. Packer intervals characterized by significant electron donor concentrations, elevated numbers of chlororespiring microorganisms, and high reductive dechlorination product to parent contaminant ratios correlated well with the production of 14 C‐labeled reductive dechlorination products in the microcosm experiments. These results indicate that, in the absence of information on discrete groundwater flowpaths, a modified approach emphasizing flowpath independent lines of evidence can provide insight into the temporal and spatial variability of contaminant biodegradation in fractured rock systems.

Ground Water Monitoring and Remediation↗

USGS2006

Selected Natural Attenuation Monitoring Data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June 2005

Previous investigations have shown that natural attenuation and biodegradation of chlorinated volatile organic compounds (VOCs) are substantial in shallow ground water beneath the 9-acre former landfill at Operable Unit 1 (OU-1), Naval Undersea Warfare Center, Division Keyport, Washington. The U.S. Geological Survey (USGS) has continued to monitor ground-water geochemistry to assure that conditions remain favorable for contaminant biodegradation. This report presents the ground-water geochemical and selected VOC data collected at OU-1 by the USGS during June 21-24, 2005, in support of long-term monitoring for natural attenuation. For June 2005, the strongly reducing conditions (sulfate reduction and methanogenesis) most favorable for reductive dechlorination of chlorinated VOCs were detected in fewer upper-aquifer wells than were detected during 2004. Redox conditions in ground water from the intermediate aquifer just downgradient of the landfill remained somewhat favorable for reductive dechlorination. Overall, the changes in redox conditions observed at individual wells have not been consistent or substantial throughout either the upper or the intermediate aquifers. In apparent contrast to changes in redox conditions, the chlorinated VOC concentrations were lower than previously measured in many of the piezometers in the northern phytoremediation plantation. The decrease in contaminant concentrations beneath the northern plantation and the end-product (ethane and ethene) evidence for reductive dechlorination are consistent with 2000-04 results. In the southern phytoremediation plantation, changes in chlorinated VOC concentrations were variable. Most notable was a substantial decrease in the sum of trichloroethene, cis-1,2-dichloroethene, and vinyl chloride concentrations at piezometer P1-9 from 75,000 to 1,000 micrograms per liter between 2004 and 2005. The high concentrations of the reductive dechlorination end-products ethane and ethene measured at the most contaminated sites (P1-6 and P1-7), as well as measurable concentrations at sites P1-9 and P1-10, are reliable evidence that reductive dechlorination of chlorinated VOCs is ongoing in the southern plantation. In the 10 passive-diffusion samplers deployed beneath the marsh stream, the highest chlorinated VOC concentrations measured were at a site (S-4) about midway along the sampled stream reach. In 2005, the sum of trichloroethene, cis-1,2-dichloroethene, and vinyl chloride concentrations increased nearly twofold in comparison to 2004. It is not certain that the apparent increase in concentrations is representative of site conditions. However, the chlorinated VOC concentrations have increased each time at the two most contaminated passive-diffusion sampler sites that have been sampled for multiple years. In the marsh stream, chlorinated VOC concentrations in surface water were low at the site (SW-S6) near the upgradient margin of the former landfill. Concentrations in the stream increased substantially after flowing past the southern phytoremediation plantation to the downstream site (MA-12). Overall, the 2005 data were consistent with previous findings of continued biodegradation of chlorinated VOCs in ground water, along with continued discharge of some chlorinated VOCs to surface water in the marsh stream.

Open-File Report↗

USGS2007

Selected Natural Attenuation Monitoring Data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June 2006

Previous investigations have shown that natural attenuation and biodegradation of chlorinated volatile organic compounds (VOCs) are substantial in shallow ground water beneath the 9-acre former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center, Division Keyport, Washington. The U.S. Geological Survey (USGS) has continued to monitor ground-water geochemistry to assure that conditions remain favorable for contaminant biodegradation. This report presents ground-water geochemical and selected VOC data collected at OU 1 by the USGS during June 12-14, 2006, in support of long-term monitoring for natural attenuation. For June 2006, the strongly reducing conditions (sulfate reduction and methanogenesis) most favorable for reductive dechlorination of VOCs were inferred for 5 of 15 upper-aquifer sites in the northern and southern phytoremediation plantations. Predominant redox conditions in ground water from the intermediate aquifer just downgradient from the landfill remained mildly reducing and somewhat favorable for reductive dechlorination. Since about 2003, measured dissolved hydrogen concentrations in the upper aquifer generally have been lower than those previously measured, although methane and sulfide have continued to be detected throughout the upper aquifer beneath the landfill. Overall, no widespread changes in ground-water redox conditions were measured that should result in either more or less efficient biodegradation of chlorinated VOCs. For the northern plantation in 2006, chlorinated VOC concentrations at piezometers P1-3 and P1-4 were lower than previously measured, and trichloroethene (TCE), cis-1,2-dichloroethene (cis-DCE), or vinyl chloride (VC) were not detected at piezometers P1-1 and P1-5. The steady decrease in contaminant concentrations and the continued detection of the reductive dechlorination end-products ethene and ethane have been consistent throughout the upper aquifer beneath the northern plantation. For the southern plantation in 2006, changes in chlorinated VOC concentrations at the piezometers were highly variable. At piezometer P1-9, the 2006 total chlorinated VOC concentration as well as the concentrations of cis-DCE and VC were measured at their highest levels to date; contaminant concentrations substantially decreased at piezometer P1-9 between June 2004 and June 2005. The reasons for the 2004-05 decrease in concentrations or the 2005-06 increase in concentrations are unknown. At piezometer P1-10, the consistent temporal trend of decreasing chlorinated VOC concentrations measured since 1999 ended, and the concentration of total chlorinated VOC in 2006 was the highest measured since 1999. The reductive dechlorination end-product ethene was measured at concentrations as high as 1,300 micrograms per liter in the upper aquifer beneath the southern plantation, which is reliable evidence that reductive dechlorination of VOCs is ongoing.

Open-File Report↗

USGS2022

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

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.

Minnesota↗

USGS2010

Fate and transport of petroleum hydrocarbons in the subsurface near Cass Lake, Minnesota

The U.S. Geological Survey (USGS) investigated the natural attenuation of subsurface petroleum hydrocarbons leaked over an unknown number of years from an oil pipeline under the Enbridge Energy Limited Partnership South Cass Lake Pumping Station, in Cass Lake, Minnesota. Three weeks of field work conducted between May 2007 and July 2008 delineated a dissolved plume of aromatic hydrocarbons and characterized the biodegradation processes of the petroleum. Field activities included installing monitoring wells, collecting sediment cores, sampling water from wells, and measuring water-table elevations. Geochemical measurements included concentrations of constituents in both spilled and pipeline oil, dissolved alkylbenzenes and redox constituents, sediment bioavailable iron, and aquifer microbial populations. Groundwater in this area flows east-southeast at approximately 26 meters per year. Results from the oil analyses indicate a high degree of biodegradation, characterized by nearly complete absence of n-alkanes. Cass Lake oil samples were more degraded than two oil samples collected in 2008 from the similarly contaminated USGS Bemidji, Minnesota, research site 40 kilometers away. Based on 19 ratios developed for comparing oil sources, the conclusion is that the oils at the two sites appear to be from the same hydrocarbon source. In the Cass Lake groundwater plume, benzene concentrations decrease by three orders of magnitude within 150 meters (m) downgradient from the oil body floating on the water table (between well MW-10 and USGS-4 well nest). The depths of the highest benzene concentrations increase with distance downgradient from the oil, a condition typical of plumes in shallow, unconfined aquifers. Background groundwater, which is nearly saturated with oxygen, becomes almost entirely anaerobic in the plume. As at the Bemidji site, the most important biodegradation processes are anaerobic and dominated by iron reduction. The similarity between the Cass Lake and Bemidji benzene degradation rates, redox conditions, and aquifer material all support a hypothesis that the Cass Lake plume, like the Bemidji plume, is decades old. As concentrations of alkylbenzenes in the oil decrease over time, the benzene concentrations in the groundwater plume will also decrease and the plume is expected to shrink. The Fox Creek wetland, about 250 m south of the Cass Lake site, is the nearest receptor to the south.

Scientific Investigations Report↗

USGS2015

Hydrogeologic characterization and assessment of bioremediation of chlorinated benzenes and benzene in wetland areas, Standard Chlorine of Delaware, Inc. Superfund Site, New Castle County, Delaware, 2009-12

Wetlands at the Standard Chlorine of Delaware, Inc. Superfund Site (SCD) in New Castle County, Delaware, are affected by contamination with chlorobenzenes and benzene from past waste storage and disposal, spills, leaks, and contaminated groundwater discharge. In cooperation with the U.S. Environmental Protection Agency, the U.S. Geological Survey began an investigation in June 2009 to characterize the hydrogeology and geochemistry in the wetlands and assess the feasibility of monitored natural attenuation and enhanced bioremediation as remedial strategies. Groundwater flow in the wetland study area is predominantly vertically upward in the wetland sediments and the underlying aquifer, and groundwater discharge accounts for a minimum of 47 percent of the total discharge for the subwatershed of tidal Red Lion Creek. Thus, groundwater transport of contaminants to surface water could be significant. The major contaminants detected in groundwater in the wetland study area included benzene, monochlorobenzene, and tri- and di-chlorobenzenes. Shallow wetland groundwater in the northwest part of the wetland study area was characterized by high concentrations of total chlorinated benzenes and benzene (maximum about 75,000 micrograms per liter [μg/L]), low pH, and high chloride. In the northeast part of the wetland study area, wetland groundwater had low to moderate concentrations of total chlorinated benzenes and benzene (generally not greater than 10,000 μg/L), moderate pH, and high sulfate concentrations. Concentrations in the groundwater in excess of 1 percent of the solubility of the individual chlorinated benzenes indicate that a contaminant source is present in the wetland sediments as dense nonaqueous phase liquids (DNAPLs). Consistently higher contaminant concentrations in the shallow wetland groundwater than deeper in the wetland sediments or the aquifer also indicate a continued source in the wetland sediments, which could include dissolution of DNAPLs and desorption from the sediments. When highly reducing, methanogenic, or sulfate-reducing conditions existed in the wetland groundwater, molar composition of the volatile organic compounds (VOCs) showed that chlorobenzene and benzene were predominant, indicating biodegradation of the chlorinated benzenes through reductive dechlorination pathways. Temporal changes in redox conditions between 2009 and 2011–12 have shifted the locations in the wetland study area where reductive dechlorination is evident. Microbial community analyses of sediment showed relatively high cell numbers and diversity of populations ( Dehalococcoides , Dehalobacter , Desulfitobacterium , and Geobacter ) that are known to contain species capable of reductive dechlorination, confirming groundwater geochemistry evidence of the occurrence of reductive dechlorination. Natural attenuation was not sufficient, however, to reduce total VOC concentrations along upward groundwater flowpaths in the wetland sediments, most likely due to the additional source of contaminants in the upper sediments. In situ microcosms that were unamended except for the addition of 13 C-labeled contaminants in some treatments, confirmed that the native microbial community was able to biodegrade the higher chlorinated benzenes through reductive dechlorination and that 1,2-dichlorobenzene, chlorobenzene, and benzene could be degraded to carbon dioxide through oxidation pathways. Microcosms that were bioaugmented with the anaerobic dechlorinating consortium WBC-2 and deployed in the wetland sediments showed reductive dechlorination of tri-, di-, and monochlorobenzene, and 13 C-chlorobenzene treatments showed complete degradation of chlorobenzene to carbon dioxide under anaerobic conditions. Experiments with a continuous flow, fixed-film bioreactor seeded with native microorganisms in groundwater from the wetland area showed both aerobic and anaerobic biodegradation of dichlorobenzenes, monochlorobenzene, and benzene, although monochlorobenzene and benzene degradation rates decreased under anaerobic conditions compared to aerobic conditions. In two bioreactors with established biofilms of WBC-2, percent removals of all chlorinated benzene compounds (medians of 86 to 94 percent) under anaerobic conditions were as high as those observed for the bioreactors seeded only with native microorganisms from the site groundwater, and benzene removal was greater in the WBC-2 bioaugmented bioreactors. The high percent removals in the WBC-2 bioreactors without the need for an acclimation period indicates that the same dechlorinators are involved in the chlorinated benzene degradation as those for the chlorinated ethanes and ethenes that the culture was developed to degrade. The ability of the WBC-2 culture to completely reduce the chlorinated benzenes and benzene, even in the presence of high sulfate and sulfide concentrations, is unique for known dechlorinating cultures. The availability of the established culture WBC-2, as well as the ability of the native wetland microbial community to degrade the site contaminants under anaerobic and aerobic conditions, provides flexibility in considering bioremediation options for the wetland areas at SCD.

Delaware↗

USGS2020

Effects of a crude-oil recovery remediation system operated 1999–2003 on groundwater plumes and unsaturated-zone vapor concentrations at a crude-oil spill site near Bemidji, Minnesota

A crude-oil spill occurred in 1979 when a pipeline burst near Bemidji, Minnesota. More than 70 percent of the 1.7 million liters of spilled crude oil was removed shortly thereafter. In response to a requirement by the State regulatory agency to remove the remaining crude to a sheen in all wells, in 1998, the pipeline company installed a dual-pump recovery system at the site. This additional remediation from 1999 to 2003 resulted in removal of about 115,000 liters of crude oil, representing between 36 and 41 percent of the volume of oil (281,000–317,000 liters) estimated to be present in 1998. Effects of the 1999–2003 remediation on groundwater plumes and unsaturated-zone vapor concentrations were evaluated by the U.S. Geological Survey using several methods including measurements of oil thicknesses in wells; field water-quality properties of dissolved oxygen, specific conductance, temperature, and pH in groundwater; and vapor concentrations of methane, carbon dioxide, nitrogen, and oxygen in the unsaturated zone. Although the recovery system decreased oil thicknesses near the remediation wells, average oil thicknesses measured in all wells at the site were not reduced substantially. Dissolved oxygen and specific conductance measurements indicate that a secondary plume was created during the remediation, caused by the disposal of pumped water from the remediation wells in an upgradient infiltration gallery. This plume expanded rapidly immediately after the start of the remediation in 1999, resulting in expansion of the anoxic zone of groundwater upgradient and beneath the existing natural attenuation plume. Beginning in 2000–1, for example, specific conductance concentrations noticeably increased in many wells at the north oil pool from about 400 to more than 700 microsiemens per centimeter. The rapid expansion of the anoxic and elevated specific conductance plume indicates that the remediation contributed substantial amounts of biodegradable dissolved organic carbon to groundwater through the infiltration gallery. The trends in vapor data collected before, during, and after the remediation generally support the research hypothesis that crude-oil removal would have an insignificant effect on vapor concentrations in the unsaturated zone. Although there were some small changes in the concentration of methane, carbon dioxide, nitrogen, and oxygen in the unsaturated zone, these changes were not coincident with the beginning or cessation of the remediation and are therefore thought to be the result of other factors affecting biodegradation rates. A decrease in methane concentrations in one representative well, for example, is thought to be the result of reduced rates of biodegradation and methane production from the increasingly more weathered crude oil. Oil-phase recovery at this site was determined to be challenging and resulted in considerable volumes of mobile and entrapped oil remaining in the subsurface despite remediation efforts.

Minnesota↗

USGS2014

Adaptations of indigenous bacteria to fuel contamination in karst aquifers in south-central Kentucky

The karst aquifer systems in southern Kentucky can be dynamic and quick to change. Microorganisms that live in these unpredictable aquifers are constantly faced with environmental changes. Their survival depends upon adaptations to changes in water chemistry, taking advantage of positive stimuli and avoiding negative environmental conditions. The U.S. Geological Survey conducted a study in 2001 to determine the capability of bacteria to adapt in two distinct regions of water quality in a karst aquifer, an area of clean, oxygenated groundwater and an area where the groundwater was oxygen depleted and contaminated by jet fuel. Water samples containing bacteria were collected from one clean well and two jet fuel contaminated wells in a conduit-dominated karst aquifer. Bacterial concentrations, enumerated through direct count, ranged from 500,000 to 2.7 million bacteria per mL in the clean portion of the aquifer, and 200,000 to 3.2 million bacteria per mL in the contaminated portion of the aquifer over a twelve month period. Bacteria from the clean well ranged in size from 0.2 to 2.5 mm, whereas bacteria from one fuel-contaminated well were generally larger, ranging in size from 0.2 to 3.9 mm. Also, bacteria collected from the clean well had a higher density and, consequently, were more inclined to sink than bacteria collected from contaminated wells. Bacteria collected from the clean portion of the karst aquifer were predominantly (,95%) Gram-negative and more likely to have flagella present than bacteria collected from the contaminated wells, which included a substantial fraction (,30%) of Gram-positive varieties. The ability of the bacteria from the clean portion of the karst aquifer to biodegrade benzene and toluene was studied under aerobic and anaerobic conditions in laboratory microcosms. The rate of fuel biodegradation in laboratory studies was approximately 50 times faster under aerobic conditions as compared to anaerobic, sulfur-reducing conditions. The optimum pH for fuel biodegradation ranged from 6 to 7. These findings suggest that bacteria have adapted to water-saturated karst systems with a variety of active and passive transport mechanisms.

Kentucky↗

USGS1992

Identification of persisten anionic surfactant-derived chemicals in sewage effluent and groundwater

Preparative isolation and fractionation procedures coupled with spectrometric analyses were used to identify surfactant-derived contaminants in sewage effluent and sewage-contaminated groundwater from a site located on Cape Cod, Massachusetts. Anionic surfactants and their biodegradation intermediates were isolated from field samples by ion exchange and fractionated by solvent extraction and adsorption chromatography. Fractions were analyzed by 13C nuclear magnetic resonance spectrometry and gas chromatography-mass spectrometry. Carboxylated residues of alkylphenol polyethoxylate surfactants were detected in sewage effluent and contaminated groundwater. Linear alkylbenzenesulfonates (LAS) were identified in sewage effluent and groundwater. Groundwater LAS composition suggested preferential removal of select isomers and homologs due to processes of biodegradation and partitioning. Tetralin and indane sulfonates (DATS), alicyclic analogs of LAS, were also identified in field samples. Although DATS are a minor portion of LAS formulations, equivalent concentrations of LAS and DATS in groundwater suggested persistence of alicyclic contaminant structures over those of linear structure. Sulfophenyl-carboxylated (SPC) LAS biodegradation intermediates were determined in sewage effluent and groundwater. Homolog distributions suggested that SPC containing 3-10 alkyl-chain carbons persist during infiltration and groundwater transport. Surfactant-derived residues detected in well F300-50 groundwater have a minimum residence time in the range of 2.7-4.6 yr. LAS detected in groundwater at 500 m from infiltration has been stable over an estimated 50-500 half lives.

Conference Paper↗

USGS2001

Potential contribution of microbial degradation to natural attenuation of MTBE in surface water systems

The potential contribution of in situ biodegradation as a mechanism for natural attenuation of MTBE in surface water was studied. Surface water sediments from streams and lakes at 11 sites throughout the US. Microbial degradation of [U-14C] MTBE was observed in surface-water-sediment microcosms under anaerobic conditions, but the efficiency and products of anaerobic MTBE biodegradation were strongly dependent on the predominant terminal electron accepting conditions. In the presence of substantial methanogenic activity, MTBE biodegradation was nominal and involved reduction of MTBE to t-butanol (TBA). Under more oxidizing conditions, minimal accumulation of 14C-TBA and significant mineralization of [U-14C] MTBE to 14CO2 were observed. Microorganisms inhabiting the bed sediments of streams and lakes could degrade MTBE effectively under a range of anaerobic terminal electron accepting conditions. Thus, anaerobic bed sediment microbial processes also might contribute to natural attenuation of MTBE in surface water systems throughout the US. This is an abstract of a paper presented at the 222nd ACS National Meting (Chicago, IL 8/26-30/2001).

ACS Division of Environmental Chemistry, Preprints↗