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At least 199 records · Page 11Linked to original sources
USGS2015

Organic contaminant transport and fate in the subsurface: evolution of knowledge and understanding

Toxic organic contaminants may enter the subsurface as slightly soluble and volatile nonaqueous phase liquids (NAPLs) or as dissolved solutes resulting in contaminant plumes emanating from the source zone. A large body of research published in Water Resources Research has been devoted to characterizing and understanding processes controlling the transport and fate of these organic contaminants and the effectiveness of natural attenuation, bioremediation, and other remedial technologies. These contributions include studies of NAPL flow, entrapment, and interphase mass transfer that have advanced from the analysis of simple systems with uniform properties and equilibrium contaminant phase partitioning to complex systems with pore-scale and macroscale heterogeneity and rate-limited interphase mass transfer. Understanding of the fate of dissolved organic plumes has advanced from when biodegradation was thought to require oxygen to recognition of the importance of anaerobic biodegradation, multiple redox zones, microbial enzyme kinetics, and mixing of organic contaminants and electron acceptors at plume fringes. Challenges remain in understanding the impacts of physical, chemical, biological, and hydrogeological heterogeneity, pore-scale interactions, and mixing on the fate of organic contaminants. Further effort is needed to successfully incorporate these processes into field-scale predictions of transport and fate. Regulations have greatly reduced the frequency of new point-source contamination problems; however, remediation at many legacy plumes remains challenging. A number of fields of current relevance are benefiting from research advances from point-source contaminant research. These include geologic carbon sequestration, nonpoint-source contamination, aquifer storage and recovery, the fate of contaminants from oil and gas development, and enhanced bioremediation.

Water Resources Research↗
USGS2017

Carbonate buffering and metabolic controls on carbon dioxide in rivers

Multiple processes support the significant efflux of carbon dioxide (CO 2 ) from rivers and streams. Attribution of CO 2 oversaturation will lead to better quantification of the freshwater carbon cycle and provide insights into the net cycling of nutrients and pollutants. CO 2 production is closely related to O 2 consumption because of the metabolic linkage of these gases. However, this relationship can be weakened due to dissolved inorganic carbon inputs from groundwater, carbonate buffering, calcification, and anaerobic metabolism. CO 2 and O 2 concentrations and other water quality parameters were analyzed in two data sets: a synoptic field study and nationwide water quality monitoring data. CO 2 and O 2 concentrations were strongly negatively correlated in both data sets ( ρ = −0.67 and ρ = −0.63, respectively), although the correlations were weaker in high-alkalinity environments. In nearly all samples, the molar oversaturation of CO 2 was a larger magnitude than molar O 2 undersaturation. We used a dynamically coupled O 2 CO 2 model to show that lags in CO 2 air-water equilibration are a likely cause of this phenomenon. Lags in CO 2 equilibration also impart landscape-scale differences in the behavior of CO 2 between high- and low-alkalinity watersheds. Although the concept of carbonate buffering and how it creates lags in CO 2 equilibration with the atmosphere is well understood, it has not been sufficiently integrated into our understanding of CO 2 dynamics in freshwaters. We argue that the consideration of carbonate equilibria and its effects on CO 2 dynamics are primary steps in understanding the sources and magnitude of CO 2 oversaturation in rivers and streams.

Global Biogeochemical Cycles↗
USGS2019

Water salinity and inundation control soil carbon decomposition during salt marsh restoration: An incubation experiment

Coastal wetlands are a significant carbon (C) sink since they store carbon in anoxic soils. This ecosystem service is impacted by hydrologic alteration and management of these coastal habitats. Efforts to restore tidal flow to former salt marshes have increased in recent decades and are generally associated with alteration of water inundation levels and salinity. This study examined the effect of water level and salinity changes on soil organic matter decomposition during a 60‐day incubation period. Intact soil cores from impounded fresh water marsh and salt marsh were incubated after addition of either sea water or fresh water under flooded and drained water levels. Elevating fresh water marsh salinity to 6 to 9 ppt enhanced CO 2 emission by 50%−80% and most typically decreased CH 4 emissions, whereas, decreasing the salinity from 26 ppt to 19 ppt in salt marsh soils had no effect on CO 2 or CH 4 fluxes. The effect from altering water levels was more pronounced with drained soil cores emitting ~10‐fold more CO 2 than the flooded treatment in both marsh sediments. Draining soil cores also increased dissolved organic carbon (DOC) concentrations. Stable carbon isotope analysis of CO 2 generated during the incubations of fresh water marsh cores in drained soils demonstrates that relict peat OC that accumulated when the marsh was saline was preferentially oxidized when sea water was introduced. This study suggests that restoration of tidal flow that raises the water level from drained conditions would decrease aerobic decomposition and enhance C sequestration. It is also possible that the restoration would increase soil C decomposition of deeper deposits by anaerobic oxidation, however this impact would be minimal compared to lower emissions expected due to the return of flooding conditions.

Ecology and Evolution↗
USGS2016

Estimating heterotrophic respiration at large scales: Challenges, approaches, and next steps

Heterotrophic respiration (HR), the aerobic and anaerobic processes mineralizing organic matter, is a key carbon flux but one impossible to measure at scales significantly larger than small experimental plots. This impedes our ability to understand carbon and nutrient cycles, benchmark models, or reliably upscale point measurements. Given that a new generation of highly mechanistic, genomic-specific global models is not imminent, we suggest that a useful step to improve this situation would be the development of “Decomposition Functional Types” (DFTs). Analogous to plant functional types (PFTs), DFTs would abstract and capture important differences in HR metabolism and flux dynamics, allowing modelers and experimentalists to efficiently group and vary these characteristics across space and time. We argue that DFTs should be initially informed by top-down expert opinion, but ultimately developed using bottom-up, data-driven analyses, and provide specific examples of potential dependent and independent variables that could be used. We present an example clustering analysis to show how annual HR can be broken into distinct groups associated with global variability in biotic and abiotic factors, and demonstrate that these groups are distinct from (but complementary to) already-existing PFTs. A similar analysis incorporating observational data could form the basis for future DFTs. Finally, we suggest next steps and critical priorities: collection and synthesis of existing data; more in-depth analyses combining open data with rigorous testing of analytical results; using point measurements and realistic forcing variables to constrain process-based models; and planning by the global modeling community for decoupling decomposition from fixed site data. These are all critical steps to build a foundation for DFTs in global models, thus providing the ecological and climate change communities with robust, scalable estimates of HR.

Ecosphere↗
USGS2024

Geographic distribution of feather δ34S in Europe

Geographic distribution models of environmentally stable isotopes (the so-called “isoscapes”) are widely employed in animal ecology, and wildlife forensics and conservation. However, the application of isoscapes is limited to elements and regions for which the spatial patterns have been estimated. Here, we focused on the ubiquitous yet less commonly used stable sulfur isotopes (δ 34 S). To predict the European δ 34 S isoscape, we used 242 feather samples from Eurasian Reed Warbler ( Acrocephalus scirpaceus ) formed at 69 European wetland sites. We quantified the relationships between sample δ 34 S and environmental covariates using a random forest regression model and applied the model to predict the geographic distribution of δ 34 S. We also quantified within-site variation in δ 34 S and complementarity with other isotopes on both individual and isoscape levels. The predicted feather δ 34 S isoscape shows only slight differences between the central and southern parts of Europe while the coastal regions were most enriched in 34 S. The most important covariates of δ 34 S were distance to coastline, surface elevation, and atmospheric concentrations of SO 2 gases. The absence of a systematic spatial pattern impedes the application of the δ 34 S isoscape, but high complementarity with other isoscapes advocates the combination of multiple isoscapes to increase the precision of animal tracing. Feather δ 34 S compositions showed considerable within-site variation with highest values in inland parts of Europe, likely attributed to wetland anaerobic conditions and redox sensitivity of sulfur. The complex European geography and topography as well as using δ 34 S samples from wetlands may contribute to the absence of a systematic spatial gradient of δ 34 S values in Europe. We thus encourage future studies to focus on the geographic distribution of δ 34 S using tissues from diverse taxa collected in various habitats over large land masses in the world (i.e., Africa, South America, or East Asia).

Ecosphere↗
USGS2013

Chronic toxicity of nickel-spiked freshwater sediments: variation in toxicity among eight invertebrate taxa and eight sediments

This study evaluated the chronic toxicity of Ni-spiked freshwater sediments to benthic invertebrates. A 2-step spiking procedure (spiking and sediment dilution) and a 2-stage equilibration period (10 wk anaerobic and 1 wk aerobic) were used to spike 8 freshwater sediments with wide ranges of acid-volatile sulfide (AVS; 0.94–38 µmol/g) and total organic carbon (TOC; 0.42–10%). Chronic sediment toxicity tests were conducted with 8 invertebrates ( Hyalella azteca, Gammarus pseudolimnaeus , Chironomus riparius, Chironomus dilutus , Hexagenia sp., Lumbriculus variegatus, Tubifex tubifex , and Lampsilis siliquoidea ) in 2 spiked sediments. Nickel toxicity thresholds estimated from species-sensitivity distributions were 97 µg/g and 752 µg/g (total recoverable Ni; dry wt basis) for sediments with low and high concentrations of AVS and TOC, respectively. Sensitive species were tested with 6 additional sediments. The 20% effect concentrations (EC20s) for Hyalella and Gammarus , but not Hexagenia , were consistent with US Environmental Protection Agency benchmarks based on Ni in porewater and in simultaneously extracted metals (SEM) normalized to AVS and TOC. For Hexagenia , sediment EC20s increased at less than an equimolar basis with increased AVS, and toxicity occurred in several sediments with Ni concentrations in SEM less than AVS. The authors hypothesize that circulation of oxygenated water by Hexagenia led to oxidation of AVS in burrows, creating microenvironments with high Ni exposure. Despite these unexpected results, a strong relationship between Hexagenia EC20s and AVS could provide a basis for conservative site-specific sediment quality guidelines for Ni.

Environmental Toxicology and Chemistry↗
USGS2017

Widespread occurrence and potential for biodegradation of bioactive contaminants in Congaree National Park, USA

Organic contaminants with designed molecular bioactivity, such as pesticides and pharmaceuticals, originate from human and agricultural sources, occur frequently in surface waters, and threaten the structure and function of aquatic and terrestrial ecosystems. Congaree National Park in South Carolina (USA) is a vulnerable park unit due to its location downstream of multiple urban and agricultural contaminant sources and its hydrologic setting, being composed almost entirely of floodplain and aquatic environments. Seventy-two water and sediment samples were collected from 16 sites in Congaree National Park during 2013 to 2015, and analyzed for 199 and 81 targeted organic contaminants, respectively. More than half of these water and sediment analytes were not detected or potentially had natural sources. Pharmaceutical contaminants were detected (49 total) frequently in water throughout Congaree National Park, with higher detection frequencies and concentrations at Congaree and Wateree River sites, downstream from major urban areas. Forty-seven organic wastewater indicator chemicals were detected in water, and 36 were detected in sediment, of which approximately half are distinctly anthropogenic. Endogenous sterols and hormones, which may originate from humans or wildlife, were detected in water and sediment samples throughout Congaree National Park, but synthetic hormones were detected only once, suggesting a comparatively low risk of adverse impacts. Assessment of the biodegradation potentials of 8 14 C-radiolabeled model contaminants indicated poor potentials for some contaminants, particularly under anaerobic sediments conditions.

South Carolina↗
USGS2009

Fate of trace organic compounds during vadose zone soil treatment in an onsite wastewater system

During onsite wastewater treatment, trace organic compounds are often present in the effluents applied to subsurface soils for advanced treatment during vadose zone percolation and groundwater recharge. The fate of the endocrine-disrupting surfactant metabolites 4-nonylphenol (NP), 4-nonylphenolmonoethoxylate (NP1EO), and 4-nonylphenolmonoethoxycarboxylate (NP1EC), metal-chelating agents ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA), antimicrobial agent triclosan, stimulant caffeine, and antibiotic sulfamethoxazole during transport through an unsaturated sandy loam soil was studied at a field-scale test site. To assess the effects of effluent quality and hydraulic loading rate (HLR) on compound fate in the soil profile, two effluents (septic tank or textile biofilter) were applied at two design HLRs (2 or 8 cm/d). Chemical concentrations were determined in the two effluents and soil pore water at 60, 120, and 240 cm below the soil infiltrative surface. Concentrations of trace organic compounds in septic tank effluent were reduced by more than 90% during transport through 240 cm (often within 60 cm) of soil, likely due to sorption and biotransformation. However, the concentration of NP increased with depth in the shallow soil profile. Additional treatment of anaerobic septic tank effluent with an aerobic textile biofilter reduced effluent concentrations of many compounds, but generally did not affect any changes in pore water concentrations. The soil profile receiving septic tank effluent (vs. textile biofilter effluent) generally had greater percent removal efficiencies. EDTA, NP, NP1EC, and sulfamethoxazole were measured in soil pore water, indicating the ability of some trace organic compounds to reach shallow groundwater. Risk is highly dependent on the degree of further treatment in the saturated zone and the types and proximity of uses for the receiving groundwater environment.

Environmental Toxicology and Chemistry↗
USGS2021

Effects of midazolam on corticosterone and blood gases in spectacled eiders prior to transmitter implantation

Stress and physical exertion may affect the physiology and behavior of wildlife during and after capture, and consequently, survival following release. Such effects may reduce the quality and quantity of the data obtained from captured wildlife. We captured spectacled eiders ( Somateria fischeri ), a species listed as threatened under the United States Endangered Species Act, in western Alaska, USA, during spring 2018 for surgical implantation of satellite transmitters. We evaluated the efficacy of midazolam, a benzodiazepine sedative given at capture, to reduce stress and physical exertion. We dosed spectacled eiders with either midazolam (5 mg/ml, = 2.2 mg/kg intramuscular; n = 20) or saline (0.7 ml intramuscular; n = 20) at the point of capture. We assessed sedation level and collected blood samples upon arrival to the field surgery site and at anesthetic induction. We found that midazolam reduced mean corticosterone concentration by 29% and median lactate concentration by 30.3% at the mean arrival time (42 min post‐dosing) relative to the control group. These effects had abated by the mean induction time (99 min post‐dosing). Unexpectedly, blood pH was reduced in the midazolam treatment relative to controls at both arrival and induction, which likely resulted from sedative‐induced respiratory depression that was easily treated with intubation and mechanical ventilation, and administration of the reversal drug, flumazenil. Low blood pH was not associated with negative post‐surgical outcomes, as had been found in spectacled eiders with acidosis caused by anaerobic metabolism typical of physical exertion. Intramuscular injection of midazolam in the field effectively reduced stress and physical exertion in spectacled eiders prior to surgical implantation of transmitters. © 2021 The Wildlife Society.

Journal of Wildlife Management↗
USGS2012

Perils of categorical thinking: "Oxic/anoxic" conceptual model in environmental remediation

Given ambient atmospheric oxygen concentrations of about 21 percent (by volume), the lower limit for reliable quantitation of dissolved oxygen concentrations in groundwater samples is in the range of 0.1–0.5 mg/L. Frameworks for assessing in situ redox condition are often applied using a simple two-category (oxic/anoxic) model of oxygen condition. The "oxic" category defines the environmental range in which dissolved oxygen concentrations are clearly expected to impact contaminant biodegradation, either by supporting aerobic biodegradation of electron-donor contaminants like petroleum hydrocarbons or by inhibiting anaerobic biodegradation of electron-acceptor contaminants like chloroethenes. The tendency to label the second category "anoxic" leads to an invalid assumption that oxygen is insignificant when, in fact, the dissolved oxygen concentration is less than detection but otherwise unknown. Expressing dissolved oxygen concentrations as numbers of molecules per volume, dissolved oxygen concentrations that fall below the 0.1 mg/L field detection limit range from 1 to 1017 molecules/L. In light of recent demonstrations of substantial oxygen-linked biodegradation of chloroethene contaminants at dissolved oxygen concentrations well below the 0.1–0.5 mg/L field detection limit, characterizing "less than detection" oxygen concentrations as "insignificant" is invalid.

Remediation Journal↗
USGS1993

Aspects of the biogeochemistry of methane in Mono Lake and the Mono Basin of California

Above-ambient levels of methane and higher hydrocarbons were detected in the atmosphere of the Mono Basin. These gases emanated from several different sources, including natural gas seeps (thermogenic and biogenic), and methanogenic activity in sediments. Seeps were distributed over nearly 33% of the lake bottom and were also present in the exposed former lakebed. They originated from one or more natural gas deposits that underlie the basin. Seeps associated with hot springs had a thermogenic character, whereas the others had the characteristics of bacterially formed gases. The radiocarbon content of methane in all seep gases was low (5-11% modern carbon), indicating an age of greater than about 20,000 years. Dissolved methane increased with depth in the sediments, ultimately reaching saturation levels (1-3 mM). The outward diffusive flux of methane into the anoxic bottom waters elevated concentrations to 60 µM during the 1984-1988 meromictic interval. The radiocarbon content of hypolimnion methane was equivalent to that of the dissolved inorganic carbon (~80% modern carbon), indicating derivation from current methanogenic activity. Oxidation by anaerobic bacteria was the major sink for this methane. Methane that escaped oxidation transited to the epilimnion where it attained supersaturation (0.1-3.0 µM) relative to the atmosphere. Measured outward fluxes over a 2-year period were highly variable, ranging from 0.01 to 4.82 mmoles CH 4 m -2 d -1 . Bacterial activity was detected in the sediments of the hypolimnion High rates of sulfate reduction (~200 µmoles L -1 d -1 ) were measured in the upper 5-cm interval but decreased > 10-fold with depth. The highest rate of methanogenic activity was ~1 µmole L -1 d -1 , as measured by reduction of 14 CO 2 . Bacteria metabolized dimethylsulfide, trimethylamine, acetate, and glucose to primarily CO 2 and some CH 4 . Turnovers of glucose (k = 0.16 d -1 ) and trimethylamine (k = 0.09 d -1 ) were highest in the upper 2.5-cm interval and decreased as much as 10-fold with depth. These results confirm that a low rate of methanogenic activity occurs in this extreme environment and is the source of methane to the hypolimnion.

California↗
USGS2020

Wetland and hydric soils

Soil and the inherent biogeochemical processes in wetlands contrast starkly with those in upland forests and rangelands. The differences stem from extended periods of anoxia, or the lack of oxygen in the soil, that characterize wetland soils; in contrast, upland soils are nearly always oxic. As a result, wetland soil biogeochemistry is characterized by anaerobic processes, and wetland vegetation exhibits specific adaptations to grow under these conditions. However, many wetlands may also have periods during the year where the soils are unsaturated and aerated. This fluctuation between aerated and nonaerated soil conditions, along with the specialized vegetation, gives rise to a wide variety of highly valued ecosystem services.

Book chapter↗
USGS1987

Effects of cover materials on leaching of constituents from dolomitic lead mine tailings

Five raised-bed test plots were used to study the effects of cover materials on the leaching of constituents from dolomitic Pb mine tailings over a 2-yr period. The cover materials studied were a fertilizer and seed mixture, anaerobically digested sewage sludge, loam and sod, and fallen leaves from silver maples ( Acer Saccharinum ); one plot was not covered. Fresh leachates and receiving pool waters were analyzed for ten metals, Si, P, inorganic anions, filterable organic carbon (FOC), and alkalinity. The mixture of fertilizer and seed decreased leaching of Pb and Zn during the first year. The leaf cover increased leaching of Pb during both years; this effect decreased as the leaves weathered. Sludge caused some increase in Pb leaching during the first year, and increased Cd leaching during both years. Concentrations of most leachate constituents decreased, and pH increased in the receiving pools. Concentrations of Pb remained higher in the receiving pool for the leaf-covered plot than in the other pools. Increases in leaching of Pb and Cd with a sludge cover were moderate, and the ability of the material to support plant growth on the tailings suggested that it may be a good medium for inducing growth of vegetative cover on the dolomitic tailings. Other organic materials may cause pronounced increase in the concentration of toxic trace metals in leachate from the tailings.

Missouri↗
USGS2000

Geochemical investigations by the U.S. Geological Survey on uranium mining, milling, and environmental restoration

Recent research by the U.S. Geological Survey has characterized contaminant sources and identified important geochemical processes that influence transport of radionuclides from uranium mining and milling wastes. 1) Selective extraction studies indicated that alkaline earth sulfates and hydrous ferric oxides are important hosts of 226 Ra in uranium mill tailings. The action of sulfate-reducing and ironreducing bacteria on these phases was shown to enhance release of radium, and this adverse result may temper decisions to dispose of uranium mill tailings in anaerobic environments. 2) Field studies have shown that although surface-applied sewage sludge/wood chip amendments aid in revegetating pyritic spoil, the nitrogen in sludge leachate can enhance pyrite oxidation, acidification of groundwater, and the consequent mobilization of metals and radionuclides. 3) In a U.S. Environmental Protection Agencyfunded study, three permeable reactive barriers consisting of phosphate-rich material, zero-valent iron, or amorphous ferric oxyhydroxide have been installed at an abandoned uranium upgrader facility near Fry Canyon, UT. Preliminary results indicate that each of the permeable reactive barriers is removing the majority of the uranium from the groundwater. 4) Studies on the geochemistry of rare earth elements as analogues for actinides such as uranium and thorium in acid mine drainage environments indicate high mobility under acid-weathering conditions but measurable attenuation associated with iron and aluminum colloid formation. Mass balances from field and laboratory studies are being used to quantify the amount of attenuation. 5) A field study in Colorado demonstrated the use of 234 U/ 238 U isotopic ratio measurements to evaluate contamination of shallow groundwater with uranium mill effluent.

Utah↗
USGS1990

Transformation of Monoaromatic hydrocarbons to organic acids in anoxic groundwater environment

The transformation of benzene and a series of alkylbenzenes was studied in anoxic groundwater of a shallow glacial-outwash aquifer near Bemidji, Minnesota, U.S.A. Monoaromatic hydrocarbons, the most water-soluble components of crude oil, were transported downgradient of an oil spill, forming a plume of contaminated groundwater. Organic acids that were not original components of the oil were identified in the anoxic groundwater. The highest concentrations of these oxidized organic compounds were found in the anoxic plume where a decrease in concentrations of structurally related alkylbenzenes was observed. These results suggest that biological transformation of benzene and alkylbenzenes to organic acid intermediates may be an important attenuation process in anoxic environments. The transformation of a complex mixture of hydrocarbons to a series of corresponding oxidation products in an anoxic subsurface environment provides new insight into in situ anaerobic degradation processes.

Minnesota↗
USGS2000

Influence of dissimilatory metal reduction on fate of organic and metal contaminants in the subsurface

Geobacter become dominant members of the microbial community when Fe(III)-reducing conditions develop as the result of organic contamination, or when Fe(III) reduction is artificially stimulated. These results suggest that further understanding of the ecophysiology of Geobacter species would aid in better prediction of the natural attenuation of organic contaminants under anaerobic conditions and in the design of strategies for the bioremediation of subsurface metal contamination.

Hydrogeology Journal↗
USGS1996

Geovibrio ferrireducens, a phylogenetically distinct dissimilatory Fe(III)-reducing bacterium

A new, phylogenetically distinct, dissimilatory, Fe(III)-reducing bacterium was isolated from surface sediment of a hydrocarbon-contaminated ditch. The isolate, designated strain PAL-1, was an obligately anaerobic, non-fermentative, motile, gram-negative vibrio. PAL-1 grew in a defined medium with acetate as electron donor and ferric pyrophosphate, ferric oxyhydroxide, ferric citrate, Co(III)-EDTA, or elemental sulfur as sole electron acceptor. PAL-1 also used proline, hydrogen, lactate, propionate, succinate, fumarate, pyruvate, or yeast extract as electron donors for Fe(III) reduction. It is the first bacterium known to couple the oxidation of an amino acid to Fe(III) reduction. PAl-1 did not reduce oxygen, Mn(IV), U(VI), Cr(VI), nitrate, sulfate, sulfite, or thiosulfate with acetate as the electron donor. Cell suspensions of PAL-1 exhibited dithionite-reduced minus air-oxidized difference spectra that were characteristic of c -type cytochromes. Analysis of the 16S rRNA gene sequence of PAL-1 showed that the strain is not related to any of the described metal-reducing bacteria in the Proteobacteria and, together with Flexistipes sinusarabici, forms a separate line of descent within the Bacteria. Phenotypically and phylogenetically, strain PAl-1 differs from all other described bacteria, and represents the type strain of a new genus and species, Geovibrio ferrireducens .

Archives of Microbiology↗
USGS2014

Insights into biodegradation through depth-resolved microbial community functional and structural profiling of a crude-oil contaminant plume

Small-scale geochemical gradients are a key feature of aquifer contaminant plumes, highlighting the need for functional and structural profiling of corresponding microbial communities on a similar scale. The purpose of this study was to characterize the microbial functional and structural diversity with depth across representative redox zones of a hydrocarbon plume and an adjacent wetland, at the Bemidji Oil Spill site. A combination of quantitative PCR, denaturing gradient gel electrophoresis, and pyrosequencing were applied to vertically sampled sediment cores. Levels of the methanogenic marker gene, methyl coenzyme-M reductase A (mcrA), increased with depth near the oil body center, but were variable with depth further downgradient. Benzoate degradation N (bzdN) hydrocarbon-degradation gene, common to facultatively anaerobic Azoarcus spp., was found at all locations, but was highest near the oil body center. Microbial community structural differences were observed across sediment cores, and bacterial classes containing known hydrocarbon degraders were found to be low in relative abundance. Depth-resolved functional and structural profiling revealed the strongest gradients in the iron-reducing zone, displaying the greatest variability with depth. This study provides important insight into biogeochemical characteristics in different regions of contaminant plumes, which will aid in improving models of contaminant fate and natural attenuation rates.

Minnesota↗