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USGS1997

Natural attenuation of chlorinated volatile organic compounds in a freshwater tidal wetland, Aberdeen Proving Ground, Maryland

Ground-water contaminant plumes that are flowing toward or currently discharging to wetland areas present unique remediation problems because of the hydrologic connections between ground water and surface water and the sensitive habitats in wetlands. Because wetlands typically have a large diversity of microorganisms and redox conditions that could enhance biodegradation, they are ideal environments for natural attenuation of organic contaminants, which is a treatment method that would leave the ecosystem largely undisturbed and be cost effective. During 1992-97, the U.S. Geological Survey investigated the natural attenuation of chlorinated volatile organic compounds (VOC's) in a contaminant plume that discharges from a sand aquifer to a freshwater tidal wetland along the West Branch Canal Creek at Aberdeen Proving Ground, Maryland. Characterization of the hydrogeology and geochemistry along flowpaths in the wetland area and determination of the occurrence and rates of biodegradation and sorption show that natural attenuation could be a feasible remediation method for the contaminant plume that extends along the West Branch Canal Creek. The aquifer, which received contaminants in the past from sources that were located upgradient of the current eastern boundary of the wetland, is about 40 to 45 feet thick in the study area. The overlying wetland sediments consist of two distinct layers that have a combined thickness of about 6 to 12 feet--an upper unit of peat and a lower unit of silty to sandy clay or clayey sand. Head distributions show strong vertical gradients, and flow directions are predominantly upward through the wetland sediments. Tidal fluctuations, however, cause some reversals in ground-water-flow directions and changes in discharge locations, which affect the distribution and transport of contaminants. The average linear velocity of ground water is estimated to be about 2 to 3 feet per year along vertical flow lines in the wetland area, and the total ground-water discharge along a 1-foot-wide strip of the wetland extending from the eastern wetland boundary to the creek is in the range of 0.13 to 0.25 feet squared per day. The major parent contaminants in the aquifer were trichloroethylene (TCE); 1,1,2,2-tetrachloroethane (PCA); carbon tetrachloride (CT); and chloroform (CF). The aquifer was typically aerobic, but ground water in the wetland sediments became increasingly anaerobic along the upward flow direction. Iron-reducing conditions were predominant in the lower wetland sediment unit composed of clayey sand and silt, and methanogenesis was predominant in an upper unit composed of peat. Total concentrations of VOC's and the relative proportions of parent compounds to anaerobic daughter products changed substantially as the contaminants were transported upward through these changing redox environments. Concentrations of the parent compounds TCE and PCA ranged from about 100 to 2,000 micrograms per liter in the aquifer beneath the wetland, whereas concentrations of daughter products were low or undetectable. In contrast, the parent compounds commonly were not detected in ground water in the wetland sediments, but the daughter compounds 1,2- dichloro-ethylene (12DCE), vinyl chloride (VC), 1,1,2-trichloroethane (112TCA), and 1,2-dichloroethane (12DCA) were observed. 12DCE and VC were the dominant daughter products in the wetland sediments, even where PCA was the primary parent contaminant discharging to the wetland. The presence of these daughter products in water in the wetland sediments indicates that TCE and PCA are degraded by reductive dechlorination reactions in the naturally anaerobic wetland sediments. Although production of daughter products was observed, total concentrations of the VOC's decreased upward through the 6- to 12-feet-thick wetland sediments and were less than 5 micrograms per liter near the surface. The daughter products are apparently further degraded by these anaerobic processes to non-chlorinated, non-toxic endproducts, or are removed by other attenuation processes such as aerobic degradation or volatilization. Several sets of anaerobic microcosms, some amended with TCE concentrations of 400 or 990 micrograms per liter (3.0 or 7.5 micromoles per liter) and one amended with PCA concentration of 480 micrograms per liter (2.9 micromoles per liter), were constructed in the laboratory using wetland sediment and ground water from the study area. These microcosm experiments confirmed field observations that 12DCE and VC are the dominant daughter products from anaerobic biodegradation of both TCE and PCA. Production of 112TCA and 12DCA also was observed in the PCA-amended microcosms, but concentrations were lower than those of 12DCE and VC. These results indicate that degradation of PCA occurs through both hydrogenolysis and dichloroelimination pathways under anaerobic conditions. Daughter products were not observed in sterile controls, except for relatively low concentrations of 12DCE in the PCA-amended controls, suggesting that the reactions were predominantly microbially mediated. Parent and daughter concentrations in the microcosms decreased to less than 5 micrograms per liter in less than 34 days under methanogenic conditions, thus showing extremely rapid biodegradation rates in these organic-rich wetland sediments. Maximum potential rate constants for biodegradation of TCE and PCA, which were calculated from the microcosm exper-iments assuming first-order degradation rates, ranged from 0.10 to 0.31 per day under methanogenic conditions, corresponding to half-lives of 2 to 7 days. The rate constant for TCE biodegradation under sulfate-reducing conditions was 0.045 West Branch, Aberdeen Proving Ground, Maryland 3 per day (half-life of 15 days), which is lower than under methanogenic conditions. These estimated rate constants for the wetland sediments are two to three orders of magnitude higher than those reported in the literature for TCE biodegradation in microcosms constructed with sandy aquifer sediments. Aerobic biodegradation rates for cis-12DCE, trans-12DCE, and VC were in the same range as those measured for TCE and PCA under anaerobic conditions in microcosm experiments. Thus, production of these daughter products by anaerobic biodegradation of TCE and PCA could be balanced by their consumption where oxygen is available in the wetland sediment, such as near roots and land surface. In the aerobic microcosm experiments, biodegradation of cis-12DCE, trans-12DCE, and VC occurred only if methane consumption occurred, indicating that methanotrophs were involved in the process. Aerobic biodegradation was fastest for vinyl chloride and slowest for TCE in the microcosm experiments. These results agree with other laboratory and field studies that have shown faster degradation by methane-utilizing cultures when the compounds are less halogenated. Equilibrium sorption isotherms were measured in 24-hour batch tests and used to estimate distribution coefficients ( K d 's) to describe the ratios of sorbed to aqueous concentrations of PCA and the daughter products cis-12DCE, trans-12DCE, and VC. The estimated K d's for PCA, cis-12DCE, trans-12DCE, and VC were about 2.3, 1.8, 2.4, and 1.3 liters per kilogram of sediment, respectively. Sorbed concentrations of PCA, cis-12DCE, and trans-12DCE in the wetland sediments, therefore, would be expected to be about twice the concentration measured in the water, whereas sorbed concentrations of VC would not be much greater than the aqueous concentrations. Coefficients of retardation, which were calculated using the K d 's and an advective flow velocity of about 2 feet per year, indicate that sorption alone would cause the movement of the contaminants in the wetland sediments to be 6 to 10 times slower than the advective ground-water flow. Biodegradation and sorption, therefore, are significant natural attenuation mechanisms for chlorinated hydrocarbons in these wetland sediments. The relatively thin layers of wetland sediments are critical in reducing contaminant concentrations and toxicity of the ground water before it discharges to the wetland surface and the creek, and natural attenuation in the wetland sediments could be an effective remediation method for the ground-water contaminants.

Maryland↗

USGS1998

Fate and transport of linear alkylbenzenesulfonate in a sewage- contaminated aquifer: A comparison of natural-gradient pulsed tracer tests

Two natural-gradient tracer tests were conducted to determine the transport and biodegradation behavior of linear alkylbenzenesulfonate (LAS) surfactant under in situ conditions in a sewage-contaminated aquifer. The tests were conducted in two biogeochemically distinct zones of the aquifer: (1) an aerobic uncontaminated zone (oxic zone) and (2) a moderately aerobic, sewage-contaminated zone (transition zone). Chromatographic separation of the surfactant mixture was observed in both zones and attributed to the retardation of the longer alkyl chain homologues during transport. No significant loss of IAS mass was observed for the oxic zone while 20% of the LAS mass injected into the transition zone was removed due to biodegradation. Biodegradation preferentially removed the longer alkyl chain homologues and the external isomers (i.e., 2- and 3-phenyl). The removal of LAS mass coincided with a decrease in dissolved oxygen concentrations, the appearance of LAS metabolites, and an increase in the number of free-living bacteria with a concomitant change in bacteria morphology. The formation of LAS metabolites accounted for 86% of the LAS mass removed in the transition zone. Over the duration of the test, sorption and biodegradation enriched the LAS mixture in the more water-soluble and biologically resistant components.Two natural-gradient tracer tests were conducted to determine the transport and biodegradation behavior of linear alkylbenzenesulfonate (LAS) surfactant under in situ conditions in a sewage-contaminated aquifer. The tests were conducted in two biogeochemically distinct zones of the aquifer: (1) an aerobic uncontaminated zone (oxic zone) and (2) a moderately aerobic, sewage-contaminated zone (transition zone). Chromatographic separation of the surfactant mixture was observed in both zones and attributed to the retardation of the longer alkyl chain homologues during transport. No significant loss of LAS mass was observed for the oxic zone while 20% of the LAS mass injected into the transition zone was removed due to biodegradation. Biodegradation preferentially removed the longer alkyl chain homologues and the external isomers (i.e., 2- and 3-phenyl). The removal of LAS mass coincided with a decrease in dissolved oxygen concentrations, the appearance of LAS metabolites, and an increase in the number of free-living bacteria with a concomitant change in bacteria morphology. The formation of LAS metabolites accounted for 86% of the LAS mass removed in the transition zone. Over the duration of the test, sorption and biodegradation enriched the LAS mixture in the more water-soluble and biologically resistant components.

Environmental Science & Technology↗

USGS2016

Relating carbon and nitrogen isotope effects to reaction mechanisms during aerobic or anaerobic degradation of RDX (Hexahydro-1,3,5-Trinitro-1,3,5-Triazine) by pure bacterial cultures

Kinetic isotopic fractionation of carbon and nitrogen during RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) biodegradation was investigated with pure bacterial cultures under aerobic and anaerobic conditions. Relatively large bulk enrichments in 15 N were observed during biodegradation of RDX via anaerobic ring cleavage (ε 15 N = −12.7‰ ± 0.8‰) and anaerobic nitro reduction (ε 15 N = −9.9‰ ± 0.7‰), in comparison to smaller effects during biodegradation via aerobic denitration (ε 15 N = −2.4‰ ± 0.2‰). 13 C enrichment was negligible during aerobic RDX biodegradation (ε 13 C = −0.8‰ ± 0.5‰) but larger during anaerobic degradation (ε 13 C = −4.0‰ ± 0.8‰), with modest variability among genera. Dual-isotope ε 13 C/ε 15 N analyses indicated that the three biodegradation pathways could be distinguished isotopically from each other and from abiotic degradation mechanisms. Compared to the initial RDX bulk δ 15 N value of +9‰, δ 15 N values of the NO 2 − released from RDX ranged from −7‰ to +2‰ during aerobic biodegradation and from −42‰ to −24‰ during anaerobic biodegradation. Numerical reaction models indicated that N isotope effects of NO 2 − production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε 15 N-NO 2 − values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO 2 − formation associated with anaerobic ring cleavage. These results indicate the potential for isotopic analysis of residual RDX for the differentiation of degradation pathways and indicate that further efforts to examine the isotopic composition of potential RDX degradation products (e.g., NO x ) in the environment are warranted.

Applied and Environmental Microbiology↗

USGS2024

Isolation and identification of microcystin-degrading bacteria in Lake Erie source waters and drinking-water plant sand filters

The increasing prevalence of cyanobacterial harmful algal blooms and the toxins they produce is a global water-quality issue. In the Western Basin of Lake Erie, high microcystin concentrations have led to water-quality advisories, process adjustments for treating drinking water, and increased water-quality monitoring. Biodegradation is an environmentally friendly and cost-effective way to reduce concentrations of microcystins in drinking water; however, few studies have been done to determine biodegradation potential of bacteria indigenous to the Lake Erie watershed. As part of a cooperative program between the U.S. Geological Survey and the U.S. Environmental Protection Agency, this study aimed to identify naturally occurring microcystin-degrading bacteria in source waters and in the sand filters of drinking-water treatment plants in the Western Basin of Lake Erie. Biodegradation of microcystin-LR was found to occur in microcosms developed with three different Lake Erie-area sources—Lake Erie water, water from storage reservoirs supplied by inland streams, and water or solid medium from sand/anthracite filters at drinking-water plants. In microplates with microcystin-LR as the sole carbon source, 10 isolates exhibited cellular respiration and were, therefore, identified as promising microcystin biodegraders; 4 of those isolates subsequently were found to have potential to form biofilms. The 10 promising isolates along with 14 additional isolates from the microcosms were identified by 16S ribosomal RNA sequencing: 15 isolates were γ-proteobacteria, 6 isolates were β-proteobacteria, 1 isolate was an α-proteobacterium, 1 isolate was a flavobacterium in the phylum Bacteroidetes , and 1 isolate was in the phylum Actinobacteria . Isolates were screened for possession of the mlrA gene (found to encode for the protein responsible for cleaving the cyclic structure of microcystin), and results indicate that, for Lake Erie source waters and elsewhere, more work would be required to identify microcystin-biodegradation pathways and products and to confirm biodegradation rates in pure culture isolates.

Lake Erie↗

USGS2016

Environmental drivers of differences in microbial community structure in crude oil reservoirs across a methanogenic gradient

Stimulating in situ microbial communities in oil reservoirs to produce natural gas is a potentially viable strategy for recovering additional fossil fuel resources following traditional recovery operations. Little is known about what geochemical parameters drive microbial population dynamics in biodegraded, methanogenic oil reservoirs. We investigated if microbial community structure was significantly impacted by the extent of crude oil biodegradation, extent of biogenic methane production, and formation water chemistry. Twenty-two oil production wells from north central Louisiana, USA, were sampled for analysis of microbial community structure and fluid geochemistry. Archaea were the dominant microbial community in the majority of the wells sampled. Methanogens, including hydrogenotrophic and methylotrophic organisms, were numerically dominant in every well, accounting for, on average, over 98% of the total Archaea present. The dominant Bacteria groups were Pseudomonas, Acinetobacter , Enterobacteriaceae, and Clostridiales, which have also been identified in other microbially-altered oil reservoirs. Comparing microbial community structure to fluid (gas, water, and oil) geochemistry revealed that the relative extent of biodegradation, salinity, and spatial location were the major drivers of microbial diversity. Archaeal relative abundance was independent of the extent of methanogenesis, but closely correlated to the extent of crude oil biodegradation; therefore, microbial community structure is likely not a good sole predictor of methanogenic activity, but may predict the extent of crude oil biodegradation. However, when the shallow, highly biodegraded, low salinity wells were excluded from the statistical analysis, no environmental parameters could explain the differences in microbial community structure. This suggests that the microbial community structure of the 5 shallow, up-dip wells was different than the 17 deeper, down-dip wells. Also, the 17 down-dip wells had statistically similar microbial communities despite significant changes in environmental parameters between oil fields. Together, this implies that no single microbial population is a reliable indicator of a reservoir's ability to degrade crude oil to methane, and that geochemistry may be a more important indicator for selecting a reservoir suitable for microbial enhancement of natural gas generation.

Louisiana↗

USGS2024

Distribution of ancient carbon in groundwater and soil gas from degradation of petroleum near the Red Hill Bulk Fuel Storage Facility, O‘ahu, Hawai‘i

The groundwater below the Red Hill Bulk Fuel Storage Facility (the facility) in Oʻahu, Hawaiʻi, contains fuel compounds from past spills. This study used carbon-14 analyses to distinguish fuel-derived carbon from background carbon, along with other biodegradation indicators, to address two goals: (1) determine the extent and migration direction of groundwater affected by residual fuel below the facility and (2) determine if residual fuel locations in the subsurface could be identified by analyzing soil gas at the surface above the facility. Groundwater from 19 wells was sampled between September 2022 and April 2023. Nonvolatile dissolved organic carbon (NVDOC) from a well presumed to be unaffected by past spills contained 38 percent ancient carbon indicating a natural source of ancient carbon in the subsurface. The NVDOC concentrations and ancient carbon percentages indicate fuel biodegradation products are likely present on the north and south of Red Hill with the greatest effects at well RHMW02 near the 2014 spill site. The NVDOC concentrations are almost three times higher than diesel range organic (DRO) concentrations in groundwater from the same sites. Major ion data indicate that iron reduction is an important biodegradation process. Soil probe samples and soil carbon traps were used to determine the carbon-14 content of soil carbon dioxide. Ancient carbon from fuel biodegradation was not detected at any soil probe or carbon trap site in contrast to a 2017 study which reported ancient carbon detections. A reanalysis of the 2017 results using a range of local values for background carbon-14 indicates that ancient carbon from fuel biodegradation was probably only detected in lower tunnel exhaust system samples and not in any soil carbon trap samples. Measurements of carbon dioxide efflux with a dynamic closed chamber were highly variable. The soil gas results indicate that soil gas measurements at land surface were not useful for detecting residual fuel at the facility.

Hawaii↗

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↗

USGS1990

Hydrocarbon-water interactions during brine migration: Evidence from hydrocarbon inclusions in calcite cements from Danish North Sea oil fields

Crude oils in primary and secondary fluid inclusions in calcite from fractures in seven offshore oil fields associated with diapiric salt structures in the Danish sector of the North Sea were analyzed by capillary column gas chromatography and compared with crude oils produced from the same reservoirs. Oils from fluid inclusions in all fields show evidence of biodegradation (decreased n - C 17 /pristane and n - C 18 /phytane ratios and loss of n-C 7 , 2-methyl hexane, and 3-methyl hexane relative to methyl cyclohexane) and water washing (absence of benzene and depletion of toluene). Some oils in inclusions are extremely enriched in C 6 and C 7 cyclic alkanes suggesting that these samples contain hydrocarbons exsolved from ascending, hotter formation waters. Compared to inclusion oils the produced oils are less biodegraded, but are water washed, indicating that both types of oil interacted with large volumes of formation water. The carbon isotopic composition of the calcite host of the fluid inclusions in the Dagmar and Skjold fields is as light as −16.5%. PDB and the sulfur isotopic composition of pyrite in and adjacent to the calcite veins in the Skjold field is as light as −39.6%. CDT, indicating that biodegradation of the oils was a source of some of the carbon in the calcite and sulfate reduction was the source of sulfur for the pyrite. The evidence for microbial degradation of petroleum is consistent with present-day reservoir temperatures (65°–96°C) but is not consistent with previous estimates of the temperatures of calcite vein filling (95°–130°C) which are much higher than the temperatures of known occurrences of biodegraded oil.

Geochimica et Cosmochimica Acta↗

USGS2015

Rates of As and trace-element mobilization caused by Fe reduction in mixed BTEX–ethanol experimental plumes

Biodegradation of organic matter, including petroleum-based fuels and biofuels, can create undesired secondary water-quality effects. Trace elements, especially arsenic (As), have strong adsorption affinities for Fe(III) (oxyhydr)-oxides and can be released to groundwater during Fe-reducing biodegradation. We investigated the mobilization of naturally occurring As, cobalt (Co), chromium (Cr), and nickel (Ni) from wetland sediments caused by the introduction of benzene, toluene, ethylbenzene, and xylenes (BTEX) and ethanol mixtures under iron- and nitrate-reducing conditions, using in situ push–pull tests. When BTEX alone was added, results showed simultaneous onset and similar rates of Fe reduction and As mobilization. In the presence of ethanol, the maximum rates of As release and Fe reduction were higher, the time to onset of reaction was decreased, and the rates occurred in multiple stages that reflected additional processes. The concentration of As increased from <1 μg/L to a maximum of 99 μg/L, exceeding the 10 μg/L limit for drinking water. Mobilization of Co, Cr, and Ni was observed in association with ethanol biodegradation but not with BTEX. These results demonstrate the potential for trace-element contamination of drinking water during biodegradation and highlight the importance of monitoring trace elements at natural and enhanced attenuation sites.

Environmental Science & Technology↗

USGS1997

Transformations of TNT and related aminotoluenes in groundwater aquifer slurries under different electron-accepting conditions

The transport and fate of pollutants is often governed by both their tendency to sorb as well as their susceptibility to biodegradation. We have evaluated these parameters for 2,4,6-trinitrotoluene (TNT) and several biodegradation products. Slurries of aquifer sediment and groundwater depleted TNT at rates of 27, 7.7 and 5.9 μM day −1 under methanogenic, sulfate-reducing and nitrate-reducing conditions, respectively. Abiotic losses of TNT were determined in autoclaved controls. Abiotic TNT loss and subsequent transformation of the products was also observed. These transformations were especially important during the first step in the reduction of TNT. Subsequent abiotic reactions could account for all of the transformations observed in bottles which were initially nitrate-reducing. Other controls removed TNT reduction products at much slower rates than slurries containing live organisms. 2-Amino-4,6-dinitrotoluene was produced in all slurries but disappeared in methanogenic and in sulfate-reducing slurries within several weeks. This compound was converted to 2,4-diamino-6-nitrotoluene in all slurries with subsequent removal of the latter from methanogenic and sulfate-reducing slurries, while it persisted in autoclaved controls and in the nitrate-reducing slurries. Aquifer slurries incubated with either 2,4- or 2,6-diaminotoluene showed losses of these compounds relative to autoclaved controls under nitrate-reducing conditions but not under sulfate-reducing or methanogenic conditions. These latter compounds are important as reduced intermediates in the biodegradation of dinitrotoluenes and as industrial chemicals. In experiments to examine sorption, exposure to landfill sediment resulted in losses of approximately 15% of diaminotoluene isomers and 25% of aminodinitrotoluene isomers from initial solution concentrations within 24 h. Isotherms confirmed that the diaminotoluenes were least strongly sorbed and the amino-dinitrotoluenes most strongly sorbed to this sediment, while TNT sorption capacity was intermediate. In our studies, 2,4,6-triaminotoluene sorption capacity was indeterminate due to its chemical instability. Coupled with biodegradation information, isotherms help describe the likelihood of contaminant removal, persistence, and movement at impacted sites.

Journal of Industrial Microbiology and Biotechnolo↗

USGS2009

Crude oil at the Bemidji Site: 25 years of monitoring, modeling, and understanding

The fate of hydrocarbons in the subsurface near Bemidji, Minnesota, has been investigated by a multidisciplinary group of scientists for over a quarter century. Research at Bemidji has involved extensive investigations of multiphase flow and transport, volatilization, dissolution, geochemical interactions, microbial populations, and biodegradation with the goal of providing an improved understanding of the natural processes limiting the extent of hydrocarbon contamination. A considerable volume of oil remains in the subsurface today despite 30 years of natural attenuation and 5 years of pump‐and‐skim remediation. Studies at Bemidji were among the first to document the importance of anaerobic biodegradation processes for hydrocarbon removal and remediation by natural attenuation. Spatial variability of hydraulic properties was observed to influence subsurface oil and water flow, vapor diffusion, and the progression of biodegradation. Pore‐scale capillary pressure‐saturation hysteresis and the presence of fine‐grained sediments impeded oil flow, causing entrapment and relatively large residual oil saturations. Hydrocarbon attenuation and plume extent was a function of groundwater flow, compound‐specific volatilization, dissolution and biodegradation rates, and availability of electron acceptors. Simulation of hydrocarbon fate and transport affirmed concepts developed from field observations, and provided estimates of field‐scale reaction rates and hydrocarbon mass balance. Long‐term field studies at Bemidji have illustrated that the fate of hydrocarbons evolves with time, and a snap‐shot study of a hydrocarbon plume may not provide information that is of relevance to the long‐term behavior of the plume during natural attenuation.

Minnesota↗

USGS2004

Selected natural attenuation monitoring data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June 2002

Previous investigations indicated that natural attenuation and biodegradation of chlorinated volatile organic compounds (CVOCs) are substantial in shallow ground water beneath the 9-acre former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center (NUWC), 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 geochemical and selected CVOC data for ground water at OU 1, collected by the USGS during June 10-14, 2002, in support of long-term monitoring for natural attenuation. Overall, the geochemical data for June 2002 indicate that redox conditions in the upper-aquifer water remain favorable for reductive dechlorination of chlorinated VOCs because strongly reducing conditions persisted beneath much of the former landfill. Redox conditions in the intermediate aquifer downgradient of the landfill also remained favorable for reductive dechlorination, although the 2002 dissolved hydrogen (H2) concentration from well MW1-28 is questionable. Changes in redox conditions were observed at certain wells during 2002, but a longer monitoring period and more thorough interpretation are needed to ascertain if phytoremediation activities are affecting redox conditions and if biodegradation processes are changing over time. The Navy intends to complete a more thorough interpretation in preparation for the 5-year review of OU 1 scheduled for 2004. There were a few substantial differences between the 2002 concentrations and previously observed concentrations of volatile organic compounds. Total CVOC concentrations in 2002 samples decreased substantially in all piezometers sampled in the northern plantation, and the largest percentages of decrease were for the compounds trichloroethene (TCE) and cis-1,2-dichloroethene (cis-DCE). Changes in total CVOC concentrations in the southern plantation were less consistent. Historically high concentrations were observed in samples from three piezometers, with particularly substantial increases in TCE and cis-DCE concentrations, and historically low concentrations were observed in two piezometers, with particularly substantial decreases in TCE and cis-DCE concentrations. Similarly to the redox chemistry, a longer monitoring period and more thorough interpretation are needed to ascertain if phytoremediation activities are affecting CVOC concentrations and if biodegradation processes are changing over time. No changes in monitoring plans are proposed for June 2003, although the practice of deploying a data sonde downhole while purging the wells will be discontinued. Downhole monitoring added uncertainty to selected measured dissolved H2 concentrations because of the possibility that the sonde and cable created a bridge that resulted in non-equilibrium dissolved H2 concentrations at the wells.

Open-File Report↗

USGS2007

Dichloroethene and vinyl chloride degradation potential in wetland sediments at Twin Lakes and Pen Branch, Savannah River National Laboratory, South Carolina

A series of 14C-radiotracer-based microcosm experiments was conducted to assess the mechanisms and products of degradation of dichloroethene (DCE) and vinyl chloride (VC) in wetland sediments at the Department of Energy (DOE) Savannah River National Laboratory. This project investigated the potential for biotic and abiotic DCE and VC degradation in wetland sediments from the Twin Lakes area of the C-BRP investigative unit and from the portion of Pen Branch located directly down gradient from the CMP investigative unit. Substantial degradation of [1,2-14C] DCE and [1,2-14C] VC to 14CO2 was observed in all viable sediment microcosms prepared under oxic conditions. These results indicate that microbial mineralization processes, involving direct oxidation or cometabolic oxidation, are the primary mechanisms of DCE and VC biodegradation in Twin Lake and Pen Branch sediments under oxic conditions. Substantial degradation of [1,2-14C] DCE and [1,2-14C] VC was observed in all viable sediment microcosms incubated under anoxic conditions. Production of 14CO2 was observed in all sediment microcosms under anoxic conditions. In general, the accumulation of mineralization products (14CO2 and 14CH4) was comparable to the accumulation of those reduced daughter products (14C-VC, 14C-ethene or 14C-ethane) traditionally identified with chloroethene reductive dechlorination. These results indicate that microbial mineralization processes can be an important component of DCE and VC degradation in Twin Lake and Pen Branch sediments under anoxic conditions. These results demonstrate that an evaluation of the efficiency of in situ DCE and VC biodegradation in Twin Lakes and Pen Branch that is based solely on the observed accumulation of reduced daughter products may underestimate substantially the total extent of contaminant biodegradation and, thus, the contribution of biodegradation to overall contaminant attenuation. No evidence of abiotic degradation of [1,2-14C] DCE or [1,2-14C] VC was observed in heat-sterilized control treatments in this study under oxic or anoxic conditions. Efforts to enrich and isolate microorganisms involved in the mineralization of [1,2-14C] cis-DCE and/or [1,2-14C] VC were unsuccessful.

South Carolina↗

USGS2009

Natural offshore oil seepage and related tarball accumulation on the California coastline — Santa Barbara Channel and the southern Santa Maria Basin; source identification and inventory

Oil spillage from natural sources is very common in the waters of southern California. Active oil extraction and shipping is occurring concurrently within the region and it is of great interest to resource managers to be able to distinguish between natural seepage and anthropogenic oil spillage. The major goal of this study was to establish the geologic setting, sources, and ultimate dispersal of natural oil seeps in the offshore southern Santa Maria Basin and Santa Barbara Basins. Our surveys focused on likely areas of hydrocarbon seepage that are known to occur between Point Arguello and Ventura, California. Our approach was to 1) document the locations and geochemically fingerprint natural seep oils or tar; 2) geochemically fingerprint coastal tar residues and potential tar sources in this region, both onshore and offshore; 3) establish chemical correlations between offshore active seeps and coastal residues thus linking seep sources to oil residues; 4) measure the rate of natural seepage of individual seeps and attempt to assess regional natural oil and gas seepage rates; and 5) interpret the petroleum system history for the natural seeps. To document the location of sub-sea oil seeps, we first looked into previous studies within and near our survey area. We measured the concentration of methane gas in the water column in areas of reported seepage and found numerous gas plumes and measured high concentrations of methane in the water column. The result of this work showed that the seeps were widely distributed between Point Conception east to the vicinity of Coal Oil Point, and that they by in large occur within the 3-mile limit of California State waters. Subsequent cruises used sidescan and high resolution seismic to map the seafloor, from just south of Point Arguello, east to near Gaviota, California. The results of the methane survey guided the exploration of the area west of Point Conception east to Gaviota using a combination of seismic instruments. The seafloor was mapped by sidescan sonar, and numerous lines of high -resolution seismic surveys were conducted over areas of interest. Biomarker and stable carbon isotope ratios were used to infer the age, lithology, organic matter input, and depositional environment of the source rocks for 388 samples of produced crude oil, seep oil, and tarballs mainly from coastal California. These samples were used to construct a chemometric fingerprint (multivariate statistics) decision tree to classify 288 additional samples, including tarballs of unknown origin collected from Monterey and San Mateo County beaches after a storm in early 2007. A subset of 9 of 23 active offshore platform oils and one inactive platform oil representing a few oil reservoirs from the western Santa Barbara Channel were used in this analysis, and thus this model is not comprehensive and the findings are not conclusive. The platform oils included in this study are from west to east: Irene, Hildago, Harvest, Hermosa, Heritage, Harmony, Hondo, Holly, Platform A, and Hilda (now removed). The results identify three “tribes” of 13 C-rich oil samples inferred to originate from thermally mature equivalents of the clayey-siliceous, carbonaceous marl, and lower calcareous-siliceous members of the Monterey Formation. Tribe 1 contains four oil families having geochemical traits of clay-rich marine shale source rock deposited under suboxic conditions with substantial higher-plant input. Tribe 2 contains four oil families with intermediate traits, except for abundant 28,30-bisnorhopane, indicating suboxic to anoxic marine marl source rock with hemipelagic input. Tribe 3 contains five oil families with traits of distal marine carbonate source rock deposited under anoxic conditions with pelagic but little or no higher-plant input. Tribes 1 and 2 occur mainly south of Point Conception in paleogeographic settings where deep burial of the Monterey Formation source rock favored generation from all three members or their equivalents. In this area, oil from the clayey-siliceous and carbonaceous marl members (Tribes 1 and 2) may overwhelm that from the lower calcareous-siliceous member (Tribe 3) because the latter is thinner and less oil-prone than the overlying members. Tribe 3 occurs mainly north of Point Conception, where shallow burial caused preferential generation from the underlying lower calcareous-siliceous member or another unit with similar characteristics. It is very desirable to be able to clearly distinguish the naturally occurring seep oils from the anthropogenically derived platform oils. Within the “training set” of oils and tars (388 samples), the biomarker parameters are sometimes sufficient to allow unique discrimination of individual platform oils. More often however, platform samples and seep samples with sources geographically close to each other are too similar to each other, with respect to the biomarker parameters, to definitively differentiate them on that basis alone. In some cases other parameters can be helpful. These other parameters are related to the degree of biogeochemical degradation or weathering that the oils or tars have experienced. These components include the typical oil distribution of n-alkane hydrocarbons and isoprenoids pristane and phytane. All of the platform oils in our sample set contain these components. On the other hand, the seep oils or tars have been exposed to significant biodegradation while in the near subsurface. The majority, but not all of seep oils or tars have been biodegraded up to or beyond the loss of n-alkanes and isoprenoids. Seep oils found in the vicinity of Coal Oil Point or Arroyo Burro are apparently the least weathered and are particularly likely to retain significant n-alkanes and isoprenoids. Therefore the combination of chemometric fingerprinting and the presence or absence of n-alkanes and isoprenoids help to differentiate anthropogenic production oils versus natural seeps oils and tars. The differentiation is not always definitive because of the close chemical similarity of some samples and the variability in the biodegradation progression. This is the case near Coal Oil Point, and near Platform A (Dos Cuadros Field) where seep oils and Platform Holly and Platform A oils are genetically very similar and cannot be definitively distinguished after a period of a few days of weathering. In contrast, oils from the Point Conception platforms can be distinguished on the basis of chemometric fingerprinting alone. In the middle of this spectrum are oils from Platforms Harmony, Heritage, and Hondo, where it is expected that oil weathering would take on the order of two weeks to a month to produce tarballs similar to those seen near Point Conception. In this case there is a much greater degree of weathering needed to proceed from produced oil to the biodegraded tar characteristic of tarball stranded on the beach. Tar deposition on beaches was monitored as part of cooperative with the County of Santa Barbara Energy Division and the U.S. Geological Survey during 2001-2003. We found tar deposition varies on a seasonal basis. In general, tarballs accumulate at a faster rate or remain longer on all beaches during the summer and fall months. The reasons for this are unclear based on our limited observations, however we speculate that factors such as prevailing winds and currents combined with more quiescent wave conditions favors the accumulation and preservation of tarballs on the beach during the summer and fall months. In contrast, winter storms, with much greater wave action remove beach sand and other materials, and stormy seas tend to break up oil that might weather into tarballs. Natural seepage is affected by the spring/neap tidal cycle; however, the link to tar deposition is unclear. Longer periods of monitoring are needed to address the variability in the data and provide a more robust statistical analysis.

California↗

USGS2009

Potential for microbial degradation of cis-dichloroethene and vinyl chloride in streambed sediment at the U.S. Department of Energy, Kansas City Plant, Missouri, 2008

A series of carbon-14 (14C) radiotracer-based microcosm experiments was conducted to assess the mechanisms and products of degradation of cis-dichloroethene (cis-DCE) and vinyl chloride (VC) in streambed sediments at the U.S. Department of Energy, Kansas City Plant in Kansas City, Missouri. The focus of the investigation was the potential for biotic and abiotic cis-DCE and VC degradation in surficial and underlying hyporheic sediment from the Blue River and its tributaries, Indian Creek and Boone Creek. Substantial degradation of [1,2-14C] cis-DCE and [1,2-14C] VC to 14C-carbon dioxide (14CO2) was observed in all viable surficial sediment microcosms prepared under oxic conditions. No significant accumulation of reductive dechlorination products was observed under these oxic incubation conditions. The results indicate that microbial mineralization processes involving direct oxidation or co-metabolic oxidation are the primary mechanisms of cis-DCE and VC biodegradation in oxic stream sediment at the Kansas City Plant. Substantial mineralization of [1,2-14C] VC also was observed in all viable surficial sediment microcosms incubated in the absence of detectable oxygen (dissolved oxygen concentrations less than 25 micrograms per liter). In general, the accumulation of mineralization products (14CO2 and 14C-methane [14CH4]) predominated with only trace-level detection of the reductive dechlorination product, 14C-ethene. In contrast, microbial degradation of [1,2-14C] cis-DCE by reductive dechlorination or mineralization was not significant in the absence of detectable oxygen. The potential for [1,2-14C] VC biodegradation also was significant in sediments from the deeper hyporheic zones under oxic conditions and in the absence of detectable oxygen. In this study, microbial degradation of [1,2-14C] cis-DCE was not significant in hyporheic sediment treatments under either oxygen condition. Taken together, the results indicate that microbial mineralization processes in streambed sediments at the Kansas City Plant can be an important component of cis-DCE and VC degradation under oxic conditions and of VC degradation even in the absence of detectable oxygen. These results demonstrate that an evaluation of the efficiency of in situ cis-DCE and VC biodegradation in streambed sediments, based solely on observed accumulations of reduced daughter products, may underestimate substantially the total extent of contaminant biodegradation and, thus, the potential importance of the hyporheic zone and streambed sediments as barriers to the discharge of contaminated groundwater.

Missouri↗

USGS2013

Organic wastewater compounds in water and sediment in and near restored wetlands, Great Marsh, Indiana Dunes National Lakeshore, 2009–11

A cooperative investigation between the U.S. Geological Survey and the National Park Service was completed from 2009 through 2011 to understand the occurrence, distribution, and environmental processes affecting concentrations of organic wastewater compounds in water and sediment in and near Great Marsh at the Indiana Dunes National Lakeshore in Beverly Shores, Indiana. Sampling sites were selected to represent hydrologic inputs to the restored wetlands from adjacent upstream residential and less developed areas and to represent discharge points of cascading cells within the restored wetland. A multiphase approach was used for the investigation. Discrete water samples and time-integrated passive samples were analyzed for 69 organic wastewater compounds. Continuous water-level information and periodic streamflow measurements characterized flow conditions at discharge points from restored wetland cells. Wetland sediments were collected and analyzed for sorptive losses of organic wastewater compounds and to evaluate of the potential for wetland sediments to biotransform organic wastewater compounds. A total of 52 organic wastewater compounds were detected in discrete water samples at 1 or more sites. Detections of organic wastewater compounds were widespread, but concentrations were generally low and 95 percent were less than 2.1 micrograms per liter. Six compounds were detected at concentrations greater than 2.1 micrograms per liter—four fecal sterols (beta-sitosterol, cholesterol, beta-stigmastanol, and 2-beta coprostanol), one plasticizer (bis-2-ethylhex ylphthalate), and a non-ionic detergent (4-nonylphenol diethoxylate). Two 1-month deployments of time-integrative passive samplers, called polar organic chemical integrative samplers, detected organic wastewater compounds at lower concentrations than were possible with discrete water samples. Isopropyl benzene (solvent), caffeine (plant alkaloid, stimulant), and hexahydrohexamethyl cyclopentabenzopyran (fragrance) were detected in more than half of the extracts from passive samplers, but they were not detected in any discrete water sample. The Yeast Estrogen Screen assay identified measurable estrogenicity in one passive sampler extract from the most downstream wetland site in both the April and November–December 2011 deployments and in passive sampler extracts from one residential and one upstream site in the November–December 2011 deployment only. Surface-water levels in the restored wetland cells were monitored continuously using submersible pressure transducers in hand-driven well points screened in the surface water. Surface-water levels in the wetland cells responded quickly to precipitation and substantially receded within 2 days following the largest rainfall events. Seasonal patterns in water levels generally showed higher and more variable surface-water levels in the wetland cells during spring and early summer. Water levels in the wetland cells fell below the elevation of the control structures and ceased to flow over the spillways during extended dry periods (primarily late summer and early fall). Daily loads of seven organic wastewater compounds, as indicators of septic system effluent, were estimated for samples collected at wetland outlet spillways when flow measurements could be made. Median daily loads of the indicator organic wastewater compounds increased in downstream order, and the largest median loads were measured at the most downstream site. Median daily loads were higher for samples collected in spring and summer than those collected in fall, as the higher seasonal water levels increased streamflow at the wetland outlet spillways. Wetland sediment samples were analyzed for 84 organic wastewater compounds, polycyclic aromatic hydrocarbons, and semivolatile organic compounds to investigate the fate of contaminants in Great Marsh. The top five detected compounds by total mass in wetland sediment samples were beta-sitosterol, beta-stigmastanol, cholesterol, bis(2-ethylhexyl) phthalate, and phenol. Polycyclic aromatic hydrocarbons also were frequently detected in wetland sediment samples. Source apportionment of polycyclic aromatic hydrocarbon detections indicated atmospheric sources of pyrogenic compounds, rather than residential sources. Comparisons of polycyclic aromatic hydrocarbon concentrations in wetland sediment samples to sediment quality target guidelines indicated the potential for harmful effects on sediment-dwelling organisms at several sites. Biodegradation of select endocrine-disrupting compounds (17α-ethinylestradiol, 4-nonylphenol, triclocarban, and bisphenol A) in shallow wetland sediments was evaluated in laboratory experiments by using carbon-14 radiolabeled model contaminants. Substantial biodegradation of certain organic wastewater compounds were demonstrated, primarily in oxic (oxygen containing) environments. One of four modeled compounds, bisphenol A, was biodegraded in anoxic (oxygen free) environments. Only sediments collected nearest residential areas exhibited degradation of the synthetic birth control pharmaceutical, 17α-ethinylestradiol, possibly owing to adaptation and acclimation of the indigenous microbial community to septic discharge and the resultant selection of a microbial capability for biodegradation of 17α-ethinylestradiol.

Indiana↗

USGS2019

Dissolved organic carbon turnover in permafrost-influenced watersheds of interior Alaska: Molecular insights and the priming effect

Increased permafrost thaw due to climate change in northern high-latitudes has prompted concern over impacts on soil and stream biogeochemistry that affect the fate of dissolved organic carbon (DOC). Few studies to-date have examined the link between molecular composition and biolability of dissolved organic matter (DOM) mobilized from different soil horizons despite its importance in understanding carbon turnover in aquatic systems. Additionally, the effect of mixed DOM sources on microbial metabolism (e.g., priming) is not well understood. No studies to-date have addressed potential priming effects in northern high-latitude or permafrost-influenced aquatic ecosystems, yet these ecosystems may be hot spots of priming where biolabile, ancient permafrost DOC mixes with relatively stable, modern stream DOC. To assess biodegradability and priming of DOC in permafrost-influenced streams, we conducted 28 day bioincubation experiments utilizing a suite of stream samples and leachates of fresh vegetation and different soil horizons, including permafrost, from Interior Alaska. The molecular composition of unamended DOM samples at initial and final time points was determined by ultrahigh resolution mass spectrometry. Initial molecular composition was correlated to DOC biodegradability, particularly the contribution of energy-rich aliphatic compounds, and stream microbial communities utilized 50–56% of aliphatics in permafrost-derived DOM within 28 days. Biodegradability of DOC followed a continuum from relatively stable stream DOC to relatively biolabile DOC derived from permafrost, active layer organic soil, and vegetation leachates. Microbial utilization of DOC was ∼3–11% for stream bioincubations and ranged from 9% (active layer mineral soil-derived) to 66% (vegetation-derived) for leachate bioincubations. To investigate the presence or absence of a priming effect, bioincubation experiments included treatments amended with 1% relative carbon concentrations of simple, biolabile organic carbon substrates (i.e., primers). The amount of DOC consumed in primed treatments was not significantly different from the control in any of the bioincubation experiments after 28 days, making it apparent that the addition of biolabile permafrost-derived DOC to aquatic ecosystems will likely not enhance the biodegradation of relatively modern, stable DOC sources. Thus, future projections of carbon turnover in northern high-latitude region streams may not have to account for a priming effect.

Alaska↗

USGS1992

Identification of persistent 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 13 C 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 F 300-50 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.

Journal of Contaminant Hydrology↗