Geology topics
Publications and source records attributed to P. M. Bradley.
Microbial reductive dechlorination of [1,2- 14 C]trichloroethene to [ 14 C] cis -dichloroethene and [ 14 C]vinyl chloride was observed at 4°C in anoxic microcosms prepared with cold temperature-adapted aquifer and river sediments from Alaska. Microbial anaerobic oxidation of [1,2- 14 C] cis -dichloroethene and [1,2- 14 C]vinyl chloride to 14 CO 2 also was observed under these conditions.
Concentrations of total lead as high as 1,600 μg/L were detected in gasoline-contaminated and uncontaminated groundwater at three gasoline-release sites in South Carolina. Total lead concentrations were highest in turbid groundwater samples from gasoline-contaminated and uncontaminated wells, whereas lower turbidity groundwater samples (collected using low-flow methods) had lower total lead concentrations. Dissolved lead concentrations in all wells sampled, however, were less than 15 μg total lead/L, the current United States Environmental Protection Agency (US EPA) maximum contaminant level (MCL). Because many total lead concentrations exceeded the MCL, the source of lead to the groundwater system at two of the three sites was investigated using a stable lead isotope ratio approach. Plots of the stable isotope ratios of lead (Pb) in groundwater as 207 Pb/ 206 Pb versus 208 Pb/ 206 Pb, and 208 Pb/ 204 Pb versus 206 Pb/ 204 Pb were similar to ratios characteristic of lead-based minerals in local rocks of the southeastern US, and were not similar to the stable lead isotopes ratios characteristic of distant lead ore deposits such as Broken Hill, Australia, used to produce tetraethyl lead in gasoline products prior to its phase-out and ban in the United States. Moreover, the isotopic composition of dissolved lead was equivalent to the isotopic composition of total lead in turbid samples collected from the same well, suggesting that the majority of the lead detected in the groundwater samples was associated with sediment particulates of indigenous aquifer material, rather than lead associated with spilled leaded gasoline. The results of this investigation indicate that (1) lead detected at some gasoline-release sites may be derived from the local aquifer material, rather than the gasoline release, and consequently may affect site-specific remediation goals; (2) non-low flow groundwater sampling methods, such as a disposable bailer, may result in turbid groundwater samples and high total lead concentrations, and; (3) stable lead isotopes can be used to clarify the source of lead detected above permissible levels in gasoline-contaminated groundwater systems.
The effect of pre-existing factors, e.g., hydrologic, geochemical, and microbiological properties, on the results of oxygen addition to a reformulated gasoline-contaminated groundwater system was studied. Oxygen addition with an oxygen-release compound (a proprietary form of magnesium peroxide produced different results with respect to dissolved oxygen (DO) generation and contaminant decrease in the two locations. Oxygen-release compound injected at the former UST source area did not significantly change measured concentrations of DO, benzene, toluene, or MTBE. Conversely, oxygen-release compound injected 200 m downgradient of the former UST source area rapidly increased DO levels, and benzene, toluene, and MTBE concentrations decreased substantially. The different results could be related to differences in hydrologic and geochemical conditions that characterized the two locations prior to oxygen addition. The lack of recharge to ground water in the paved UST source area led to a much larger geochemical sink for DO compared to ground water in the unpaved area.
The potential for [U-14C] TBA biodegradation was examined in laboratory microcosms under a range of terminal electron accepting conditions. TBA mineralization to CO2 was substantial in surface-water sediments under oxic, denitrifying, or Mn(IV)-reducing conditions and statistically significant but low under SO4-reducing conditions. Thus, anaerobic TBA biodegradation may be a significant natural attenuation mechanism for TBA in the environment, and stimulation of in situ TBA bioremediation by addition of suitable terminal electron acceptors may be feasible. No degradation of [U-14C] TBA was observed under methanogenic or Fe(III)-reducing conditions.
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No abstract available.
The search for extraterrestrial life may be facilitated if ecosystems can be found on Earth that exist under conditions analogous to those present on other planets or moons. It has been proposed, on the basis of geochemical and thermodynamic considerations, that geologically derived hydrogen might support subsurface microbial communities on Mars and Europa in which methanogens form the base of the ecosystem1-5. Here we describe a unique subsurface microbial community in which hydrogen-consuming, methane-producing Archaea far outnumber the Bacteria. More than 90% of the 16s ribosomal DNA sequences recovered from hydrothermal waters circulating through deeply buried igneous rocks in Idaho are related to hydrogen-using methanogenic microorganisms. Geochemical characterization indicates that geothermal hydrogen, not organic carbon, is the primary energy source for this methanogen-dominated microbial community. These results demonstrate that hydrogen-based methanogenic communities do occur in Earth's subsurface, providing an analogue for possible subsurface microbial ecosystems on other planets.
Previous investigations demonstrated that respiratoly reductive dechlorination of vinyl chloride (VC) can be efficient even at H 2 concentrations (≤2 n M ) that are characteristic of SO 4 -reducing conditions. In the study reported here, microorganisms indigenous to a lake-bed sediment completely mineralized [1,2- 14 C] ethene to 14 14CO 2 when incubated under SO 4 -reducing conditions. Together, these observations argue for a novel mechanism for the net anaerobic oxidation of VC to CO 2 : reductive dechlorination of VC to ethene followed by anaerobic oxidation of ethene to CO 2 . Moreover, the results of this study suggest that reliance on ethene and/or ethane accumulation as a quantitative indicator of complete reductive dechlorination of chioroethene contaminants may not be warranted.
The U.S. Geological Survey (USGS) evaluated the natural attenuation of chlorinated volatile organic compounds (CVOCs) in ground water beneath the former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center, Division Keyport, Washington. The predominant contaminants in ground water are trichloroethene (TCE) and its degradation byproducts cis-1,2-dichloroethene (cisDCE) and vinyl chloride (VC). The Navy planted two hybrid poplar plantations on the landfill in spring of 1999 to remove and control the migration of CVOCs in shallow ground water. Previous studies provided evidence that microbial degradation processes also reduce CVOC concentrations in ground water at OU 1, so monitored natural attenuation is a potential alternative remedy if phytoremediation is ineffective. This report describes the current (2000) understanding of natural attenuation of CVOCs in ground water at OU 1 and the impacts that phytoremediation activities to date have had on attenuation processes. The evaluation is based on ground-water and surface-water chemistry data and hydrogeologic data collected at the site by the USGS and Navy contractors between 1991 and 2000. Previously unpublished data collected by the USGS during 1996-2000 are presented. Natural attenuation of CVOCs in shallow ground water at OU 1 is substantial. For 1999-2000 conditions, approximately 70 percent of the mass of dissolved chlorinated ethenes that was available to migrate from the landfill was completely degraded in shallow ground water before it could migrate to the intermediate aquifer or discharge to surface water. Attenuation of CVOC concentrations appears also to be substantial in the intermediate aquifer, but biodegradation appears to be less significant; those conclusions are less certain because of the paucity of data downgradient of the landfill beneath the tide flats. Attenuation of CVOC concentrations is also substantial in surface water as it flows through the adjacent marsh and out to the tide flats. Attenuation processes other than dilution reduce the CVOC flux in marsh surface water by about 40 percent by the time the water discharges to the tide flats. Despite the importance of natural attenuation processes at reducing both the contaminant concentrations and the contaminant mass at OU 1, natural attenuation alone was not effective enough in the year 2000 to meet current numerical remediation goals for the site. That was in part due to the relatively short distance between the landfill and the adjacent marsh, and in part due to the extremely high CVOC concentrations directly beneath the landfill. Phytoremediation activities had some apparent effect on contaminant concentrations in ground water and surface water, but ground-water redox conditions to date (2000) were not affected by the February 1999 asphalt removal for tree planting. The poplar trees in the phytoremediation plantations were not yet mature in 2000, so the lack of discernible changes to date is understandable. Concentration changes of some redox-sensitive compounds suggest that increased recharge following asphalt removal diluted ambient landfill ground water. CVOC concentrations increased in some downgradient wells in both the northern and southern plantations after asphalt removal, whereas CVOC concentrations decreased in some upgradient wells in the southern plantation. A clear increase in CVOC concentrations in marsh surface water followed asphalt removal, apparently from increased contaminant discharge in ground water beneath the southern plantation. The results of the natural attenuation evaluation suggest than minor modifications to the current sampling plan may be beneficial to understanding the future impacts of phytoremediation and natural attenuation on the fate and distribution of CVOCs at OU 1.
Microbial degradation of methyl tert-butyl ether (MTBE) was observed in surface water-sediment microcosms under anaerobic conditions. The efficiency and products of anaerobic MTBE biodegradation were 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 the toxic product, tert-butyl alcohol (TBA). In the absence of significant methanogenic activity, accumulation of [14C]TBA generally decreased, and mineralization of [U-14C]MTBE to 14CO2 generally increased as the oxidative potential of the predominant terminal electron acceptor increased in the order of SO4, Fe(III), Mn(IV) < NO3 < O2. Microbial mineralization of MTBE to CO2 under Mn(IV)or SO4-reducing conditions has not been reported previously. The results of this study indicate that microorganisms inhabiting the sediments of streams and lakes can degrade MTBE effectively under a range of anaerobic terminal electron-accepting conditions. Thus, anaerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States.
Microbial communities indigenous to a shallow groundwater system near Beaufort, SC, degraded milligram per liter concentrations of methyl tert -butyl ether (MTBE) under natural and artificial oxic conditions. Significant MTBE biodegradation was observed where anoxic, MTBE-contaminated groundwater discharged to a concrete-lined ditch. In the anoxic groundwater adjacent to the ditch, concentrations of MTBE were >1 mg/L. Where groundwater discharge occurs, dissolved oxygen (DO) concentrations beneath the ditch exceeded 1.0 mg/L to a depth of 1.5 m, and MTBE concentrations decreased to <1 μg/L prior to discharge. MTBE mass flux calculations indicate that 96% of MTBE mass loss occurs in the relatively small oxic zone prior to discharge. Samples of a natural microbial biofilm present in the oxic zone beneath the ditch completely degraded [U- 14 C]MTBE to [ 14 C]CO 2 in laboratory liquid culture studies, with no accumulation of intermediate compounds. Upgradient of the ditch in the anoxic, MTBE- and BTEX-contaminated aquifer, addition of a soluble oxygen release compound resulted in oxic conditions and rapid MTBE biodegradation by indigenous microorganisms. In an observation well located closest to the oxygen addition area, DO concentrations increased from 0.4 to 12 mg/L in <60 days and MTBE concentrations decreased from 20 to 3 mg/L. In the same time period at a downgradient observation well, DO increased from <0.2 to 2 mg/L and MTBE concentrations decreased from 30 to <5 mg/L. These results indicate that microorganisms indigenous to the groundwater system at this site can degrade milligram per liter concentrations of MTBE under natural and artificial oxic conditions.
Microorganisms indigenous to stream and lake bed sediments, collected from 11 sites throughout the United States, demonstrated significant mineralization of the fuel oxygenate, methyl-tert-butyl ether (MTBE). Mineralization of [U-14C]MTBE to 14CO2 ranged from 15 to 66% over 50 days and did not differ significantly between sediments collected from MTBE contaminated sites and from sites with no history of MTBE exposure. This result suggests that even the microbial communities indigenous to newly contaminated surface water systems will exhibit some innate ability to attenuate MTBE under aerobic conditions. The magnitude of MTBE mineralization was related to the sediment grain size distribution. A pronounced, inverse correlation (p < 0.001; r2 = 0.73) was observed between the final recovery of 14CO2 and the percentage content of silt and clay sized grains (grain diameter < 0.125 mm). The results of this study indicate that the microorganisms that inhabit the bed sediments of streams and lakes can degrade MTBE efficiently and that this capability is widespread in the environment. Thus aerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States and may contribute to the reported transience of MTBE in some surface waters.
Mineralization of [U-14C] methyl t-butyl ether (MTBE) to 14CO2 without accumulation of t-butyl alcohol (TBA) was observed in surface-water sediment microcosms under denitrifying conditions. Methanogenic activity and limited transformation of MTBE to TBA were observed in the absence of denitrification. Results indicate that bed sediment microorganisms can effectively degrade MTBE to nontoxic products under denitrifying conditions.
To evaluate the potential contribution of in situ biodegradation as a mechanism for natural attenuation of MTBE in surface water, surface water sediments were collected from streams and lakes at 11 sites throughout the US and the ability of the indigenous microorganisms to mineralize [U-14C] MTBE to 14CO2 under aerobic conditions was examined. Mineralization of [U-14C] MTBE to 14CO2 ranged from 15 to 66% over 50 days and did not differ significantly between sediments collected from MTBE contaminated sites and from sites with no history of MTBE exposure. The microorganisms, which inhabit the bed sediments of streams and lakes could degrade MTBE efficiently and this capability is widespread in the environment. 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. 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.
The hypothesis that artificial oxic conditions will lead to MTBE biodegradation by indigenous microorganisms in anoxic, gasoline-contaminated aquifers was examined by adding oxygen in the form of a metal peroxide slurry to an anoxic part of gasoline-contaminated aquifer in South Carolina. Field observations of relatively rapid aerobic MTBE biodegradation following oxygen addition suggest that the indigenous bacteria have become acclimated not only to mg/L concentrations of MTBE in the gasoline plume, but also to periodic delivery of oxygen by recharge events. Significant natural attenuation of MTBE could occur if the oxygen limitations naturally associated with gasoline releases can be removed, either under natural conditions where discharging anoxic groundwater comes into contact with oxygen, or artificial conditions where oxygen can be added to aquifers containing mg/L concentrations of MTBE. This final solution might be an effective strategy for intercepting characteristically long MTBE plumes, particularly at sites not characterized by groundwater discharge to land surface. This is an abstract of a paper presented at the 222nd ACS National Meting (Chicago, IL 8/26-30/2001).
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).
Oxygen in the form of a metal peroxide slurry (MgO2 and water) was added to an anoxic part of a gasoline-contaminated aquifer in South Carolina to test the hypothesis that artificial oxic conditions will lead to MTBE biodegradation by indigenous microorganisms in anoxic, gasoline-contaminated aquifers. The slurry slowly released dissolved oxygen upon hydrolysis with groundwater, and was a proprietary mixture consisting of ??? 25-35 wt % MgO2. Significant natural attenuation of MTBE could occur if the oxygen limitations naturally associated with gasoline releases could be removed, either under natural conditions where discharging anoxic groundwater comes into contact with oxygen, or artificial conditions where oxygen could be added to aquifers containing milligram per liter concentrations of MTBE. This final solution might be an effective strategy for intercepting characteristically long MTBE plumes, particularly at those sites not characterized by groundwater discharge to land surface.
Under methanogenic conditions, microbial degradation of [1,2- 14 C]vinyl chloride (VC) resulted in significant (14 ± 3% maximum recovery) but transient recovery of radioactivity as 14 C-acetate. Subsequently, 14 C-acetate was degraded to 14 CH 4 and 14 CO 2 (18 ± 2% and 54 ± 3% final recoveries, respectively). In contrast, under 2-bromoethanesulfonic acid (BES) amended conditions, 14 C-acetate recovery remained high (27 ± 1% maximum recovery) throughout the study, no 14 CH 4 was produced, and the final recovery of 14 CO 2 was only 35 ± 4%. These results demonstrate that oxidative acetogenesis may be an important mechanism for anaerobic VC biodegradation. Moreover, these results (1) demonstrate that microbial degradation of VC to CH 4 and CO 2 may involve oxidative acetogenesis followed by acetotrophic methanogenesis and (2) suggest that oxidative acetogenesis may be the initial step in the net oxidation of VC to CO 2 reported previously under Fe(III)-reducing, SO 4 -reducing, and humic acids-reducing conditions.