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At least 109 records · Page 6Linked to original sources

USGS2026

Structural evolution of iron coordination in proteins across Earth’s oxygenation history

Protein metal-binding sites support essential biological functions shaped by protein fold, subunit interactions, and cofactor chemistry. Because these sites encode both biochemical function and environmental constraint, they offer a route to connect protein evolution with changes in Earth’s surface environment through time. Of particular interest is iron (Fe), the most widely used metal in biology and a cofactor central to both anaerobic and aerobic metabolism. Here, we systematically compare the immediate chemical environments of functionally essential Fe-binding sites in three-dimensional protein structures to test whether Fe coordination spheres differ across oxygen contexts. Using a curated dataset of experimentally determined structures, we identify a clear shift in the local chemistry of Fe-binding environments from anaerobic to aerobic proteins. Aerobic Fe sites are significantly more hydrophilic than anaerobic ones, and amino-acid composition analyses show reduced cysteine use in aerobic Fe-binding neighborhoods. These patterns suggest that as Earth’s surface environments became more oxygenated, proteins retained Fe as a core redox metal while reconfiguring local coordination chemistry in ways less vulnerable to oxidative damage. More broadly, this study introduces and applies the Coordination Sphere Analysis and Comparison (CSAC) workflow, an open and archived Python workflow for extracting local metal-binding environments from structure datasets, providing a framework for linking metalloprotein structure to evolutionary and geobiological transitions across Earth history.

Discover Life↗

USGS1984

Stable isotope geochemistry of acid mine drainage: Experimental oxidation of pyrite

Sulfate and water from experiments in which pyrite was oxidized at a pH of 2.0 were analyzed for sulfur and oxygen stable isotopes. Experiments were conducted under both aerobic and anaerobic sterile conditions, as well as under aerobic conditions in the presence of Thiobacillus ferrooxidans, to elucidate the pathways of oxidation. Oxygen isotope fractionation between SO2-4 and H2O varied from +4.0 %. (anaerobic, sterile) to + 18.0 %. (aerobic, with T. ferrooxidans.). The oxygen isotope composition of dissolved oxygen utilized in both chemical and microbially-mediated oxidation was also determined (+11.4 %., by T. ferrooxidans; +18.4 %., chemical). Contributions of water-derived oxygen and dissolved oxygen to the sulfate produced in the oxidation of pyrite could thus be estimated. Water-derived oxygen constituted from 23 to ~ 100 percent of the oxygen in the sulfate produced in the experiments, and this closely approximates the range of contribution in natural acid mine drainage. Oxidation of sulfides in anaerobic, water-saturated environments occurs primarily by chemical oxidation pathways, whereas oxidation of sulfides in well-aerated, unsaturated zone environments occurs dominantly by microbially mediated pathways.

Geochimica et Cosmochimica Acta↗

USGS1987

Aqueous pyrite oxidation by dissolved oxygen and by ferric iron

Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.

Geochimica et Cosmochimica Acta↗

USGS1994

Effect of atrazine on potential denitrification in aquifer sediments

Agriculturaf use of fertilizers and herbicides has often resulted in nitrate and atrazine contamination of the shallow aquifers that underlay cultivated fields. In several cases, the concentrations of atrazine and nitrate dissolved in ground water are positively correlated (Spalding ef al., 1979; Chen and Druliner, 1987; Spalding et al., 1989). Because simultaneous application of nitrate fertilizers and the herbicide, atrazine, is common, the co-occurrence of these contaminants in ground water is not entirely unexpected. However, the possibility also exists that this co-occurrence may ret&t interactions of atrazine with nitrate in the subsurface environment. R&ton and Cervelh (1980), McElhannon ei al. (1984) and Mills (1984) have reported that atrazine inhibits denitrification in‘soil’lf this i‘s indeed the case, atrazine contamination may contribute to nitrate preservation and accumulation in anaerobic aquifers by inhibiting denitrification, the principal mechanism for nitrate removal in anaerobic systems. Huwever, the effect of atrazine on the rate of denit~ficat~on in soils remains controversial, because atrazine has been reported variously to enhance denitrification (Cervelli and Ralston, 1983) or to have no effect on denitrification in soils (Bollag and Henninger, 1976; Yeomans and Bremner, IQ85, 1987). Moreover, the effect of dissolved atrazine concentrations on the rate of denitrification in aquifer sediments has not been reported. Our purpose was to determine the elects of dissolved atrazine concentrations on potential rates ofdenitri~~t~on in aquifer sediments from two different agricultural areas to evaluate the hypothesis that, by inhibiting denitrification, atrazine contributes to nitrate preservation in anaerobic aquifer systems.

Soil Biology and Biochemistry↗

USGS2013

The effect of coal bed dewatering and partial oxidation on biogenic methane potential

Coal formation dewatering at a site in the Powder River Basin was associated with enhanced potential for secondary biogenic methane determined by using a bioassay. We hypothesized that dewatering can stimulate microbial activity and increase the bioavailability of coal. We analyzed one dewatered and two water-saturated coals to examine possible ways in which dewatering influences coal bed natural gas biogenesis by looking at differences with respect to the native coal microbial community, coal-methane organic intermediates, and residual coal oxidation potential. Microbial biomass did not increase in response to dewatering. Small Subunit rRNA sequences retrieved from all coals sampled represented members from genera known to be aerobic, anaerobic and facultatively anaerobic. A Bray Curtis similarity analysis indicated that the microbial communities in water-saturated coals were more similar to each other than to the dewatered coal, suggesting an effect of dewatering. There was a higher incidence of long chain and volatile fatty acid intermediates in incubations of the dewatered coal compared to the water-saturated coals, and this could either be due to differences in microbial enzymatic activities or to chemical oxidation of the coal associated with O 2 exposure. Dilute H 2 O 2 treatment of two fractions of structural coal (kerogen and bitumen + kerogen) was used as a proxy for chemical oxidation by O 2 . The dewatered coal had a low residual oxidation potential compared to the water-saturated coals. Oxidation with 5% H 2 O 2 did increase the bioavailability of structural coal, and the increase in residual oxidation potential in the water saturated coals was approximately equivalent to the higher methanogenic potential measured in the dewatered coal. Evidence from this study supports the idea that coal bed dewatering could stimulate biogenic methanogenesis through partial oxidation of the structural organics in coal once anaerobic conditions are restored.

Montana;Wyoming↗

USGS2002

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: Groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally attenuated by a combination of active anaerobic and aerobic biotransformation processes. ?? 2002 Elsevier Science B.V. All rights reserved.

Journal of Contaminant Hydrology↗

USGS1997

Microbial reduction of iodate

The different oxidation species of iodine have markedly different sorption properties. Hence, changes in iodine redox states can greatly affect the mobility of iodine in the environment. Although a major microbial role has been suggested in the past to account for these redox changes, little has been done to elucidate the responsible microorganisms or the mechanisms involved. In the work presented here, direct microbial reduction of iodate was demonstrated with anaerobic cell suspensions of the sulfate reducing bacterium Desulfovibrio desulfuricans which reduced 96% of an initial 100 ??M iodate to iodide at pH 7 in 30 mM NaHCO3 buffer, whereas anaerobic cell suspensions of the dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens were unable to reduce iodate in 30 mM NaHCO3 buffer (pH 7). Both D. desulfuricans and S. putrefaciens were able to reduce iodate at pH 7 in 10 mM HEPES buffer. Both soluble ferrous iron and sulfide, as well as iron monosulfide (FeS) were shown to abiologically reduce iodate to iodide. These results indicate that ferric iron and/or sulfate reducing bacteria are capable of mediating both direct, enzymatic, as well as abiotic reduction of iodate in natural anaerobic environments. These microbially mediated reactions may be important factors in the fate and transport of 129I in natural systems.

Water, Air, & Soil Pollution↗

USGS1989

Oxidation of aromatic contaminants coupled to microbial iron reduction

THE contamination of sub-surface water supplies with aromatic compounds is a significant environmental concern1,2. As these contaminated sub-surface environments are generally anaerobic, the microbial oxidation of aromatic compounds coupled to nitrate reduction, sulphate reduction and methane production has been studied intensively1-7. In addition, geochemical evidence suggests that Fe(III) can be an important electron acceptor for the oxidation of aromatic compounds in anaerobic groundwater. Until now, only abiological mechanisms for the oxidation of aromatic compounds with Fe(III) have been reported8-12. Here we show that in aquatic sediments, microbial activity is necessary for the oxidation of model aromatic compounds coupled to Fe(III) reduction. Furthermore, a pure culture of the Fe(III)-reducing bacterium GS-15 can obtain energy for growth by oxidizing benzoate, toluene, phenol or p-cresol with Fe(III) as the sole electron acceptor. These results extend the known physiological capabilities of Fe(III)-reducing organisms and provide the first example of an organism of any type which can oxidize an aromatic hydrocarbon anaerobically.

Nature↗

USGS2022

Subsurface hydrocarbon degradation strategies in low- and high-sulfate coal seam communities identified with activity-based metagenomics

Environmentally relevant metagenomes and BONCAT-FACS derived translationally active metagenomes from Powder River Basin coal seams were investigated to elucidate potential genes and functional groups involved in hydrocarbon degradation to methane in coal seams with high- and low-sulfate levels. An advanced subsurface environmental sampler allowed the establishment of coal-associated microbial communities under in situ conditions for metagenomic analyses from environmental and translationally active populations. Metagenomic sequencing demonstrated that biosurfactants, aerobic dioxygenases, and anaerobic phenol degradation pathways were present in active populations across the sampled coal seams. In particular, results suggested the importance of anaerobic degradation pathways under high-sulfate conditions with an emphasis on fumarate addition. Under low-sulfate conditions, a mixture of both aerobic and anaerobic pathways was observed but with a predominance of aerobic dioxygenases. The putative low-molecular-weight biosurfactant, lichysein, appeared to play a more important role compared to rhamnolipids. The methods used in this study—subsurface environmental samplers in combination with metagenomic sequencing of both total and translationally active metagenomes—offer a deeper and environmentally relevant perspective on community genetic potential from coal seams poised at different redox conditions broadening the understanding of degradation strategies for subsurface carbon.

npj Biofilms and Microbiomes↗

USGS2008

Acetylene as fast food: Implications for development of life on anoxic primordial earth and in the outer solar system

Acetylene occurs, by photolysis of methane, in the atmospheres of jovian planets and Titan. In contrast, acetylene is only a trace component of Earth's current atmosphere. Nonetheless, a methane-rich atmosphere has been hypothesized for early Earth; this atmosphere would also have been rich in acetylene. This poses a paradox, because acetylene is a potent inhibitor of many key anaerobic microbial processes, including methanogenesis, anaerobic methane oxidation, nitrogen fixation, and hydrogen oxidation. Fermentation of acetylene was discovered ∼25 years ago, and Pelobacter acetylenicus was shown to grow on acetylene by virtue of acetylene hydratase, which results in the formation of acetaldehyde. Acetaldehyde subsequently dismutates to ethanol and acetate (plus some hydrogen). However, acetylene hydratase is specific for acetylene and does not react with any analogous compounds. We hypothesize that microbes with acetylene hydratase played a key role in the evolution of Earth's early biosphere by exploiting an available source of carbon from the atmosphere and in so doing formed protective niches that allowed for other microbial processes to flourish. Furthermore, the presence of acetylene in the atmosphere of a planet or planetoid could possibly represent evidence for an extraterrestrial anaerobic ecosystem. Astrobiology 8, 45–58.

Astrobiology↗

USGS2016

Natural inactivation of Escherichia coli in anoxic and reduced groundwater

Aims Inactivation rates of E. coli in groundwater have most often been determined in aerobic and oxidized systems. This study examined E. coli inactivation rates in anaerobic and extremely reduced groundwater systems that have been identified as recharge zones. Methods and Results Groundwater from six artesian wells was diverted to above ground, flow through mesocosms that contained laboratory grown E. coli in diffusion chambers. All groundwater was anaerobic and extremely reduced (ORP < - 300 mV). Cells were plated onto mTEC agar during 21 day incubation periods. All data fit a bi-phasic inactivation model, with > 95% of the E. coli population being inactivated < 11.0 hrs (mean k = 0.488± 0.188 h −1 ). Conclusions The groundwater geochemical conditions enhanced the inactivation of E. coli to rates approximately 21-fold greater than previously published inactivation rate in groundwater (mean k = 0.023 ± 0.030 h −1 ). Also, mTEC agar inhibits E. coli growth following exposure to anaerobic and reduced groundwater. Significance and Impact of the Study Aquifer recharge zones with geochemical characteristics observed in this study complement above ground engineered processes (e.g., filtration, disinfection), while increasing the overall indicator microorganism log-reduction rate of a facility.

Journal of Applied Microbiology↗

USGS1987

Rapid assay for microbially reducible ferric iron in aquatic sediments

The availability of ferric iron for microbial reduction as directly determined by the activity of iron-reducing organisms was compared with its availability as determined by a newly developed chemical assay for microbially reducible iron. The chemical assay was based on the reduction of poorly crystalline ferric iron by hydroxylamine under acidic conditions. There was a strong correlation between the extent to which hydroxylamine could reduce various synthetic ferric iron forms and the susceptibility of the iron to microbial reduction in an enrichment culture of iron-reducing organisms. When sediments that contained hydroxylamine-reducible ferric iron were incubated under anaerobic conditions, ferrous iron accumulated as the concentration of hydroxylamine-reducible ferric iron declined over time. Ferrous iron production stopped as soon as the hydroxylamine-reducible ferric iron was depleted. In anaerobic incubations of reduced sediments that did not contain hydroxylamine-reducible ferric iron, there was no microbial iron reduction, even though the sediments contained high concentrations of oxalate-extractable ferric iron. A correspondence between the presence of hydroxylamine-reducible ferric iron and the extent of ferric iron reduction in anaerobic incubations was observed in sediments from an aquifer and in fresh- and brackish-water sediments from the Potomac River estuary. The assay is a significant improvement over previously described procedures for the determination of hydroxylamine-reducible ferric iron because it provides a correction for the high concentrations of solid ferrous iron which may also be extracted from sediments with acid. This is a rapid, simple technique to determine whether ferric iron is available for microbial reduction.

Potomac River estuary↗

USGS1994

Spatial variability in biodegradation rates as evidenced by methane production from an aquifer

Accurate predictions of carbon and energy cycling rates in the environment depend on sampling frequencies and on the spatial variability associated with biological activities. We examined the variability associated with anaerobic biodegradation rates at two sites in an alluvial sand aquifer polluted by municipal landfill leachate. In situ rates of methane production were measured for almost a year, using anaerobic wells installed at two sites. Methane production ranged from 0 to 560 μmol · m -2 · day -1 at one site (A), while a range of 0 to 120,000 μmol · m -2 · day -1 was measured at site B. The mean and standard deviations associated with methane production at site A were 17 and 57 μmol · m -2 · day -1 , respectively. The comparable summary statistics for site B were 2,000 and 9,900 μmol · m -2 · day -1 . The coefficients of variation at sites A and B were 340 and 490%, respectively. Despite these differences, the two sites had similar seasonal trends, with the maximal rate of methane production occurring in summer. However, the relative variability associated with the seasonal rates changed very little. Our results suggest that (i) two spatially distinct sites exist in the aquifer, (ii) methanogenesis is a highly variable process, (iii) the coefficient of variation varied little with the rate of methane production, and (iv) in situ anaerobic biodegradation rates are lognormally distributed.

Applied and Environmental Microbiology↗

USGS1995

Assessment of intrinsic bioremediation of jet fuel contamination in a shallow aquifer, Beaufort, South Carolina

Field and laboratory studies show that microorganisms indigenous to the ground-water system underlying Tank Farm C, Marine Corps Air Station Beaufort, S.C., degrade petroleum hydrocarbons under aerobic and anaerobic conditions. Under aerobic conditions, sediments from the shallow aquifer underlying the site mineralized radiolabeled (14C) toluene to 14CO2 with first-order rate constants of about -0.29 per day. Sediments incubated under anaerobic conditions mineralized radiolabeled toluene more slowly, with first-order rate constants of -0.001 per day. Although anaerobic rates of biodegradation are low, they are significant in the hydrologic and geochemical context of the site. Because of low hydraulic conductivities (1.9-9.1 feet per day) and low hydraulic gradients (about 0.004 feet per feet), ground water flows slowly (approximately 20 feet per year) at this site. Furthermore, aquifer sediments contain organic-rich peat that has a high sorptive capacity. Under these conditions, hydrocarbon contaminants have moved no further than 10 feet downgradient of the jet fuel free product. Digital solute-transport simulations, using the range of model parameters measured at the site, show that dissolved contaminants will be completely degraded before they are discharged from the aquifer into adjacent surface-water bodies. These results show that natural attenuation processes are containing the migration of soluble hydrocarbons, and that intrinsic bioremediation is a potentially effective remedial strategy at this site.

South Carolina↗

USGS2000

Biodegradation of chlorinated ethenes at a karst site in middle Tennessee

This report presents results of field and laboratory investigations examining the biodegradation of chlorinated ethenes in a karst aquifer contaminated with trichloroethylene (TCE). The study site, located in Middle Tennessee, was selected because of the presence of TCE degradation byproducts in the karst aquifer and available site hydrologic and chlorinated-ethene information. Additional chemical, biological, and hydrologic data were gathered to evaluate whether the occurrence of TCE degradation byproducts in the karst aquifer was the result of biodegradation within the aquifer or simply transport into the aquifer. Geochemical analysis established that sulfate-reducing conditions, essential for reductive dechlorination of chlorinated solvents, existed in parts of the contaminated karst aquifer. Other areas of the aquifer fluctuated between anaerobic and aerobic conditions and contained compounds associated with cometabolism, such as ethane, methane, ammonia, and dissolved oxygen. A large, diverse bacteria population inhabits the contaminated aquifer. Bacteria known to biodegrade TCE and other chlorinated solvents, such as sulfate-reducers, methanotrophs, and ammonia-oxidizers, were identified from karst-aquifer water using the RNA-hybridization technique. Results from microcosms using raw karst-aquifer water found that aerobic cometabolism and anaerobic reductive-dechlorination degradation processes were possible when appropriate conditions were established in the microcosms. These chemical and biological results provide circumstantial evidence that several biodegradation processes are active in the aquifer. Additional site hydrologic information was developed to determine if appropriate conditions persist long enough in the karst aquifer for these biodegradation processes to be significant. Continuous monitoring devices placed in four wells during the spring of 1998 indicated that pH, specific conductance, dissolved oxygen, and oxidation-reduction potentials changed very little in areas isolated from active ground-water flow paths. These stable areas in the karst aquifer had geochemical conditions and bacteria conducive to reductive dechlorination of chlorinated ethenes. Other areas of the karst aquifer were associated with active ground-water flow paths and fluctuated between anaerobic and aerobic conditions in response to rain events. Associated with this dynamic environment were bacteria and geochemical conditions conducive to cometabolism. In summary, multiple lines of evidence developed from chemical, biological, and hydrologic data demonstrate that a variety of biodegradation processes are active in this karst aquifer.

Tennessee↗

USGS1975

Chemical quality and temperature of water in Flaming Gorge Reservoir, Wyoming and Utah, and the effect of the reservoir on the Green River

The major tributaries to Flaming Gorge Reservoir contribute an average of about 97 percent of the total streamflow and 82 percent of the total load of dissolved solids. The Green River is the largest tributary, and for the 1957-72 water years it contributed 81 percent of the total streamflow and 70 percent of the total load of dissolved solids. The principal constituents in the tributary streamflow are calcium and sulfate during periods of lowest flow and calcium and bicarbonate during periods of highest flow. Flaming Gorge Dam was closed in November 1962, and the most significant load changes of chemical constituents due to the net effect of inflow, outflow, leaching, and chemical precipitation in the reservoir have been load changes of sulfate and bicarbonate. The average increase of dissolved load of sulfate in the reservoir for the 1969-72 water years was 110,000 tons (99,790 t) per year, which was 40,000 tons (36,287 t) per year less than for the 1963-66 water years. The average decrease of dissolved load of bicarbonate in the reservoir for 1969-72 was 40,000 tons (36,287 t) per year, which was the same as the decrease for 1963-66. Anaerobic conditions were observed in the deep, uncirculated part of the reservoir near the dam during the 1971 and 1972 water years, and anaerobic or near-anaerobic conditions were observed near the confluence of the Blacks Fork and Green River during the summers of 1971 and 1972. The water in Flaming Gorge Reservoir is in three distinct layers, and the upper two layers (the epilimnion and the metalimnion) mixed twice during each of the 1971-72 water years. The two circulation periods were in the spring and fall. The water in the deepest layer (the hypolimnion) did not mix with the waters of the upper zones because the density difference was too great and because the deep, narrow shape of the basin probably inhibits mixing. The depletion of flow in the Green River downstream from Flaming Gorge Dam between closure of the dam and the end of the 1972 water year was 4,500,000 acre-feet (5,550.8 hm 3 ). Of this total, water stored in the reservoir accounted for 3,500,000 acre-feet (4,317.2 hm 3 ), evaporation consumed 700,000 acre-feet (863.4 hm 3 ), and 300,000 acre-feet (370.0 hm 3 ) went into bank storage. The net load of dissolved solids added to the river system during the 1963-72 water years, due to leaching and chemical precipitation, was 1,730,000 tons (1,569,421 t). The leaching rate was 200,000 tons (181,436 t) per year for 1963-68,115,000 tons (104,326 t) per year for 1969-70 and 150,000 tons (136,077 t) per year for 1971-72. It appears that the leaching rates should decrease in the future since the reservoir level in 1972 was near maximum pool level. The most significant increase in concentration of the chemical constituents in the water below the reservoir involved the sulfate ion, which increased from about 115 milligrams per litre (42 percent of the anions) in 1957 to about 200 milligrams per litre (54 percent), in 1972. But the highest concentration, about 290 milligrams per litre (58 percent), occurred in 1963, immediately after closure of the dam. Prior to closure of the dam, the average monthly temperature of the Green River below the damsite ranged from 0 ° C to 19.5 ° C as compared to 3.5 ° C to 10.0 ° C after closure.

Utah↗

USGS2003

Inorganic nitrogen transformations in the bed of the Shingobee River, Minnesota: Integrating hydrologic and biological processes using sediment perfusion cores

Inorganic N transformations were examined in streambed sediments from the Shingobee River using sediment perfusion cores. The experimental design simulated groundwater-stream water mixing within sediment cores, which provided a well-defined one-dimensional representation of in situ hydrologic conditions. Two distinct hydrologic and chemical settings were preserved in the sediment cores: the lowermost sediments, perfused with groundwater, remained anaerobic during the incubations, whereas the uppermost sediments, perfused with oxic water pumped from the overlying water column, simulated stream water penetration into the bed. The maintenance of oxic and anoxic zones formed a biologically active aerobic-anaerobic interface. Ammonium (NH4+) dissolved in groundwater was transported conservatively through the lower core zone but was removed as it mixed with aerated recycle water. Concurrently, a small quantity of nitrate (NO3-) equaling ???25% of the NH4+ loss was produced in the upper sediments. The NH4+ and NO3- profiles in the uppermost sediments resulted from coupled nitrification-denitrification, because assimilation and sorption were negligible. We hypothesize that anaerobic microsites within the aerated upper sediments supported denitrification. Rates of nitrification and denitrification in the perfusion cores ranged 42-209 and 53-160 mg N m-2 day-1, respectively. The use of modified perfusion cores permitted the identification and quantification of N transformations and verified process control by surface water exchange into the shallow hyporheic zone of the Shingobee River.

Minnesota↗

USGS2000

Redox conditions and the efficiency of chlorinated ethene biodegradation: Laboratory studies

The potential for biodegradation of highly reduced groundwater contaminants is greatest under aerobic conditions and least under CO2-reducing (methanogenic) conditions. Laboratory studies conducted using [1,2-14C] vinyl chloride (VC) indicate the same pattern applies to the anaerobic oxidation of relatively reduced chloroethylenes. Recent studies, showing that CH4 can be a significant product of microbial degradation of VC under methanogenic conditions, clarified mechanisms underlying anaerobic VC mineralization and emphasized the redox dependence of this process. A microcosm study conducted with stream bed sediments demonstrated rapid degradation of [1,2-14C] VC and simultaneous production of 14CO2 and 14CH4. The results of acetate mineralization studies indicated that these sediments contained active acetotrophic methanogens. VC degradation involved an initial transformation to acetate via oxidative acetogenesis followed by acetotrophic methanogenesis to yield CO2 and CH4 as final products. Based on these recent results, a conceptual model for anaerobic microbial degradation of VC to non-chlorinated products can be proposed.

Conference Paper↗