Predominant Terminal Electron-accepting Process Research Articles

Predominant terminal electron accepting processes during organic matter degradation: Spatio-temporal changes in Ashtamudi estuary, Kerala, India

Anaerobic microbial communities in the anoxic zones degrade organic matter in estuarine sediments. Thermodynamic energy yield for the oxidation reactions with various electron acceptors decreases in the order of O2> NO3- > Mn4+> Fe3+> SO42- > CO2. The predominant terminal electron accepting (TEA) process has an influence on the biogeochemical cycles of nutrients as well as the production of important greenhouse gases such as nitrous oxide and methane from estuarine sediments. The research questions of this study were (1) what are the environmental factors (pH, salinity, organic carbon, sulphate, redox potential) explaining variability in TEA activities such as nitrate reduction rate (NRR), iron reduction rate (IRR), sulphate reduction rate (SRR) and methane production rate (MPR) and (2) which is the predominant TEA process during degradation of organic matter. To determine the TEA activities, sediment samples collected from 13 sampling stations of Ashtamudi estuary during monsoon 2014 and summer 2015 were incubated with sulphate depleted artificial seawater, under anaerobic conditions for 72 h, in microcosms. Spatial variations dominated temporal variations for environmental variables. Nevertheless, biogeochemical processes showed a distinct seasonal variation. Total TEA activity was higher during summer than monsoon, indicating the higher heterotrophic microbial activity favored by high temperature. Individually, SRR was the maximum during summer, while NRR, IRR and MPR were the maximum during monsoon. Sulphate reduction was observed to be the predominant electron accepting process in all sampling stations with cumulative values of 3125.79 and 4046.07 nmol cm-3 day-1 during monsoon and summer respectively. This was followed by NRR, IRR and MPR. Although thermodynamically more favorable, NRR could not predominate due to scarcity of nitrate in sediments. Nevertheless, two-fold and five-fold increase in methanogenesis and denitrification were observed respectively during monsoon in sampling stations, which cannot be ignored, owing to the importance of methane and nitrous oxide as a potent greenhouse gas.

Real-time monitoring of subsurface microbial metabolism with graphite electrodes.

Monitoring in situ microbial activity in anoxic submerged soils and aquatic sediments can be labor intensive and technically difficult, especially in dynamic environments in which a record of changes in microbial activity over time is desired. Microbial fuel cell concepts have previously been adapted to detect changes in the availability of relatively high concentrations of organic compounds in waste water but, in most soils and sediments, rates of microbial activity are not linked to the concentrations of labile substrates, but rather to the turnover rates of the substrate pools with steady state concentrations in the nM–μM range. In order to determine whether levels of current produced at a graphite anode would correspond to the rates of microbial metabolism in anoxic sediments, small graphite anodes were inserted in sediment cores and connected to graphite brush cathodes in the overlying water. Currents produced were compared with the rates of [2-14C]-acetate metabolism. There was a direct correlation between current production and the rate that [2-14C]-acetate was metabolized to 14CO2 and 14CH4 in sediments in which Fe(III) reduction, sulfate reduction, or methane production was the predominant terminal electron-accepting process. At comparable acetate turnover rates, currents were higher in the sediments in which sulfate-reduction or Fe(III) reduction predominated than in methanogenic sediments. This was attributed to reduced products (Fe(II), sulfide) produced at distance from the anode contributing to current production in addition to the current that was produced from microbial oxidation of organic substrates with electron transfer to the anode surface in all three sediment types. The results demonstrate that inexpensive graphite electrodes may provide a simple strategy for real-time monitoring of microbial activity in a diversity of anoxic soils and sediments.

Functional Diversity and Electron Donor Dependence of Microbial Populations Capable of U(VI) Reduction in Radionuclide-Contaminated Subsurface Sediments

In order to elucidate the potential mechanisms of U(VI) reduction for the optimization of bioremediation strategies, the structure-function relationships of microbial communities were investigated in microcosms of subsurface materials cocontaminated with radionuclides and nitrate. A polyphasic approach was used to assess the functional diversity of microbial populations likely to catalyze electron flow under conditions proposed for in situ uranium bioremediation. The addition of ethanol and glucose as supplemental electron donors stimulated microbial nitrate and Fe(III) reduction as the predominant terminal electron-accepting processes (TEAPs). U(VI), Fe(III), and sulfate reduction overlapped in the glucose treatment, whereas U(VI) reduction was concurrent with sulfate reduction but preceded Fe(III) reduction in the ethanol treatments. Phyllosilicate clays were shown to be the major source of Fe(III) for microbial respiration by using variable-temperature Mössbauer spectroscopy. Nitrate- and Fe(III)-reducing bacteria (FeRB) were abundant throughout the shifts in TEAPs observed in biostimulated microcosms and were affiliated with the genera Geobacter, Tolumonas, Clostridium, Arthrobacter, Dechloromonas, and Pseudomonas. Up to two orders of magnitude higher counts of FeRB and enhanced U(VI) removal were observed in ethanol-amended treatments compared to the results in glucose-amended treatments. Quantification of citrate synthase (gltA) levels demonstrated a stimulation of Geobacteraceae activity during metal reduction in carbon-amended microcosms, with the highest expression observed in the glucose treatment. Phylogenetic analysis indicated that the active FeRB share high sequence identity with Geobacteraceae members cultivated from contaminated subsurface environments. Our results show that the functional diversity of populations capable of U(VI) reduction is dependent upon the choice of electron donor.

A Simple Pore Water Hydrogen Diffusion Syringe Sampler

Molecular hydrogen (H(2)) is an important intermediate product and electron donor in microbial metabolism. Concentrations of dissolved H(2) are often diagnostic of the predominant terminal electron-accepting processes in ground water systems or aquatic sediments. H(2) concentrations are routinely measured in ground water monitoring wells but are rarely measured in saturated aquatic sediments due to a lack of simple and practical sampling methods. This report describes the design and development (including laboratory and field testing) of a simple, syringe-based H(2) sampler in (1) saturated, riparian sediments, (2) surface water bed sediments, and (3) packed intervals of a fractured bedrock borehole that are inaccessible by standard pumped methods.

Evidence for aceticlastic methanogenesis in the presence of sulfate in a gas condensate-contaminated aquifer.

The anaerobic metabolism of acetate was studied in sediments and groundwater from a gas condensate-contaminated aquifer in an aquifer where geochemical evidence implicated sulfate reduction and methanogenesis as the predominant terminal electron-accepting processes. Most-probable-number tubes containing acetate and microcosms containing either [2-(14)C]acetate or [U-(14)C]acetate produced higher quantities of CH(4) compared to CO(2) in the presence or absence of sulfate.(14)CH(4) accounted for 70 to 100% of the total labeled gas in the [(14)C]acetate microcosms regardless of whether sulfate was present or not. Denaturing gradient gel electrophoresis of the acetate enrichments both with and without sulfate using Archaea-specific primers showed identical predominant bands that had 99% sequence similarity to members of Methanosaetaceae. Clone libraries containing archaeal 16S rRNA gene sequences amplified from sediment from the contaminated portion of the aquifer showed that 180 of the 190 clones sequenced belonged to the Methanosaetaceae. The production of methane and the high frequency of sequences from the Methanosaetaceae in acetate enrichments with and without sulfate indicate that aceticlastic methanogenesis was the predominant fate of acetate at this site even though sulfate-reducing bacteria would be expected to consume acetate in the presence of sulfate.

Characterization of Redox Processes in Shallow Groundwater of Owens Dry Lake, California

Redox status of shallow groundwaters (1-3 m depths) at Owens Dry Lake was studied to help guide mitigation efforts for attenuating dust generation from the dry lakebed. Redox conditions were characterized by Eh, oxidative capacity (OXC), and terminal electron accepting processes (TEAPs) as well as examining the energetics of TEAPs. Groundwater chemistry related to redox status was determined by major solute concentrations, dissolved gases (O2, H2, CH4), aqueous redox species (NO3, Mn2+, Fe2+/ Fe3+, SO4(2-)/HS-, DOC), and major redox sensitive components in the solid phase (extractable Fe/Mn). All of these measures of redox status indicate that sulfate reduction is the major process regulating redox conditions in most shallow groundwaters of Owens Dry Lake. Dissolved sulfate concentrations were regulated primarily by evaporation resulting in increasing concentrations as water migrates from the shoreline (<1 mM) to the center (up to 417 mM) of the dry lakebed. Eh values were generally in the range of -240 to -170 mV. The oxidative capacity demonstrates the dominant contribution of sulfate to OXC. The dominance of sulfate restricts further redox development, such as methanogenesis. Dissolved H2 concentrations ranged from 0.5 to 7.8 nM. According to the empirically defined H2 ranges, sulfate reduction was the most predominant TEAP. Moreover, thermodynamic calculations of TEAPs for H2 utilization support favorable energetics for both sulfate reduction and methanogenesis. The calculated available energy yield for sulfate reduction in the shallow groundwater of Owens Dry Lake was higher than other systems due to the high sulfate concentration.

Metabolism of organic compounds in anaerobic, hydrothermal sulphate-reducing marine sediments.

Previous studies of hot (>80 degrees C) microbial ecosystems have primarily relied on the study of pure cultures or analysis of 16S rDNA sequences. In order to gain more information on anaerobic metabolism by natural communities in hot environments, sediments were collected from a shallow marine hydrothermal vent system in Baia di Levante, Vulcano, Italy and incubated under strict anaerobic conditions at 90 degrees C. Sulphate reduction was the predominant terminal electron-accepting process in the sediments. The addition of molybdate inhibited sulphate reduction in the sediments and resulted in a linear accumulation of acetate and hydrogen over time. [U-14C]- acetate was completely oxidized to 14CO2, and the addition of molybdate inhibited 14CO2 production by 60%. [U-14C]-glucose was oxidized to 14CO2, and this was inhibited when molybdate was added. When the pool sizes of short-chain fatty acids were artificially increased, radiolabel from [U-14C]-glucose accumulated in the acetate pool. L-[U-14C]-glutamate, [ring-14C]-benzoate and [U-14C]-palmitate were also anaerobically oxidized to 14CO2 in the sediments, but molybdate had little effect on the oxidation of these compounds. These results demonstrate that natural microbial communities living in a hot, microbial ecosystem can oxidize acetate and a range of other organic electron donors under sulphate-reducing conditions and suggest that acetate is an important extracellular intermediate in the anaerobic degradation of organic matter in hot microbial ecosystems.

Assessment of natural attenuation of chlorinated aliphatics and BTEX in subarctic groundwater.

We examined biogeochemistry and microbiology associated with natural attenuation of trichloroethene (TCE), trichloroethane (TCA), and benzene in a subarctic aquifer. Identification of a predominant terminal electron-accepting process (TEAP) and characterization of typical natural attenuation footprints was difficult. Hydrogen and ferrous iron concentrations suggested that iron reduction was the predominant TEAP; calculated in situ Gibbs free energies for iron reduction were energetically feasible at all wells although a source of ferric iron has not been conclusively determined. The presence of dissolved sulfide and favorable free energies for sulfate reduction provided support of concurrent iron and sulfate reduction. Methanogenesis from H2/CO2 was generally not energetically favorable. The presence of TCE and TCA degradation intermediates suggested that biological reductive dechlorination occurred, although proportions of intermediates relative to parent compounds remained stable. By September 2000, contaminant concentrations were within regulatory standards at most sampling points. However, low rates of microbial activity and incomplete degradation imply that intrinsic bioremediation did not likely represent an important contribution to contaminant removal atthis site, where dilution appeared to be the primary attenuation mechanism.

An assessment of natural biotransformation of petroleum hydrocarbons and chlorinated solvents at an aquifer plume transect

Field biogeochemical characterization and laboratory microcosm studies were performed to assess the potential for future biotransformation of trichloroethylene (TCE) and toluene in a plume containing petroleum hydrocarbons and chlorinated solvents at the former Wurtsmith Air Force Base in Oscoda, MI. In situ terminal electron accepting processes (TEAPs), contaminant composition and microbial phylogeny were studied at a plume transect 100 m downgradient of the source. The presence of reduced electron acceptors, relevant microbial communities, and elevated dissolved methane and carbon dioxide concentrations at the transect, as well as downgradient accumulation of BTEX metabolites and dechlorination products, indicated that past or current reductive dechlorination at the transect was likely driven by BTEX biodegradation in the methanogenic zone. However, TCE and toluene mineralization in sediment–groundwater microcosms without added electron acceptors did not exceed 5% during 300 days of incubation and was nearly invariant with original sediment TEAP, even following amendments of nitrogen and phosphorus. Mineralization rates were on the order of 0.0015–0.03 μmol/g day. After 8 months, microcosms showed evidence of methanogenesis, but CH 4 and CO 2 production arose from the degradation of contaminants other than toluene. Cis-dichloroethylene was observed in only one methanogenic microcosm after more than 500 days. It appears likely that spatially and temporally dynamic redox zonation at the plume transect will prevent future sustained reductive dehalogenation of highly chlorinated solvents, for during the course of a year, the predominant TEAP at the highly contaminated water table shifted from methanogenesis to iron- and sulfate-reduction. It is recommended that biotransformation studies combine considerations of long-term, spatially relevant changes in redox zonation with laboratory-scale studies of electron donor utilization and cometabolic substrate transformation to yield a more accurate assessment of natural bioattenuation of specific pollutants in aquifers contaminated by undefined organic waste mixtures.

Anaerobic Bioremediation of Benzene under Sulfate-Reducing Conditions in a Petroleum-Contaminated Aquifer

The addition of sulfate to an anaerobic petroleum-contaminated aquifer in which benzene was a major soluble contaminant resulted in removal of benzene from the groundwater. The loss in benzene was associated with a decrease in sulfate along the groundwater flow path, relative to a conservative bromide tracer. Studies with [2-14C]acetate and molybdate demonstrated that sulfate reduction was the predominant terminal electron-accepting process (TEAP) in the sulfate-amended sediments, and studies with [14C]benzene indicated that benzene oxidation was dependent upon sulfate reduction. Abundant ferrous iron in the subsurface likely prevented the generation of free sulfide in the groundwater during the field trial. Comparisons of benzene and sulfate depletion in the treatment zone indicated that benzene degradation could account for 53% of the sulfate depletion. These results suggest that the addition of sulfate stimulated the activity of benzene-degrading, sulfate-reducing microorganisms. This is the first field study demonstrating that it is possible to stimulate anaerobic benzene degradation in a petroleum-contaminated aquifer.

Evidence for microbial Fe(III) reduction in anoxic, mining-impacted lake sediments (Lake Coeur d'Alene, Idaho).

Mining-impacted sediments of Lake Coeur d'Alene, Idaho, contain more than 10% metals on a dry weight basis, approximately 80% of which is iron. Since iron (hydr)oxides adsorb toxic, ore-associated elements, such as arsenic, iron (hydr)oxide reduction may in part control the mobility and bioavailability of these elements. Geochemical and microbiological data were collected to examine the ecological role of dissimilatory Fe(III)-reducing bacteria in this habitat. The concentration of mild-acid-extractable Fe(II) increased with sediment depth up to 50 g kg(-1), suggesting that iron reduction has occurred recently. The maximum concentrations of dissolved Fe(II) in interstitial water (41 mg liter(-1)) occurred 10 to 15 cm beneath the sediment-water interface, suggesting that sulfidogenesis may not be the predominant terminal electron-accepting process in this environment and that dissolved Fe(II) arises from biological reductive dissolution of iron (hydr)oxides. The concentration of sedimentary magnetite (Fe(3)O(4)), a common product of bacterial Fe(III) hydroxide reduction, was as much as 15.5 g kg(-1). Most-probable-number enrichment cultures revealed that the mean density of Fe(III)-reducing bacteria was 8.3 x 10(5) cells g (dry weight) of sediment(-1). Two new strains of dissimilatory Fe(III)-reducing bacteria were isolated from surface sediments. Collectively, the results of this study support the hypothesis that dissimilatory reduction of iron has been and continues to be an important biogeochemical process in the environment examined.

Anaerobic benzene degradation.

Although many studies have indicated that benzene persists under anaerobic conditions in petroleum-contaminated environments, it has recently been documented that benzene can be anaerobically oxidized with most commonly considered electron acceptors for anaerobic respiration. These include: Fe(III), sulfate, nitrate, and possibly humic substances. Benzene can also be converted to methane and carbon dioxide under methanogenic conditions. There is evidence that benzene can be degraded under in situ conditions in petroleum-contaminated aquifers in which either Fe(III) reduction or methane production is the predominant terminal electron-accepting process. Furthermore, evidence from laboratory studies suggests that benzene may be anaerobically degraded in petroleum-contaminated marine sediments under sulfate-reducing conditions. Laboratory studies have suggested that within the Fe(III) reduction zone of petroleum-contaminated aquifers, benzene degradation can be stimulated with the addition of synthetic chelators which make Fe(III) more available for microbial reduction. The addition of humic substances and other compounds that contain quinone moieties can also stimulate anaerobic benzene degradation in laboratory incubations of Fe(III)-reducing aquifer sediments by providing an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides. Anaerobic benzene degradation in aquifer sediments can be stimulated with the addition of sulfate, but in some instances an inoculum of benzene-oxidizing, sulfate-reducing microorganisms must also be added. In a field trial, sulfate addition to the methanogenic zone of a petroleum-contaminated aquifer stimulated the growth and activity of sulfate-reducing microorganisms and enhanced benzene removal. Molecular phylogenetic studies have provided indications of what microorganisms might be involved in anaerobic benzene degradation in aquifers. The major factor limiting further understanding of anaerobic benzene degradation is the lack of a pure culture of an organism capable of anaerobic benzene degradation.

Thermodynamic control on hydrogen concentrations in anoxic sediments

Molecular hydrogen plays a central role in bacterially mediated anoxic sediment chemistry, as both an important electron transfer agent and a key thermodynamic control. We studied the response of hydrogen concentrations to changes in temperature, specific electron acceptor, sulfate concentration, and pH in a series of laboratory experiments using sediments from Cape Lookout Bight, North Carolina. Hydrogen concentrations were found to depend significantly on each of these factors in a fashion that suggests thermodynamic control. In general, the change in hydrogen concentrations was apparently driven by a necessity to maintain a constant ΔG for the predominant terminal electron-accepting process. We hypothesize this situation derives from highly competetive conditions that force terminal metabolic bacteria to operate right at their thermodynamic limits. The response of hydrogen to individual controls in the laboratory experiments was reflected in relatively quantitiative fashion in down-core, seasonal, and inter-environmental variations observed in sediment cores from Cape Lookout Bight and the White Oak River, NC.

Metabolic Adaptation and in Situ Attenuation of Chlorinated Ethenes by Naturally Occurring Microorganisms in a Fractured Dolomite Aquifer near Niagara Falls, New York

A combination of hydrogeological, geochemical, and microbiological methods was used to document the biotransformation of trichloroethene (TCE) to ethene, a completely dechlorinated and environmentally benign compound, by naturally occurring microorganisms within a fractured dolomite aquifer. Analyses of groundwater samples showed that three microbially produced TCE breakdown products (cis-1,2-dichloroethene, vinyl chloride, and ethene) were present in the contaminant plume. Hydrogen (H2) concentra tions in groundwater indicated that iron reduction was the predominant terminal electron-accepting process in the most contaminated geologic zone of the site. Laboratory microcosms prepared with groundwater demonstrated complete sequential dechlorination of TCE to ethene. Microcosm assays also revealed that reductive dechlorination activity was present in waters from the center but not from the periphery of the contaminant plume. This dechlorination activity indicated that naturally occurring microorganisms have adapted to utilize chlorinated ethenes and suggested that dehalorespiring rather than cometabolic, microbial processes were the cause of the dechlorination. The addition of pulverized dolomite to microcosms enhanced the rate of reductive dechlorination, suggesting that hydrocarbons in the dolomite aquifer may serve as electron donors to drive microbially mediated reductive dechlorination reactions. Biodegradation of the chlorinated ethenes appears to contribute significantly to decontamination of the site.

Distribution of terminal electron-accepting processes in an aquifer having multiple contaminant sources

Concentrations of electron acceptors, electron donors, and H 2 in groundwater were measured to determine the distribution of terminal electron-accepting processes (TEAPs) in an alluvial aquifer having multiple contaminant sources. Upgradient contaminant sources included two separate hydrocarbon point sources, one of which contained the fuel oxygenate methyl tertbutyl ether (MTBE). Infiltrating river water was a source of dissolved NO 3, SO 4 and organic carbon (DOC) to the downgradient part of the aquifer. Groundwater downgradient from the MTBE source had larger concentrations of electron acceptors (dissolved O 2 and SO 4) and smaller concentrations of TEAP end products (dissolved inorganic C, Fe 2+ and CH 4) than groundwater downgradient from the other hydrocarbon source, suggesting that MTBE was not as suitable for supporting TEAPs as the other hydrocarbons. Measurements of dissolved H 2 indicated that SO 4 reduction predominated in the aquifer during a period of high water levels in the aquifer and river. The predominant TEAP shifted to Fe 3+ reduction in upgradient areas after water levels receded but remained SO 4 reducing downgradient near the river. This distribution of TEAPs is the opposite of what is commonly observed in aquifers having a single contaminant point source and probably reflects the input of DOC and SO 4 to the aquifer from the river. Results of this study indicate that the distribution of TEAPs in aquifers having multiple contaminant sources depends on the composition and location of the contaminants and on the availability of electron acceptors.

Stable Carbon Isotope Evidence of Biodegradation Zonation in a Shallow Jet-Fuel Contaminated Aquifer

δ13C values in dissolved inorganic carbon (DIC) ranged from −28 to +11.9‰ in a sandy, noncarbonate shallow aquifer contaminated with jet-fuel petroleum hydrocarbons. This range was observed over a 4-year study in shallow and deep monitoring wells and comprised δ13C values representative of the aerobic and anaerobic microbial biodegradation of 13C-depleted jet fuel (δ13C ∼ −27‰). The δ13C DIC values were found to be influenced by the extent of rainwater infiltration of dissolved oxygen or sulfate or, conversely, by the absence of recharge, lack of dissolved oxygen or sulfate input to the aquifer, and the ensuing methanogenic conditions. After some recharge events delivered dissolved oxygen or sulfate to the shallow part of the aquifer, low to medium DIC δ13C values were measured, and reflected biodegradation of 13C-depleted jet fuel under aerobic (δ13C DIC ∼ −26‰) or sulfate-reducing (δ13C DIC ∼ −18‰) conditions; the deeper part of the aquifer isolated from recharge was methanogenic and had higher δ13C DIC values. Conversely, when rainfall was absent and dissolved oxygen and sulfate concentrations were low in the aquifer, higher DIC δ13C values were measured in both shallow and deep contaminated groundwater (δ13C DIC up to +11.9‰) where H2 concentrations indicated that the predominant terminal electron-accepting process was methanogenesis. The highest δ13C values (+2.6 to +11.9‰) were from contaminated groundwater that contained no dissolved oxygen and little sulfate, CH4 concentrations up to 1985 μmol/L, and acetate concentrations exceeding 12 000 μmol/L. These results suggest that stable carbon isotopes in DIC can be used to indicate the zonation of 13C-depleted hydrocarbon biodegradation processes under the influence of hydrologically controlled electron-acceptor availability.

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 1. Sulfate from confining beds as an oxidant in microbial CO 2 production

A primary source of dissolved inorganic carbon (DIC) in the Black Creek aquifer of South Carolina is carbon dioxide produced by microbially mediated oxidation of sedimentary organic matter. Groundwater chemistry data indicate, however, that the available mass of inorganic electron acceptors (oxygen, Fe(III), and sulfate) and observed methane production is inadequate to account for observed CO 2 production. Although sulfate concentrations are low (approximately 0.05–0.10 mM) in aquifer water throughout the flow system, sulfate concentrations are greater in confining-bed pore water (0.4–20 mM). The distribution of culturable sulfate-reducing bacteria in these sediments suggests that this concentration gradient is maintained by greater sulfate-reducing activity in sands than in clays. Calculations based on Fick's Law indicate that possible rates of sulfate diffusion to aquifer sediments are sufficient to explain observed rates of CO 2 production (about 10 −5 mmoll −1 year −1), thus eliminating the apparent electron-acceptor deficit. Furthermore, concentrations of dissolved hydrogen in aquifer water are in the range characteristic of sulfate reduction (2–6 nM), which provides independent evidence that sulfate reduction is the predominant terminal electron-accepting process in this system. The observed accumulation of pyrite- and calcite-cemented sandstones at sand-clay interfaces is direct physical evidence that these processes have been continuing over the history of these sediments.

Hydrogen concentrations as an indicator of the predominant terminal electron-accepting reactions in aquatic sediments

Factors controlling the concentration of dissolved hydrogen gas in anaerobic sedimentary environments were investigated. Results, presented here or previously, demonstrated that, in sediments, only microorganisms catalyze the oxidation of H 2 coupled to the reduction of nitrate, Mn(IV), Fe(III), sulfate, or carbon dioxide. Theoretical considerations suggested that, at steady-state conditions, H 2 concentrations are primarily dependent upon the physiological characteristics of the microorganism(s) consuming the H 2 and that organisms catalyzing H 2 oxidation, with the reduction of a more electrochemically positive electron acceptor, can maintain lower H 2 concentrations than organisms using electron acceptors which yield less energy from H 2 oxidation. The H 2 concentrations associated with the specified predominant terminal electron-accepting reactions in bottom sediments of a variety of surface water environments were: methanogenesis, 7–10 nM; sulfate reduction, 1–1.5 nM; Fe(III) reduction, 0.2 nM; Mn(IV) or nitrate reduction, less than 0.05 nM. Sediments with the same terminal electron acceptor for organic matter oxidation had comparable H 2 concentrations, despite variations in the rate of organic matter decomposition, pH, and salinity. Thus, each terminal electron-accepting reaction had a unique range of steady-state H 2 concentrations associated with it. Preliminary studies in a coastal plain aquifer indicated that H 2 concentrations also vary in response to changes in the predominant terminal electron-accepting process in deep subsurface environments. These studies suggest that H 2 measurements may aid in determining which terminal electron-accepting reactions are taking place in surface and subsurface sedimentary environments.

Competitive Mechanisms for Inhibition of Sulfate Reduction and Methane Production in the Zone of Ferric Iron Reduction in Sediments

Mechanisms for inhibition of sulfate reduction and methane production in the zone of Fe(III) reduction in sediments were investigated. Addition of amorphic iron(III) oxyhydroxide to sediments in which sulfate reduction was the predominant terminal electron-accepting process inhibited sulfate reduction 86 to 100%. The decrease in electron flow to sulfate reduction was accompanied by a corresponding increase in electron flow to Fe(III) reduction. In a similar manner, Fe(III) additions also inhibited methane production in sulfate-depleted sediments. The inhibition of sulfate reduction and methane production was the result of substrate limitation, because the sediments retained the potential for sulfate reduction and methane production in the presence of excess hydrogen and acetate. Sediments in which Fe(III) reduction was the predominant terminal electron-accepting process had much lower concentrations of hydrogen and acetate than sediments in which sulfate reduction or methane production was the predominant terminal process. The low concentrations of hydrogen and acetate in the Fe(III)-reducing sediments were the result of metabolism by Fe(III)-reducing organisms of hydrogen and acetate at concentrations lower than sulfate reducers or methanogens could metabolize them. The results indicate that when Fe(III) is in a form that Fe(III)-reducing organisms can readily reduce, Fe(III)-reducing organisms can inhibit sulfate reduction and methane production by outcompeting sulfate reducers and methanogens for electron donors.