Methylmercury Oxidative Degradation Potentials in Contaminated and Pristine Sediments of the Carson River, Nevada

Sediments from mercury-contaminated and uncontaminated reaches of the Carson River, Nevada, were assayed for sulfate reduction, methanogenesis, denitrification, and monomethylmercury (MeHg) degradation. Demethylation of [(sup14)C]MeHg was detected at all sites as indicated by the formation of (sup14)CO(inf2) and (sup14)CH(inf4). Oxidative demethylation was indicated by the formation of (sup14)CO(inf2) and was present at significant levels in all samples. Oxidized/reduced demethylation product ratios (i.e., (sup14)CO(inf2)/(sup14)CH(inf4) ratios) generally ranged from 4.0 in surface layers to as low as 0.5 at depth. Production of (sup14)CO(inf2) was most pronounced at sediment surfaces which were zones of active denitrification and sulfate reduction but was also significant within zones of methanogenesis. In a core taken from an uncontaminated site having a high proportion of oxidized, coarse-grain sediments, sulfate reduction and methanogenic activity levels were very low and (sup14)CO(inf2) accounted for 98% of the product formed from [(sup14)C]MeHg. There was no apparent relationship between the degree of mercury contamination of the sediments and the occurrence of oxidative demethylation. However, sediments from Fort Churchill, the most contaminated site, were most active in terms of demethylation potentials. Inhibition of sulfate reduction with molybdate resulted in significantly depressed oxidized/reduced demethylation product ratios, but overall demethylation rates of inhibited and uninhibited samples were comparable. Addition of sulfate to sediment slurries stimulated production of (sup14)CO(inf2) from [(sup14)C]MeHg, while 2-bromoethanesulfonic acid blocked production of (sup14)CH(inf4). These results reveal the importance of sulfate-reducing and methanogenic bacteria in oxidative demethylation of MeHg in anoxic environments.     

A Microbial Arsenic Cycle in Sediments of an Acidic Mine Impoundment: Herman Pit,Clear Lake,California

The involvement of prokaryotes in the redox reactions of arsenic occurring between its +5 [arsenate; As(V)] and +3 [arsenite; As(III)] oxidation states has been well established. Most research to date has focused upon circum-neutral pH environments (e.g., freshwater or estuarine sediments) or arsenic-rich “extreme” environments like hot springs and soda lakes. In contrast, relatively little work has been conducted in acidic environments. With this in mind we conducted experiments with sediments taken from the Herman Pit, an acid mine drainage impoundment of a former mercury (cinnabar) mine. Due to the large adsorptive capacity of the abundant Fe(III)-rich minerals, we were unable to initially detect in solution either As(V) or As(III) added to the aqueous phase of live sediment slurries or autoclaved controls, although the former consumed added electron donors (i.e., lactate, acetate, hydrogen), while the latter did not. This prompted us to conduct further experiments with diluted slurries using the live materials from the first incubation as inoculum. In these experiments we observed reduction of As(V) to As(III) under anoxic conditions and reduction rates were enhanced by addition of electron donors. We also observed oxidation of As(III) to As(V) in oxic slurries as well as in anoxic slurries amended with nitrate. We noted an acid-tolerant trend for sediment slurries in the cases of As(III) oxidation (aerobic and anaerobic) as well as for anaerobic As(V) reduction. These observations indicate the presence of a viable microbial arsenic redox cycle in the sediments of this extreme environment, a result reinforced by the successful amplification of arsenic functional genes (aioA, and arrA) from these materials.     

Dimethyl sulfide metabolism in salt marsh sediments

Abstract Anoxic sediment slurries prepared from Spartina salt marsh soils contained dimethyl sulfide (DMS) at concentrations ranging from 1 to 10 μM. DMS was produced in slurries over the initial 1–24 h incubation. After the initial period of production, DMS decreased to undetectable levels and methane thiol (MSH) was produced. Inhibition of methanogenesis caused a 20% decrease in the rate of DMS consumption, while inhibition of sulfate reduction caused a 80% decrease in DMS consumption. When sulfate reduction and methanogenesis were simultaneously inhibited, DMS did not decrease. DMS contributed about 28% to the methane production rate, while DMS probably contributed only 1% or less to the sulfate reduction rate. Incubation of the sediment slurries under an atmosphere of air resulted in similar DMS consumption compared to anaerobic incubations, but MSH and CH₄ were not evolved.
Sediments from the marsh released significant quantities of DMS when treated with cold alkali, indicating that potentially significant sources of DMS existed in the sediments. Values of base-hydrolyzable DMS as high as 190 μmol per liter of sediment were observed near the sediment surface, and values always decreased with depth in the sediment. Simple flux experiments with small intact sediment cores, showed that DMS was emitted from the marsh surface when cores were injected with glutaraldehyde or molybdate and 2-bromoethanesulfonate (BES), but nit when cores were left uninhibited. These results showed that DMS was readily metabolized by microbes in marsh sediments and that this metabolism may be responsible for reducing the emission of DMS from the marsh surface.     

Benzene Oxidation Coupled to Sulfate Reduction

Highly reduced sediments from San Diego Bay, Calif., that were incubated under strictly anaerobic conditions metabolized benzene within 55 days when they were exposed initially to 1 (mu)M benzene. The rate of benzene metabolism increased as benzene was added back to the benzene-adapted sediments. When a [(sup14)C]benzene tracer was included with the benzene added to benzene-adapted sediments, 92% of the added radioactivity was recovered as (sup14)CO(inf2). Molybdate, an inhibitor of sulfate reduction, inhibited benzene uptake and production of (sup14)CO(inf2) from [(sup14)C]benzene. Benzene metabolism stopped when the sediments became sulfate depleted, and benzene uptake resumed when sulfate was added again. The stoichiometry of benzene uptake and sulfate reduction was consistent with the hypothesis that sulfate was the principal electron acceptor for benzene oxidation. Isotope trapping experiments performed with [(sup14)C]benzene revealed that there was no production of such potential extracellular intermediates of benzene oxidation as phenol, benzoate, p-hydroxybenzoate, cyclohexane, catechol, and acetate. The results demonstrate that benzene can be oxidized in the absence of O(inf2), with sulfate serving as the electron acceptor, and suggest that some sulfate reducers are capable of completely oxidizing benzene to carbon dioxide without the production of extracellular intermediates. Although anaerobic benzene oxidation coupled to chelated Fe(III) has been documented previously, the study reported here provides the first example of a natural sediment compound that can serve as an electron acceptor for anaerobic benzene oxidation.     

Microbial Aldicarb Transformation in Aquifer, Lake, and Salt Marsh Sediments

The microbial transformation of [N-methyl-(sup14)C]aldicarb, a carbamate pesticide, occurred in aquifer, lake, and salt marsh sediments. Microbial degradation of aldicarb took place within 21 days in aquifer sediments from sites previously exposed to aldicarb (Jamesport, Long Island, N.Y.) but did not occur in sediments which were not previously exposed (Connetquot State Park, Long Island, N.Y.). At the Jamesport sites, higher aldicarb transformation rates occurred in deep, anoxic sediments than in shallow, oxic sediments. There was a significant negative relationship (P < 0.05) between transformation rates and ambient dissolved O(inf2) levels. Aldicarb hydrolysis rates in Jamesport sediments were 10- to 1,000-fold lower than rates previously reported for soils. In addition, aldicarb degradation rates were not significantly correlated with measurements of bacterial activity and density previously determined in the same sediments. Substantially higher aldicarb degradation rates were found in anoxic lake and salt marsh than in aquifer sediments. Furthermore, we investigated the anaerobic microbial processes involved in aldicarb transformation by adding organic substrates (acetate, glucose), an alternative electron acceptor (nitrate), and microbial inhibitors (molybdate, 2-bromoethanesulfonic acid) to anoxic aquifer, lake, and salt marsh sediments. The results suggest that a methanogenic consortium was important in aldicarb transformation or in the use of aldicarb-derived products such as methylamine. In addition, microbial aldicarb transformation proceeded via different pathways under oxic and anoxic conditions. In the presence of O(inf2), aldicarb transformation was mainly via an oxidation pathway, while in the absence of O(inf2), degradation took place through a hydrolytic pathway (including the formation of methylamine precursors). Under anoxic conditions, therefore, aldicarb can be transformed by microbial consortia to yield products which can be of direct benefit to natural populations of methanogens present in sediments.     

Lipid Biomarkers of Suspended Particulate Organic Matter in Lake Bled (NW Slovenia)

Aquifer sediments from Norman, Oklahoma, were used to study the potential for microbial reduction of Cr(VI) to Cr(III). Black, clay-like sediments rapidly reduced Cr(VI) in both autoclaved and viable microcosms, indicating an abiotic mechanism. Lightcolored sandy sediments slowly reduced Cr(VI) only in viable microcosms, indicating a biological process. Cr(VI) reduction in these sediments had a pH optimum of 6.8 and temperature optima of 22°C and 50°C. Nearly complete inhibition of Cr(VI) reduction was observed when sandy sediments were shaken in the presence of oxygen. The addition of nitrate but not sulfate, selenate, or ferrous iron to sandy sediments inhibited Cr(VI) reduction. When electron acceptors were supplied in combinations with Cr(VI), reduction of Cr(VI) was greatest in the absence of nitrate. No loss of sulfate and no production of Fe(II) occurred in the presence of Cr(VI). The addition of molybdate to the microcosms did not affect Cr(VI) reduction in sandy sediments until very high concentrations (40 times the Cr[VI] concentration) were used. Interestingly, the addition of bromoethanesulfonic acid in amounts less than, or slightly greater than, the Cr(VI) concentration partially inhibited Cr(VI) reduction in sandy sediments. In the absence of this bacterial inhibitor, the sandy sediments produced methane. A methanogenic enrichment capable of reducing Cr(VI) during growth was obtained from sandy sediments. However, the enrichment produced methane only when Cr(VI) was absent, indicating that a shift in electron flow from methane production to Cr(VI) reduction may have occurred. These studies showed that Cr(VI) reduction in sandy aquifer sediments is a biologically mediated, anaerobic process that is inhibited by oxygen and partially inhibited by nitrate. The lack of sulfate reduction and sulfide production, as well as a lack of inhibition of Cr(VI) reduction by molybdate, argues against an indirect mechanism for Cr(VI) reduction, in which the sulfide produced during sulfate reduction would chemically reduce Cr(VI). Rather, Cr(VI) reduction may be mediated by a community of microorganisms that ordinarily use methanogenesis as the terminal electron-accepting process.     

Effects of imposed salinity gradients on dissimilatory arsenate reduction, sulfate reduction, and other microbial processes in sediments from two California soda lakes

Salinity effects on microbial community structure and on potential rates of arsenate reduction, arsenite oxidation, sulfate reduction, denitrification, and methanogenesis were examined in sediment slurries from two California soda lakes. We conducted experiments with Mono Lake and Searles Lake sediments over a wide range of salt concentrations (25 to 346 g liter(-1)). With the exception of sulfate reduction, rates of all processes demonstrated an inverse relationship to total salinity. However, each of these processes persisted at low but detectable rates at salt saturation. Denaturing gradient gel electrophoresis analysis of partial 16S rRNA genes amplified from As(V) reduction slurries revealed that distinct microbial populations grew at low (25 to 50 g liter(-1)), intermediate (100 to 200 g liter(-1)), and high (>300 g liter(-1)) salinity. At intermediate and high salinities, a close relative of a cultivated As-respiring halophile was present. These results suggest that organisms adapted to more dilute conditions can remain viable at high salinity and rapidly repopulate the lake during periods of rising lake level. In contrast to As reduction, sulfate reduction in Mono Lake slurries was undetectable at salt saturation. Furthermore, sulfate reduction was excluded from Searles Lake sediments at any salinity despite the presence of abundant sulfate. Sulfate reduction occurred in Searles Lake sediment slurries only following inoculation with Mono Lake sediment, indicating the absence of sulfate-reducing flora. Experiments with borate-amended Mono Lake slurries suggest that the notably high (0.46 molal) concentration of borate in the Searles Lake brine was responsible for the exclusion of sulfate reducers from that ecosystem.     

Microbial carbon monoxide consumption in salt marsh sediments

We have examined sediments from a fringing salt marsh in Maine to further understand marine CO metabolism, about which relatively little is known. Intact cores from the marsh emitted CO during dark oxic incubations, but emission rates were significantly higher during anoxic incubations, which provided evidence for simultaneous production and aerobic consumption in surface sediments. CO emission rates were also elevated when cores were exposed to light, which indicated that photochemical reactions play a role in CO production. A kinetic analysis of marsh surface sediments yielded an apparent K(m) of about 82 ppm, which exceeded values reported for well-aerated soils that consume atmospheric CO (65nM). Surface (0-0.2 cm depth interval) sediment slurries incubated under oxic conditions rapidly consumed CO, and methyl fluoride did not inhibit uptake, which indicated that neither ammonia nor methane oxidizers contributed to the observed activity. In contrast, aerobic CO uptake was inhibited by additions of readily available organic substrates (pyruvate, glucose and glycine), but not by cellulose. CO was also consumed by surface and sub-surface sediment slurries incubated under anaerobic conditions, but rates were less than during aerobic incubations. Molybdate and nitrate or nitrite, but not 2-bromoethanesulfonic acid, partially inhibited anaerobic uptake. These results suggest that sulfidogens and acetogens, but not dissimilatory nitrate reducers or methanogens, actively consume CO. Sediment-free plant roots also oxidized CO aerobically; rates for Spartina patens and Limonium carolinianum roots were significantly higher than rates for Spartina alterniflora roots. Thus plants may also impact CO cycling in estuarine environments.     

Precipitation of Arsenic Trisulfide by Desulfotomaculum auripigmentum

A newly discovered bacterium, Desulfotomaculum auripigmentum, precipitates arsenic trisulfide (As(inf2)S(inf3)). Precipitation of As(inf2)S(inf3) by this organism results from its reduction of As(V) to As(III) and S(VI) to S(-II). At the As(III) concentration range of interest (0.1 to 1 mM), the stability of As(inf2)S(inf3) is highly sensitive to pH and [S(-II)]. Thus, the relative rates at which D. auripigmentum reduces As(V) and S(VI) are critical to its formation of As(inf2)S(inf3). Other As(V)- or S(VI)-reducing bacteria are unable to precipitate As(inf2)S(inf3) either due to their inability to reduce both As(V) and S(VI) or because they reduce S(VI) too rapidly. Electron microscopy of thin sections showed that the precipitate forms both intra- and extracellularly. Microbial As(inf2)S(inf3) formation nucleates precipitation of the mineral in the bulk milieu, whereas heat-killed cells alone do not serve as templates for its formation. Precipitation of As(inf2)S(inf3) by D. auripigmentum suggests that As(inf2)S(inf3) formation may be important in the biogeochemical cycle of arsenic.     

Effects of Imposed Salinity Gradients on Dissimilatory Arsenate Reduction, Sulfate Reduction, and Other Microbial Processes in Sediments from Two California Soda Lakes

Salinity effects on microbial community structure and on potential rates of arsenate reduction, arsenite oxidation, sulfate reduction, denitrification, and methanogenesis were examined in sediment slurries from two California soda lakes. We conducted experiments with Mono Lake and Searles Lake sediments over a wide range of salt concentrations (25 to 346 g liter⁻¹). With the exception of sulfate reduction, rates of all processes demonstrated an inverse relationship to total salinity. However, each of these processes persisted at low but detectable rates at salt saturation. Denaturing gradient gel electrophoresis analysis of partial 16S rRNA genes amplified from As(V) reduction slurries revealed that distinct microbial populations grew at low (25 to 50 g liter⁻¹), intermediate (100 to 200 g liter⁻¹), and high (>300 g liter⁻¹) salinity. At intermediate and high salinities, a close relative of a cultivated As-respiring halophile was present. These results suggest that organisms adapted to more dilute conditions can remain viable at high salinity and rapidly repopulate the lake during periods of rising lake level. In contrast to As reduction, sulfate reduction in Mono Lake slurries was undetectable at salt saturation. Furthermore, sulfate reduction was excluded from Searles Lake sediments at any salinity despite the presence of abundant sulfate. Sulfate reduction occurred in Searles Lake sediment slurries only following inoculation with Mono Lake sediment, indicating the absence of sulfate-reducing flora. Experiments with borate-amended Mono Lake slurries suggest that the notably high (0.46 molal) concentration of borate in the Searles Lake brine was responsible for the exclusion of sulfate reducers from that ecosystem.     

Kinetics of Inhibition of Methane Oxidation by Nitrate, Nitrite, and Ammonium in a Humisol

The kinetics of inhibition of CH(inf4) oxidation by NH(inf4)(sup+), NO(inf2)(sup-), and NO(inf3)(sup-) in a humisol was investigated. Soil slurries exhibited nearly standard Michaelis-Menten kinetics, with half-saturation constant [K(infm(app))] values for CH(inf4) of 50 to 200 parts per million of volume (ppmv) and V(infmax) values of 1.1 to 2.5 nmol of CH(inf4) g of dry soil(sup-1) h(sup-1). With one soil sample, NH(inf4)(sup+) acted as a simple competitive inhibitor, with an estimated K(infi) of 8 (mu)M NH(inf4)(sup+) (18 nM NH(inf3)). With another soil sample, the response to NH(inf4)(sup+) addition was more complex and the inhibitory effect of NH(inf4)(sup+) was greater than predicted by a simple competitive model at low CH(inf4) concentrations (<50 ppmv). This was probably due to NO(inf2)(sup-) produced through NH(inf4)(sup+) oxidation. Added NO(inf2)(sup-) was inherently more inhibitory of CH(inf4) oxidation at low CH(inf4) concentrations, and more NO(inf2)(sup-) was produced as the CH(inf4)-to-NH(inf4)(sup+) ratio decreased and the competitive balance shifted. NaNO(inf3) was a noncompetitive inhibitor of CH(inf4) oxidation, but inhibition was evident only at >10 mM concentrations, which also altered soil pHs. Similar concentrations of NaCl were also inhibitory of CH(inf4) oxidation, so there may be no special inhibitory mechanism of nitrate per se.     

Seasonal oscillation of microbial iron and sulfate reduction in saltmarsh sediments (Sapelo Island, GA, USA)

Seasonal variations in anaerobic respiration pathways were investigated at three saltmarsh sites using chemical data, sulfate reduction rate measurements, enumerations of culturable populations of anaerobic iron-reducing bacteria (FeRB), and quantification of in situ 16S rRNA hybridization signals targeted for sulfate-reducing bacteria (SRB). Bacterial sulfate reduction in the sediments followed seasonal changes in temperature and primary production of the saltmarsh, with activity levels lowest in winter and highest in summer. In contrast, a dramatic decrease in the FeRB population size was observed during summer at all sites. The collapse of FeRB populations during summer was ascribed to high rates of sulfide production by SRB, resulting in abiotic reduction of bioavailable Fe(III) (hydr)oxides. To test this hypothesis, sediment slurry incubations at 10, 20 and 30 °C were carried out. Increases in temperature and labile organic carbon availability (acetate or lactate additions) increased rates of sulfate reduction while decreasing the abundance of culturable anaerobic FeRB. These trends were not reversed by the addition of amorphous Fe(III) (hydr)oxides to the slurries. However, when sulfate reduction was inhibited by molybdate, no decline in FeRB growth was observed with increasing temperature. Addition of dissolved sulfide adversely impacted propagation of FeRB whether molybdate was added or not. Both field and laboratory data therefore support a sulfide-mediated limitation of microbial iron respiration by SRB. When total sediment respiration rates reach their highest levels during summer, SRB force a decline in the FeRB populations. As sulfate reduction activity slows down after the summer, the FeRB are able to recover.     

Redox Transformations of Arsenic Oxyanions in Periphyton Communities

Periphyton (Cladophora sp.) samples from a suburban stream lacking detectable dissolved As were able to reduce added As(V) to As(III) when incubated under anoxic conditions and, conversely, oxidized added As(III) to As(V) with aerobic incubation. Both types of activity were abolished in autoclaved controls, thereby demonstrating its biological nature. The reduction of As(V) was inhibited by chloramphenicol, indicating that it required the synthesis of new protein. Nitrate also inhibited As(V) reduction, primarily because it served as a preferred electron acceptor to which the periphyton community was already adapted. However, part of the inhibition was also caused by microbial reoxidation of As(III) linked to nitrate. Addition of [¹⁴C]glucose to anoxic samples resulted in the production of ¹⁴CO₂, suggesting that the observed As(V) reduction was a respiratory process coupled to the oxidation of organic matter. The population density of As(V)-reducing bacteria within the periphyton increased with time and with the amount of As(V) added, reaching values as high as ~10⁶ cells ml⁻¹ at the end of the incubation. This indicated that dissimilatory As(V) reduction in these populations was linked to growth. However, As(V)-respiring bacteria were found to be present, albeit at lower numbers (~10² ml⁻¹), in freshly sampled periphyton. These results demonstrate the presence of a bacterial population within the periphyton communities that is capable of two key arsenic redox transformations that were previously studied in As-contaminated environments, which suggests that these processes are widely distributed in nature. This assumption was reinforced by experiments with estuarine samples of Cladophora sericea in which we detected a similar capacity for anaerobic As(V) reduction and aerobic As(III) oxidation.     

Adaptation of Psychrophilic and Psychrotrophic Sulfate-Reducing Bacteria to Permanently Cold Marine Environments

The potential for sulfate reduction at low temperatures was examined in two different cold marine sediments, Mariager Fjord (Denmark), which is permanently cold (3 to 6(deg)C) but surrounded by seasonally warmer environments, and the Weddell Sea (Antarctica), which is permanently below 0(deg)C. The rates of sulfate reduction were measured by the (sup35)SO(inf4)(sup2-) tracer technique at different experimental temperatures in sediment slurries. In sediment slurries from Mariager Fjord, sulfate reduction showed a mesophilic temperature response which was comparable to that of other temperate environments. In sediment slurries from Antarctica, the metabolic activity of psychrotrophic bacteria was observed with a respiration optimum at 18 to 19(deg)C during short-term incubations. However, over a 1-week incubation, the highest respiration rate was observed at 12.5(deg)C. Growth of the bacterial population at the optimal growth temperature could be an explanation for the low temperature optimum of the measured sulfate reduction. The potential for sulfate reduction was highest at temperatures well above the in situ temperature in all experiments. The results from sediment incubations were compared with those obtained from pure cultures of sulfate-reducing bacteria by using the psychrotrophic strain ltk10 and the mesophilic strain ak30. The psychrotrophic strain reduced sulfate optimally at 28(deg)C in short-term incubations, even though it could not grow at temperatures above 24(deg)C. Furthermore, this strain showed its highest growth yield between 0 and 12(deg)C. In contrast, the mesophilic strain ak30 respired and grew optimally and showed its highest growth yield at 30 to 35(deg)C.     

Microbial sulfate reduction in acidic (pH 3) strip-mine lakes

Abstract ³⁵SO₄ reduction was detected in slurries of sediments obtained from Reservoir 29 (pH 3.8) and Lake B (pH 6.2), two acid strip-mine lakes in Indiana. The rates varied seasonally and were higher in summer and fall than in the spring. The optimal pH for sulfate reduction in Reservoir 29 sediments was 5, but samples had increased activity at pH 7 within 24 h after adjusting the pH to this value. In Lake B, the optimal pH for sulfate reduction was the in situ pH (6.2). Sulfate reduction in both lakes was stimulated 2–3-fold by increasing p _H2. High concentrations (5 mM) of organic acids inhibited sulfate reduction at pH 3.8, but stimulation was observed at concentrations of 0.1 mM. Acid-volatile sulfides accounted for about 70% of the products of ³⁵SO₄ reduction.     

Interactions between the Fe(III)-reducing bacterium Geobacter sulfurreducens and arsenate, and capture of the metalloid by biogenic Fe(II)

Previous work has shown that microbial communities in As-mobilizing sediments from West Bengal were dominated by Geobacter species. Thus, the potential of Geobacter sulfurreducens to mobilize arsenic via direct enzymatic reduction and indirect mechanisms linked to Fe(III) reduction was analyzed. G. sulfurreducens was unable to conserve energy for growth via the dissimilatory reduction of As(V), although it was able to grow in medium containing fumarate as the terminal electron acceptor in the presence of 500 muM As(V). There was also no evidence of As(III) in culture supernatants, suggesting that resistance to 500 muM As(V) was not mediated by a classical arsenic resistance operon, which would rely on the intracellular reduction of As(V) and the efflux of As(III). When the cells were grown using soluble Fe(III) as an electron acceptor in the presence of As(V), the Fe(II)-bearing mineral vivianite was formed. This was accompanied by the removal of As, predominantly as As(V), from solution. Biogenic siderite (ferrous carbonate) was also able to remove As from solution. When the organism was grown using insoluble ferrihydrite as an electron acceptor, Fe(III) reduction resulted in the formation of magnetite, again accompanied by the nearly quantitative sorption of As(V). These results demonstrate that G. sulfurreducens, a model Fe(III)-reducing bacterium, did not reduce As(V) enzymatically, despite the apparent genetic potential to mediate this transformation. However, the reduction of Fe(III) led to the formation of Fe(II)-bearing phases that are able to capture arsenic species and could act as sinks for arsenic in sediments.     

Anaerobic Microflora of Everglades Sediments: Effects of Nutrients on Population Profiles and Activities

Everglades sediments (wetland soils) near sources of agricultural runoff had low redox potentials, were blackened with sulfide, and displayed high porewater phosphorus (total) concentrations and high water column conductivities. These sediments yielded 10(sup3)- to 10(sup4)-fold-higher numbers of culturable anaerobes, including methanogens, sulfate reducers, and acetate producers, than did sediments from Everglades and Lake Okeechobee comparative control sites not as directly associated with agricultural runoff. These observations demonstrated that there was a general, rather than specific, enhancement of the anaerobic microflora in the sediments most likely influenced by agricultural runoff. Despite these differences in microfloral patterns, methylmercury and total mercury levels were similar among these contrasting sediments. Although available sulfate and phosphorus appeared to stimulate the productivity of sulfate reducers in Everglades sediments, the number of culturable sulfate reducers did not directly correspond to the concentration of sulfate and phosphorus in porewaters. Microcosms supplemented with sulfate, nitrate, and phosphate altered the initial capacities of the sediment microflora to produce acetate and methane from endogenous matter. For sediments nearest sources of agricultural runoff, phosphorus temporarily enhanced acetate formation and initially suppressed methane production, sulfate enhanced acetate formation but did not significantly alter the production of methane, and nitrate totally suppressed the initial production of both methane and acetate. In regards to the latter, microbes capable of dissimilating nitrate to ammonium were present in greater culturable numbers than denitrifiers. In microcosms, acetate was a major source of methane, and supplemental hydrogen was directed towards the synthesis of acetate via CO(inf2)-dependent acetogenesis. These findings demonstrate that Everglades sediments nearest agricultural runoff have enhanced anaerobic microbial profiles and that the anaerobic microflora are poised to respond rapidly to phosphate, sulfate, and nitrate input.     

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.     

Quantification of ammonia-oxidizing bacteria and factors controlling nitrification in salt marsh sediments

To elucidate the geomicrobiological factors controlling nitrification in salt marsh sediments, a comprehensive approach involving sediment geochemistry, process rate measurements, and quantification of the genetic potential for nitrification was applied to three contrasting salt marsh habitats: areas colonized by the tall (TS) or short (SS) form of Spartina alterniflora and unvegetated creek banks (CBs). Nitrification and denitrification potential rates were strongly correlated with one another and with macrofaunal burrow abundance, indicating that coupled nitrification-denitrification was enhanced by macrofaunal burrowing activity. Ammonia monooxygenase (amoA) gene copy numbers were used to estimate the ammonia-oxidizing bacterial population size (5.6 x 10(4) to 1.3 x 10(6) g of wet sediment(-1)), which correlated with nitrification potentials and was 1 order of magnitude higher for TS and CB than for SS. TS and CB sediments also had higher Fe(III) content, higher Fe(III)-to-total reduced sulfur ratios, higher Fe(III) reduction rates, and lower dissolved sulfides than SS sediments. Iron(III) content and reduction rates were positively correlated with nitrification and denitrification potential and amoA gene copy number. Laboratory slurry incubations supported field data, confirming that increased amounts of Fe(III) relieved sulfide inhibition of nitrification. We propose that macrofaunal burrowing and high concentrations of Fe(III) stimulate nitrifying bacterial populations, and thus may increase nitrogen removal through coupled nitrification-denitrification in salt marsh sediments.     

Microbiological and Geochemical Characterization of Microbial Fe(III) Reduction in Salt Marsh Sediments

Population densities of anaerobic Fe(III)-reducing bacteria (FeRB) and aerobic heterotrophs were inversely correlated in the surficial (0-2 cm) layers of Sapelo Island, Georgia, salt marsh sediments. In surficial sediments where densities of aerobic heterotrophs were low, the density of culturable FeRB correlated positively with the concentration of amorphous Fe(III) oxyhydroxides extractable by ascorbate. High FeRB densities and a decrease with depth of ascorbate-extractable Fe(III) were observed in the upper 6 cm of a tidal creek core. Culturable sulfate-reducing bacteria (SRB) and SRB-targeted rRNA signals were also detected in the upper 6-cm depth. The disappearance of FeRB below 6 cm, however, coincided with a large increase in the abundance of SRB. Thus, when FeRB are not limited by the availability of readily reducible amorphous Fe(III) oxyhydroxides, FeRB may outcompete SRB for growth substrates. Shewanella putrefaciens- and Geobacteraceae-targeted rRNA signals were at or below detection limits in all sediment samples, indicating that these FeRB are not predominant members of the active FeRB populations. The ubiquitous presence of FeRB at the sites studied challenges the traditional view that dissimilatory Fe(III) reduction is not an important pathway of organic carbon oxidation in salt marsh sediments.