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1.
Iron sulfide plaques have been observed on roots of wild rice (Zizania palustris) and other wetland plants grown in sulfur-impacted freshwater ecosystems, but the mechanism of their formation and ramifications for plants have not been investigated. We exposed a model annual wetland plant, Zizania palustris, to elevated sulfate concentrations (3.1 mM) and quantified the development of iron oxide and iron sulfide precipitates on root surfaces throughout the plant life cycle. During the onset of seed production, root surfaces amended with sulfate transitioned within 1 week from iron (hydr)oxide plaques to iron sulfide plaques. During the same week, Fe(III) decreased on roots of plants not amended with sulfate but FeS did not accumulate. Prior to FeS accumulation, sulfate-amended plants had taken up the same amount of N as unamended plants. After FeS accumulation, total plant nitrogen did not increase further on sulfate-amended plants, indicating a cessation in nitrogen uptake, whereas total plant N continued to increase in unamended plants. Sulfate-amended plants produced fewer and lighter seeds with less nitrogen than unamended plants. FeS precipitation on roots may be associated with elevated sulfide and inhibited nitrogen uptake before the end of the plant’s life cycle, thus affecting the populations of this annual aquatic plant. We propose a mechanism by which a physiologically-induced decline in radial oxygen loss near the end of a plant’s life cycle initiates a precipitous decline in redox potential at the root surface and in adjacent porewater, initiating accumulation of iron sulfide plaques. These plaques could be an important locus for iron sulfide accumulation in wetland sediments.  相似文献   

2.
The spiking of metals into sediments lowers pH, raises the oxidative state, and exacerbates the partitioning of Fe, Mn, and spiked metal to the porewater. This study reports the geochemical response of three sediments of varying metal-binding capacity to Cu-/Zn-additions and the influence of pH-adjustment on the major metal-partitioning processes. The increase in redox potential and porewater metal concentrations observed in metal-spiked sediment was minimized by sediment neutralization to pH 7 irrespective of sediment type. In the presence of minimal sulfide concentrations, porewater metal concentrations suggested a greater affinity of copper for organic carbon than zinc, which was thought more dependent on iron oxyhydroxide phases. The amount of iron in the porewater of metal-spiked pH adjusted sediment was, in turn, affected by the type and concentration of spiked metal in the porewater. Increasing porewater concentrations of copper and zinc corresponded to decreasing and increasing porewater iron concentrations, respectively. Porewater copper appeared to act as a toxicant of Fe(III) reducing bacteria, while porewater zinc is thought to have had a stimulatory effect. The present study provides further insight on geochemical changes occurring to metal-spiked sediments and their implications for the interpretation of toxicity tests.  相似文献   

3.
The hydrothermally influenced sediments of Tutum Bay, Ambitle Island, Papua New Guinea, are ideal for investigating the chemolithotrophic activities of micro-organisms involved in arsenic cycling because hydrothermal vents there expel fluids with arsenite (As(III)) concentrations as high as 950 μg L(-1) . These hot (99 °C), slightly acidic (pH ~6), chemically reduced, shallow-sea vent fluids mix with colder, oxidized seawater to create steep gradients in temperature, pH, and concentrations of As, N, Fe, and S redox species. Near the vents, iron oxyhydroxides precipitate with up to 6.2 wt% arsenate (As(V)). Here, chemical analyses of sediment porewaters from 10 sites along a 300-m transect were combined with standard Gibbs energies to evaluate the energy yields (-ΔG(r)) from 19 potential chemolithotrophic metabolisms, including As(V) reduction, As(III) oxidation, Fe(III) reduction, and Fe(II) oxidation reactions. The 19 reactions yielded 2-94 kJ mol(-1) e(-) , with aerobic oxidation of sulphide and arsenite the two most exergonic reactions. Although anaerobic As(V) reduction and Fe(III) reduction were among the least exergonic reactions investigated, they are still potential net metabolisms. Gibbs energies of the arsenic redox reactions generally correlate linearly with pH, increasing with increasing pH for As(III) oxidation and decreasing with increasing pH for As(V) reduction. The calculated exergonic energy yields suggest that micro-organisms could exploit diverse energy sources in Tutum Bay, and examples of micro-organisms known to use these chemolithotrophic metabolic strategies are discussed. Energy modeling of redox reactions can help target sampling sites for future microbial collection and cultivation studies.  相似文献   

4.
Seasonal cycling of Fe in saltmarsh sediments   总被引:2,自引:1,他引:1  
This study combines an analysis of porewater chemistry with new, solid phase wet chemical extractions to examine the seasonal cycling of Fe in vegetated and unvegetated (cyanobacterial mat) saltmarsh sediments. Saltmarsh sediments are shown to contain more solid phase reactive Fe than other marine sediments studied so far. From the partitioning and speciation of solid Fe, and solid/soluble reduced S analysis in 10 sediment cores, we have observed that a majority of solid Fe in these sediments is cycled rapidly and completely between oxidized reactive Fe and reduced Fe as pyrite. Vegetated porewaters showed a lower pH and much higher Fe(II) concentrations on average than unvegetated porewaters in the top 10 cm, whereas sulfate, alkalinity, and sulfide concentrations were similar in the two environments. The amorphous Fe(III) oxide fraction showed a high negative correlation to solid and soluble reduced S (r 2 = –0.86 and –0.71, respectively) in surface vegetated sediments whereas the crystalline Fe(III) oxide fraction showed a high negative correlation (r 2 = –0.96) to sulfide only at depth. Though reactive Fe was observed in unvegetated sediments, no seasonal trend was apparent and the speciation of solid Fe revealed that most of it was reduced. Solid phase and porewater chemistry support the dominant role of the biota (Spartina alterniflora and bacteria) in controlling the reactivity of Fe and suggest that the current definition of solid phase, reactive Fe should be expanded to include crystalline Fe(III) minerals which are available for pyrite formation in saltmarsh sediments. In support of previous saltmarsh studies, we present evidence that the redox cycle of solid Fe is controlled by sulfate reduction and sediment oxidation which respond to both annual cycles (light, temperature) and to short-term, episodic effects such as weather and tides.  相似文献   

5.
Marinobacter santoriniensis NKSG1T is a mesophilic, dissimilatory arsenate-reducing and arsenite-oxidizing bacterium isolated from an arsenate-reducing enrichment culture. The inoculum was obtained from arsenic-rich shallow marine hydrothermal sediment from Santorini, Greece, with evidence of arsenic redox cycling. Growth studies demonstrated M. santoriniensis NKSG1T is capable of conserving energy from the reduction of arsenate [As(V)] with acetate or lactate as the electron donor, and of oxidizing arsenite [As(III)] heterotrophically with oxygen as the electron acceptor. The oxidation of As(III) coincided with the expression of the aoxB gene encoding for the catalytic molybdopterin subunit of the heterodimeric arsenite oxidase operon, indicating the reaction is enzymatically controlled, and M. santoriniensis NKSG1T is a heterotrophic As(III)-oxidizing bacterium. Although it is clear that this organism also performs dissimilatory As(V) reduction, no amplification of the arrA arsenate reductase gene was attained using a range of primers and PCR conditions. Marinobacter santoriniensis NKSG1T belongs to a genus of bacteria widely occurring in marine environments, including hydrothermal sediments, and is among the first marine bacteria shown to be capable of either anaerobic As(V) respiration or aerobic As(III) oxidation.  相似文献   

6.
Repeated anaerobic microbial redox cycling of iron   总被引:4,自引:0,他引:4  
Some nitrate- and Fe(III)-reducing microorganisms are capable of oxidizing Fe(II) with nitrate as the electron acceptor. This enzymatic pathway may facilitate the development of anaerobic microbial communities that take advantage of the energy available during Fe-N redox oscillations. We examined this phenomenon in synthetic Fe(III) oxide (nanocrystalline goethite) suspensions inoculated with microflora from freshwater river floodplain sediments. Nitrate and acetate were added at alternate intervals in order to induce repeated cycles of microbial Fe(III) reduction and nitrate-dependent Fe(II) oxidation. Addition of nitrate to reduced, acetate-depleted suspensions resulted in rapid Fe(II) oxidation and accumulation of ammonium. High-resolution transmission electron microscopic analysis of material from Fe redox cycling reactors showed amorphous coatings on the goethite nanocrystals that were not observed in reactors operated under strictly nitrate- or Fe(III)-reducing conditions. Microbial communities associated with N and Fe redox metabolism were assessed using a combination of most-probable-number enumerations and 16S rRNA gene analysis. The nitrate-reducing and Fe(III)-reducing cultures were dominated by denitrifying Betaproteobacteria (e.g., Dechloromonas) and Fe(III)-reducing Deltaproteobacteria (Geobacter), respectively; these same taxa were dominant in the Fe cycling cultures. The combined chemical and microbiological data suggest that both Geobacter and various Betaproteobacteria participated in nitrate-dependent Fe(II) oxidation in the cycling cultures. Microbially driven Fe-N redox cycling may have important consequences for both the fate of N and the abundance and reactivity of Fe(III) oxides in sediments.  相似文献   

7.
Viruses play important roles in marine surface ecosystems, but little is known about viral ecology and virus-mediated processes in deep-sea hydrothermal microbial communities. In this study, we examined virus-like particle (VLP) abundances in planktonic and attached microbial communities, which occur in physical and chemical gradients in both deep and shallow submarine hydrothermal environments (mixing waters between hydrothermal fluids and ambient seawater and dense microbial communities attached to chimney surface areas or macrofaunal bodies and colonies). We found that viruses were widely distributed in a variety of hydrothermal microbial habitats, with the exception of the interior parts of hydrothermal chimney structures. The VLP abundance and VLP-to-prokaryote ratio (VPR) in the planktonic habitats increased as the ratio of hydrothermal fluid to mixing water increased. On the other hand, the VLP abundance in attached microbial communities was significantly and positively correlated with the whole prokaryotic abundance; however, the VPRs were always much lower than those for the surrounding hydrothermal waters. This is the first report to show VLP abundance in the attached microbial communities of submarine hydrothermal environments, which presented VPR values significantly lower than those in planktonic microbial communities reported before. These results suggested that viral lifestyles (e.g., lysogenic prevalence) and virus interactions with prokaryotes are significantly different among the planktonic and attached microbial communities that are developing in the submarine hydrothermal environments.  相似文献   

8.
A species of Dechlorospirillum was isolated from an Fe(II)-oxidizing, opposing-gradient-culture enrichment using an inoculum from a circumneutral, freshwater creek that showed copious amounts of Fe(III) (hydr)oxide precipitation. In gradient cultures amended with a redox indicator to visualize the depth of oxygen penetration, Dechlorospirillum sp. strain M1 showed Fe(II)-dependent growth at the oxic-anoxic interface and was unable to utilize sulfide as an alternate electron donor. The bacterium also grew with acetate as an electron donor under both microaerophilic and nitrate-reducing conditions, but was incapable of organotrophic Fe(III) reduction or nitrate-dependent Fe(II) oxidation. Although members of the genus Dechlorospirillum are primarily known as perchlorate and nitrate reducers, our results suggest that some species are members of the microbial communities involved in iron redox cycling at the oxic-anoxic transition zones in freshwater sediments.  相似文献   

9.
Aerobic organisms are faced with a dilemma. Environmental iron is found primarily in the relatively inert Fe(III) form, whereas the more metabolically active ferrous form is a strong pro-oxidant. This conundrum is solved by the redox cycling of iron between Fe(III) and Fe(II) at every step in the iron metabolic pathway. As a transition metal ion, iron can be “metabolized” only by this redox cycling, which is catalyzed in aerobes by the coupled activities of ferric iron reductases (ferrireductases) and ferrous iron oxidases (ferroxidases).  相似文献   

10.
Siderophores, biogenic chelating agents that facilitate Fe(III) uptake through the formation of strong complexes, also form strong complexes with Mn(III) and exhibit high reactivity with Mn (hydr)oxides, suggesting a pathway by which Mn may disrupt Fe uptake. In this review, we evaluate the major biogeochemical mechanisms by which Fe and Mn may interact through reactions with microbial siderophores: competition for a limited pool of siderophores, sorption of siderophores and metal–siderophore complexes to mineral surfaces, and competitive metal-siderophore complex formation through parallel mineral dissolution pathways. This rich interweaving of chemical processes gives rise to an intricate tapestry of interactions, particularly in respect to the biogeochemical cycling of Fe and Mn in marine ecosystems.  相似文献   

11.
Biochemistry of arsenic detoxification   总被引:28,自引:0,他引:28  
Rosen BP 《FEBS letters》2002,529(1):86-92
All living organisms have systems for arsenic detoxification. The common themes are (a) uptake of As(V) in the form of arsenate by phosphate transporters, (b) uptake of As(III) in the form of arsenite by aquaglyceroporins, (c) reduction of As(V) to As(III) by arsenate reductases, and (d) extrusion or sequestration of As(III). While the overall schemes for arsenic resistance are similar in prokaryotes and eukaryotes, some of the specific proteins are the products of separate evolutionary pathways.  相似文献   

12.
The sedimentary pyrite sulfur isotope (δ34S) record is an archive of ancient microbial sulfur cycling and environmental conditions. Interpretations of pyrite δ34S signatures in sediments deposited in microbial mat ecosystems are based on studies of modern microbial mat porewater sulfide δ34S geochemistry. Pyrite δ34S values often capture δ34S signatures of porewater sulfide at the location of pyrite formation. However, microbial mats are dynamic environments in which biogeochemical cycling shifts vertically on diurnal cycles. Therefore, there is a need to study how the location of pyrite formation impacts pyrite δ34S patterns in these dynamic systems. Here, we present diurnal porewater sulfide δ34S trends and δ34S values of pyrite and iron monosulfides from Middle Island Sinkhole, Lake Huron. The sediment–water interface of this sinkhole hosts a low-oxygen cyanobacterial mat ecosystem, which serves as a useful location to explore preservation of sedimentary pyrite δ34S signatures in early Earth environments. Porewater sulfide δ34S values vary by up to ~25‰ throughout the day due to light-driven changes in surface microbial community activity that propagate downwards, affecting porewater geochemistry as deep as 7.5 cm in the sediment. Progressive consumption of the sulfate reservoir drives δ34S variability, instead of variations in average cell-specific sulfate reduction rates and/or sulfide oxidation at different depths in the sediment. The δ34S values of pyrite are similar to porewater sulfide δ34S values near the mat surface. We suggest that oxidative sulfur cycling and other microbial activity promote pyrite formation in and immediately adjacent to the microbial mat and that iron geochemistry limits further pyrite formation with depth in the sediment. These results imply that primary δ34S signatures of pyrite deposited in organic-rich, iron-poor microbial mat environments capture information about microbial sulfur cycling and environmental conditions at the mat surface and are only minimally affected by deeper sedimentary processes during early diagenesis.  相似文献   

13.
Zhang G  Han X  Elser JJ 《Oecologia》2011,167(1):253-264
Mosses play an integral role in the hydrologic regimes of ecosystems where they cover the soil surface, and thus affect biogeochemical cycling of elements influenced by soil oxidation–reduction (redox) reactions, including the plant growth-limiting nutrients, nitrogen and phosphorus (P). In rich fens where P often limits plant growth, we hypothesized that feedbacks between mosses and redox conditions would determine P availability to shallow-rooted forb species that constitute much of these wetlands’ unusually high plant species diversity. In a moss removal experiment in three fens, forb tissue P and microbial P were greater while anion exchange membrane (AEM) resin P was lower where mosses occurred than where they were removed, suggesting both higher availability and greater demand for P in moss-covered soils. Coupled physicochemical and biological mechanisms drove moss effects on P cycling, ultimately through effects on soil oxygenation or reduction: higher redox potential underlying mosses corresponded to greater microbial activity, phosphatase enzyme activity, and colonization by arbuscular mycorrhizal fungi (AMF), all of which can promote greater P availability to plants. These more oxidized soils stimulated: (1) greater microbial activity and root vigor; (2) correspondingly greater P demand via microbial uptake, forb uptake, and iron (Fe)-P reactions; and (3) greater P supply through soil and root phosphatase activity and AMF colonization. This work demonstrates that mosses improve vascular plant P acquisition by alleviating stresses caused by reducing conditions that would otherwise prevail in shallow underlying soils, thus providing a mechanism by which mosses facilitate plant species diversity in rich fens.  相似文献   

14.
Pore water and solid phase samples were collected from the upper 50 cm of a peat profile at four sites within a 10 m2 area in Kleinstuck Marsh, a minerotropic fen located in Kalamazoo, MI. Although the chosen sites are in close proximity to each other, they differ with respect to vegetation species and density. Pore water analyses for a suite of redox sensitive species (pH, alkalinity, dissolved Mn(II), Fe(II), Fe(III), sulfide, sulfate), together with Fe and Mn distributions inferred from operationally-defined sequential extractions, demonstrate that Fe(III) and Mn(IV) reduction occurs in the shallow peat at three of the four sites. At the fourth site, the only site containing the invasive purple loosestrife (Lythrum salicaria), accumulation of dissolved sulfide in the pore waters and increased levels of oxidizable phases in the shallow peat point to increased net sulfate reduction relative to the other three sites. Speciation calculations indicate that pore water concentrations of phosphate, especially below ∼10 cm depth, are largely controlled by the solubility of phases such as strengite or hydroxylapatite, and that at all but the loosestrife site, dissolved Ca and Mg are likely determined by carbonate solubility. Fe and Mn distribution among operationally defined solid phase fractions are consistent with reductive dissolution of FMO in the uppermost peat, leading to precipitation of Fe sulfides and Mn carbonates deeper in the peat profile. Zn, Co, Cr and Ni distributions are consistent with release from FMO to form sulfides or organic associations deeper in the peat. Pb and Cu may also be released by reductive dissolution of FMO, or more likely, shift from primary association with organic matter to increased association with sulfides under more sulfidic conditions. This study highlights the existence of extreme lateral variations in peat pore water and solid phase geochemical profiles, even over quite small areas.  相似文献   

15.
砷是一种无处不在的有毒类金属,其强致癌性引起了人类的广泛关注。在自然环境中,砷的转化存在物理化学过程和生物过程,其中微生物介导的砷转化是环境砷行为的主要影响因素。微生物的耐砷特性与砷吸收、氧化还原、甲基化、区隔化和外排等过程密切相关。砷在微生物体内的转运转化主要与砷解毒有关,但某些微生物可利用氧化还原过程产生的能量以维持其生长需求。本文综述了微生物介导的砷吸收、转化、区隔化和外排机制,这对阐明砷的地球化学循环过程及指导砷污染土壤和水体修复、阻控农作物砷吸收等方面具有重要意义。  相似文献   

16.
Recent studies of bacterial Fe(II) oxidation at circumneutral pH by a newly-isolated lithotrophic β-Proteobacterium (strain TW2) are reviewed in relation to a conceptual model that accounts for the influence of biogenic Fe(III)-binding ligands on patterns of Fe(II) oxidation and Fe(III) oxide deposition in opposing gradients of Fe(II) and O2. The conceptual model envisions complexation of Fe(III) by biogenic ligands as mechanism which alters the locus of Fe(III) oxide deposition relative to Fe(II) oxidation so as to delay/retard cell encrustation with Fe(III) oxides. Experiments examining the potential for bacterial Fe redox cycling in microcosms containing ferrihydrite-coated sand and a coculture of a lithotrophic Fe(II)-oxidizing bacterium (strain TW2) and a dissimilatory Fe(III)-reducing bacterium (Shewanella algae strain BrY) are described and interpreted in relation to an extended version of the conceptual model in which Fe(III)-binding ligands promote rapid microscale Fe redox cycling. The coculture systems showed minimal Fe(III) oxide accumulation at the sand-water interface, despite intensive O2 input from the atmosphere and measurable dissolved O2 to a depth of 2 mm below the sand-water interface. In contrast, a distinct layer of oxide precipitates formed in systems containing Fe(III)-reducing bacteria alone. Voltammetric microelectrode measurements revealed much lower concentrations of dissolved Fe(II) in the coculture systems. Examination of materials from the cocultures by fluorescence in situ hybridization indicated close physical juxtapositioning of Fe(II)-oxidizing and Fe(III)reducing bacteria in the upper few mm of sand. Together these results indicate that Fe(II)-oxidizing bacteria have the potential to enhance the coupling of Fe(II) oxidation and Fe(III) reduction at redox interfaces, thereby promoting rapid microscale cycling of Fe.  相似文献   

17.
Iron redox cycling in metal-rich, hypersaline, anoxic brines plays a central role in the biogeochemical evolution of life on Earth, and similar brines with the potential to harbor life are thought to exist elsewhere in the solar system. To investigate iron biogeochemical cycling in a terrestrial analog we determined the iron redox chemistry and isotopic signatures in the cryoencapsulated liquid brines found in frozen Lake Vida, East Antarctica. We used both in situ voltammetry and the spectrophotometric ferrozine method to determine iron speciation in Lake Vida brine (LVBr). Our results show that iron speciation in the anoxic LVBr was, unexpectedly, not free Fe(II). Iron isotope analysis revealed highly depleted values of ?2.5‰ for the ferric iron of LVBr that are similar to iron isotopic signatures of Fe(II) produced by dissimilatory iron reduction. The presence of Fe(III) in LVBr therefore indicates dynamic iron redox cycling beyond iron reduction. Furthermore, extremely low δ18O–SO4 2? values (?9.7‰) support microbial iron-sulfur cycling reactions. In combination with evidence for chemodenitrification resulting in iron oxidation, we conclude that coupled abiotic and biotic redox reactions are driving the iron cycle in Lake Vida brine. Our findings challenge the current state of knowledge of anoxic brine chemistry and may serve as an analogue for icy brines found in the outer reaches of the solar system.  相似文献   

18.
Although siderophores are generally viewed as biological iron uptake agents, recent evidence has shown that they may play significant roles in the biogeochemical cycling and biological uptake of other metals. One such siderophore that is produced by A. vinelandii is the triscatecholate protochelin. In this study, we probe the solution chemistry of protochelin and its complexes with environmentally relevant trace metals to better understand its effect on metal uptake and cycling. Protochelin exhibits low solubility below pH 7.5 and degrades gradually in solution. Electrochemical measurements of protochelin and metal–protochelin complexes reveal a ligand half-wave potential of 200 mV. The Fe(III)Proto3− complex exhibits a salicylate shift in coordination mode at circumneutral to acidic pH. Coordination of Mn(II) by protochelin above pH 8.0 promotes gradual air oxidation of the metal center to Mn(III), which accelerates at higher pH values. The Mn(III)Proto3− complex was found to have a stability constant of log β110 = 41.6. Structural parameters derived from spectroscopic measurements and quantum mechanical calculations provide insights into the stability of the Fe(III)Proto3−, Fe(III)H3Proto, and Mn(III)Proto3− complexes. Complexation of Co(II) by protochelin results in redox cycling of Co, accompanied by accelerated degradation of the ligand at all solution pH values. These results are discussed in terms of the role of catecholate siderophores in environmental trace metal cycling and intracellular metal release.  相似文献   

19.
20.
Tidal freshwater ecosystems experience acute seawater intrusion associated with periodic droughts, but are expected to become chronically salinized as sea level rises. Here we report the results from an experimental manipulation in a tidal freshwater Zizaniopsis miliacea marsh on the Altamaha River, GA where diluted seawater was added to replicate marsh plots on either a press (constant) or pulse (2 months per year) basis. We measured changes in porewater chemistry (SO42?, Cl?, organic C, inorganic nitrogen and phosphorus), ecosystem CO2 and CH4 exchange, and microbial extracellular enzyme activity. We found that press (chronic) seawater additions increased porewater chloride and sulfate almost immediately, and ammonium and phosphate after 2–4 months. Chronic increases in salinity also decreased net ecosystem exchange, resulting in reduced CO2 and CH4 emissions from press plots. Our pulse treatment, designed to mimic natural salinity incursion in the Altamaha River (September and October), temporarily increased porewater ammonium concentrations but had few lasting effects on porewater chemistry or ecosystem carbon balance. Our findings suggest that long-term, chronic saltwater intrusion will lead to reduced C fixation and the potential for increased nutrient (N, P) export while acute pulses of saltwater will have temporary effects.  相似文献   

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