Hydrologic and biogeochemical controls on trace element export from northern Wisconsin wetlands

Wetlands play an important role in determining the water quality of streams and are generally considered to act as a sink for many reactive species. However, retention of chemical constituents varies seasonally and is affected by hydrologic and biogeochemical processes including water source, mineral weathering, DOC and SPM cycling, redox status, precipitation/dissolution/adsorption, and seasonal events. Relatively little is known about the influence of these factors on trace element cycling in wetland-influenced streams. To explore the role of wetlands with respect to the retention/release of trace elements to streams, we examined temporal and spatial patterns of concentrations of a large suite of trace elements (via ICP-MS) and geochemical drivers in five streams and wetland rivulets draining natural wetlands in a northern Wisconsin watershed as well as in their groundwater sources (terrestrial recharge, lake recharge, and older lake recharge). We performed principal components analyses of the concentrations of elements and their geochemical drivers in both the streams and rivulets to assist in the identification of factors regulating trace element concentrations. Variation in trace and major element concentrations among the streams was strongly related to the proportion of terrestrial recharge contributing to the stream. A dominant influence of water source on rivulet chemistry was supported by association of groundwater-sourced elements (Ba, Ca, Cs, Mg, Na, Si, Sr) with the primary statistical factor. DOC appeared in the first principal component factor for the streams and in the second factor for the rivulets. Strong correlations of Al, Cd, Ce, Cu, La, Pb, Ti, and Zn with DOC supported the important influence of DOC on trace metal cycling. A number of elements in the rivulets (Al, La, Pb, Ti) and streams (Al, Ce, Cr, Cu, La, Pb, Ti, Zn) had a significant particulate cycle. Redox cycling and precipitation/dissolution reactions involving Fe and Mn likely impacted Cu and Mo as evidenced by the low levels in the rivulets. Variance in Fe, Mn and the metal oxy-anions was associated with factors related to redox cycling and adsorption reactions in the wetland sediments. In streams, DOC and metals with a high affinity for DOC were associated with a factor which also included negative loadings for groundwater-sourced elements, reflecting the importance of seasonal hydrologic events which flush DOC and metals from wetland sediments and dilute groundwater sourced metals. Redox processes were of secondary importance in the streams but of primary significance in the rivulets, documenting the importance of anoxic conditions in wetland sediments on groundwater en route to the stream.     

Bioremediation of metal‐contaminated surface and groundwaters

Microorganisms immobilize, mobilize, or transform metals by extracellular precipitation reactions, intracellular accumulation, oxidation and reduction reactions, methylation and demethylation, and extracellular binding and complexation. Nearly all of these microbe/metal interactions occur within the wetlands approach to acid mine drainage treatment, a process that is rapidly gaining support as a low‐maintenance, cost‐effective approach to solving an important environmental problem. Several proprietary processes, which employ nonliving microorganisms that are immobilized in polymer matrixes, are entering the water treatment market. These processes take advantage of negatively charged functional groups on cell walls and exopolymers of microorganisms that bind cationic metals. These biosorbents effectively remove low concentrations (<1 to about 20 mg/L) of heavy metal cations in the presence of high concentrations of alkaline earth metals (Ca²⁺ and Mg²⁺) and organic contaminants to levels lower than the U.S. National Drinking Water Standards. Immobilization of the biomass in polymer matrixes yields products that have substantial chemical and mechanical integrity. These immobilized products lend themselves to application in conventionally engineered systems such as up‐flow and down‐flow columns, expanded‐bed systems, dispersed‐bed systems, and low‐maintenance trough systems. Biosorption will probably play an important role in achieving the strict environmental standards now being enforced.     

Microbially influenced corrosion as a model system for the study of metal microbe interactions: a unifying electron transfer hypothesis

The general term biomineralisation refers to biologically induced mineralisation in which an organism modifies its local microenvironment creating conditions such that there is chemical precipitation of mineral phases extracellularly. Most usually this results from an oxidation or reduction carried out by some microbial species, with the formation of a recognised biomineralised product. These reactions play a major role in microbial physiology and ecology, and are of central importance to such engineering consequences as microbial mining and microbially influenced corrosion. This paper will examine metal microbe interactions, both in naturally occurring microbial ecosystems and in two particular cases of biocorrosion, with the objective of putting forward a unifying hypothesis relevant to the understanding of each of these apparently disparate processes.     

Habitat heterogeneity influences the response of microbial communities to severe low‐flow periods in alluvial wetlands

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Microbially Influenced Corrosion as a Model System for the Study of Metal Microbe Interactions: A Unifying Electron Transfer Hypothesis

The general term biomineralisation refers to biologically induced mineralisation in which an organism modifies its local microenvironment creating conditions such that there is chemical precipitation of mineral phases extracellularly. Most usually this results from an oxidation or reduction carried out by some microbial species, with the formation of a recognised biomineralised product. These reactions play a major role in microbial physiology and ecology, and are of central importance to such engineering consequences as microbial mining and microbially influenced corrosion. This paper will examine metal microbe interactions, both in naturally occurring microbial ecosystems and in two particular cases of biocorrosion, with the objective of putting forward a unifying hypothesis relevant to the understanding of each of these apparently disparate processes.     

Metal immobilisation by biofilms: Mechanisms and analytical tools

In biofilm environments, heavy metal and radionuclide pollutants are removed by a variety of mechanisms, including biosorption, precipitation as sulfides or phosphates and microbial reductive precipitation. Even if the elemental composition and localization of the precipitate trapped in the biofilm is well described thanks to spectroscopic and microscopic techniques, this review highlights that little is known about metal immobilisation mechanisms in microbial biofilms, i.e., mass transfer of metals, mechanisms involved in (bio)sorption and precipitation and the influence of physicochemical micro-environments within the biofilm matrix. The review shows the advantage of using a combination of different techniques to evaluate the fate of metals within microbial biofilms. By combining a variety of techniques (e.g., selective extraction, microscopy, spectroscopy and miniaturised sensors ...), it is possible to gain high-resolution structural and chemical information of biofilms on a level of the individual cell. This approach will facilitate the characterization of the metal immobilisation sites and the metal sorption and (bio)crystallisation mechanisms in biofilms. The results provided by the combination of these techniques will allow to predict the amount of metal accumulation in biofilms as well as their chemical speciation. This review demonstrates that an interdisciplinary approach is required to study metal fate within the biofilm matrix. This revised version was published online in June 2006 with corrections to the Cover Date.     

Associations between redox‐sensitive trace metals and microbial communities in a Proterozoic ocean analogue

Constraints on Precambrian ocean chemistry are dependent upon sediment geochemistry. However, diagenesis and metamorphism can destroy primary biosignatures, making it difficult to consider biology when interpreting geochemical data. Modern analogues for ancient ecosystems can be useful tools for identifying how sediment geochemistry records an active biosphere. The Middle Island Sinkhole (MIS) in Lake Huron is an analogue for shallow Proterozoic waters due to its low oxygen water chemistry and microbial communities that exhibit diverse metabolic functions at the sediment–water interface. This study uses sediment trace metal contents and microbial abundances in MIS sediments and an oxygenated Lake Huron control site (LH) to infer mechanisms for trace metal burial. The adsorption of trace metals to Mn‐oxyhydroxides is a critical burial pathway for metals in oxic LH sediments, but not for the MIS mat and sediments, consistent with conventional understanding of Mn cycling. Micronutrient trace metals (e.g., Zn) are associated with organic matter regardless of oxygen and sulfide availability. Although U and V are conventionally considered to be organically complexed in suboxic and anoxic conditions, U and organic covary in oxic LH sediments, and Mn‐oxyhydroxide cycling dominates V deposition in the anoxic MIS sediments. Significant correlations between Mo and organic matter across all redox regimes have major implications for our interpretations of Mo isotope systematics in the geologic record. Finally, while microbial groups vary between the sampling locales (e.g., the cyanobacteria in the MIS microbial mat are not present in LH sediments), LH and MIS ultimately have similar relationships between microbial assemblages and metal burial, making it difficult to link trace metal burial to microbial metabolisms. Together, these results indicate that bulk sediment trace metal composition does not capture microbiological processes; more robust trace metal geochemistry such as isotopes and speciation may be critical for understanding the intersections between microbiology and sediment geochemistry.     

Microbial extracellular polymeric substances: central elements in heavy metal bioremediation

Extracellular polymeric substances (EPS) of microbial origin are a complex mixture of biopolymers comprising polysaccharides, proteins, nucleic acids, uronic acids, humic substances, lipids, etc. Bacterial secretions, shedding of cell surface materials, cell lysates and adsorption of organic constituents from the environment result in EPS formation in a wide variety of free-living bacteria as well as microbial aggregates like biofilms, bioflocs and biogranules. Irrespective of origin, EPS may be loosely attached to the cell surface or bacteria may be embedded in EPS. Compositional variation exists amongst EPS extracted from pure bacterial cultures and heterogeneous microbial communities which are regulated by the organic and inorganic constituents of the microenvironment. Functionally, EPS aid in cell-to-cell aggregation, adhesion to substratum, formation of flocs, protection from dessication and resistance to harmful exogenous materials. In addition, exopolymers serve as biosorbing agents by accumulating nutrients from the surrounding environment and also play a crucial role in biosorption of heavy metals. Being polyanionic in nature, EPS forms complexes with metal cations resulting in metal immobilization within the exopolymeric matrix. These complexes generally result from electrostatic interactions between the metal ligands and negatively charged components of biopolymers. Moreover, enzymatic activities in EPS also assist detoxification of heavy metals by transformation and subsequent precipitation in the polymeric mass. Although the core mechanism for metal binding and / or transformation using microbial exopolymer remains identical, the existence and complexity of EPS from pure bacterial cultures, biofilms, biogranules and activated sludge systems differ significantly, which in turn affects the EPS-metal interactions. This paper presents the features of EPS from various sources with a view to establish their role as central elements in bioremediation of heavy metals.     

Heavy metal pollution in aquatic ecosystems and its phytoremediation using wetland plants: an ecosustainable approach

This review addresses the global problem of heavymetal pollution originating from increased industrialization and urbanization and its amelioration by using wetland plants both in a microcosm as well as natural/field condition. Heavymetal contamination in aquatic ecosystems due to discharge of industrial effluents may pose a serious threat to human health. Alkaline precipitation, ion exchange columns, electrochemical removal, filtration, and membrane technologies are the currently available technologies for heavy metal removal. These conventional technologies are not economical and may produce adverse impacts on aquatic ecosystems. Phytoremediation of metals is a cost-effective "green" technology based on the use of specially selected metal-accumulating plants to remove toxic metals from soils and water. Wetland plants are important tools for heavy metal removal. The Ramsar convention, one of the earlier modern global conservation treaties, was adopted at Ramsar, Iran, in 1971 and became effective in 1975. This convention emphasized the wise use of wetlands and their resources. This review mentions salient features of wetland ecosystems, their vegetation component, and the pros and cons involved in heavy metal removal. Wetland plants are preferred over other bio-agents due to their low cost, frequent abundance in aquatic ecosystems, and easy handling. The extensive rhizosphere of wetland plants provides an enriched culture zone for the microbes involved in degradation. The wetland sediment zone provides reducing conditions that are conducive to the metal removal pathway. Constructed wetlands proved to be effective for the abatement of heavymetal pollution from acid mine drainage; landfill leachate; thermal power; and municipal, agricultural, refinery, and chlor-alkali effluent. the physicochemical properties of wetlands provide many positive attributes for remediating heavy metals. Typha, Phragmites, Eichhornia, Azolla, Lemna, and other aquatic macrophytes are some of the potent wetland plants for heavy metal removal. Biomass disposal problem and seasonal growth of aquatic macrophytes are some limitations in the transfer of phytoremediation technology from the laboratory to the field. However, the disposed biomass of macrophytes may be used for various fruitful applications. An ecosustainable model has been developed through the author's various works, which may ameliorate some of the limitations. The creation of more areas for phytoremediation may also aid in wetlands conservation. Genetic engineering and biodiversity prospecting of endangered wetland plants are important future prospects in this regard.     

Effects of temperature on metal tolerance and the accumulation of Zn and Pb by metal-tolerant fungi isolated from urban runoff treatment wetlands

Aims:  To investigate the ability of two fungi to accumulate Zn and Pb, the effect of temperature on their metal tolerance and possible mechanisms involved in metal accumulation.
Methods and results:  Beauveria bassiana and Rhodotorula mucilaginosa isolated from constructed wetlands receiving urban runoff were grown in modified glycerol asparagine medium containing elevated levels of Zn and Pb at 30°C. Beauveria bassiana accumulated up to 0·64% of available Zn and 8·44% of Pb. The corresponding values for R. mucilaginosa were up to 2·05% for Zn and 16·55% for Pb. Radial growth of colonies grown at 4° and 30°C on agar containing Zn or Pb indicated that metal tolerance was not seriously affected by a decrease in temperature. Transmission electron microscopy and emission dispersion x-ray spectrophotometry suggested that the mechanism of resistance in B. bassiana may be associated with the precipitation of Pb (possibly in the form of oxalates).
Conclusion:  The processes of biosorption could potentially occur throughout the year with both living and dead cells able to accumulate metals.
Significance and Impact of the Study:  Identified precipitation processes could be an important mechanism in metal removal in wetland substrates serving as long-term storage sinks.     

Patterns of metal distribution in hypersaline microbialites during early diagenesis: Implications for the fossil record

The use of metals as biosignatures in the fossil stromatolite record requires understanding of the processes controlling the initial metal(loid) incorporation and diagenetic preservation in living microbialites. Here, we report the distribution of metals and the organic fraction within the lithifying microbialite of the hypersaline Big Pond Lake (Bahamas). Using synchrotron‐based X‐ray microfluorescence, confocal, and biphoton microscopies at different scales (cm–μm) in combination with traditional geochemical analyses, we show that the initial cation sorption at the surface of an active microbialite is governed by passive binding to the organic matrix, resulting in a homogeneous metal distribution. During early diagenesis, the metabolic activity in deeper microbialite layers slows down and the distribution of the metals becomes progressively heterogeneous, resulting from remobilization and concentration as metal(loid)‐enriched sulfides, which are aligned with the lamination of the microbialite. In addition, we were able to identify globules containing significant Mn, Cu, Zn, and As enrichments potentially produced through microbial activity. The similarity of the metal(loid) distributions observed in the Big Pond microbialite to those observed in the Archean stromatolites of Tumbiana provides the foundation for a conceptual model of the evolution of the metal distribution through initial growth, early diagenesis, and fossilization of a microbialite, with a potential application to the fossil record.     

Microorganisms and heavy metal toxicity

The environmental and microbiological factors that can influence heavy metal toxicity are discussed with a view to understanding the mechanisms of microbial metal tolerance. It is apparent that metal toxicity can be heavily influenced by environmental conditions. Binding of metals to organic materials, precipitation, complexation, and ionic interactions are all important phenomena that must be considered carefully in laboratory and field studies. It is also obvious that microbes possess a range of tolerance mechanisms, most featuring some kind of detoxification. Many of these detoxification mechanisms occur widely in the microbial world and are not only specific to microbes growing in metal-contaminated environments.     

湿地系统中植物和土壤在治理重金属污染中的作用

重金属污染环境的治理是目前环境工程的核心课题。湿地作为水陆相互作用形成的独特生态系统,在重金属污染治理中的作用倍受关注。对湿地植物、土壤在治理重金属污染中所起的关键作用及其机理做一综述,并对治理重金属污染的湿地构建提出几点建议。     

Millimeter‐scale resolution of trace metal distributions in microbial mats from a hypersaline environment in Baja California,Mexico

Microbial mats from two ponds with different salinities from the saltern of Guerrero Negro (Mexico) points toward millimeter‐scale coherent variations in trace metal (Me) concentrations (Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn). Total, HCl‐leachable and pyrite‐associated Me showed a trend of increasing concentrations with increasing depth suggesting gradual addition of reactive Me probably as a result of metal sulfide precipitation at depth. The trends in Me profiles can be ascribed to the establishment and maintenance of microzones that promote geochemical processes, bacterial population distributions, and differential mass transport within the mats. Degrees of trace metal pyritization (1 ± 1% for Zn to 24 ± 7% for Cd) as well as metals associated with the pyrite fraction (<1.4–36 ± 18 nmol g^?1 for Zn and Mn, respectively) were low, as expected from a reactive Fe‐limited system like Guerrero Negro. Calculated enrichment factors showed that Ni (2.6 ± 2.1), Co (5.5 ± 4.0), Pb (9.4 ± 7.4), and Cd (57 ± 39) were, on average, enriched in the microbial mats of Guerrero Negro. Natural enrichments of Cd, Pb, and Co in sediments along the coast of Baja California and metabolical requirements of Co and Ni by the predominant cyanobacteria in the Guerrero Negro mats may explain these enrichments. Metal characteristics in microbial mats could be advantageously used as biosignatures to identify their presence in the geological record or in other planetary systems.     

Microbial and plant derived biomass for removal of heavy metals from wastewater

Discharge of heavy metals from metal processing industries is known to have adverse effects on the environment. Conventional treatment technologies for removal of heavy metals from aqueous solution are not economical and generate huge quantity of toxic chemical sludge. Biosorption of heavy metals by metabolically inactive non-living biomass of microbial or plant origin is an innovative and alternative technology for removal of these pollutants from aqueous solution. Due to unique chemical composition biomass sequesters metal ions by forming metal complexes from solution and obviates the necessity to maintain special growth-supporting conditions. Biomass of Aspergillus niger, Penicillium chrysogenum, Rhizopus nigricans, Ascophyllum nodosum, Sargassum natans, Chlorella fusca, Oscillatoria anguistissima, Bacillus firmus and Streptomyces sp. have highest metal adsorption capacities ranging from 5 to 641 mg g(-1) mainly for Pb, Zn, Cd, Cr, Cu and Ni. Biomass generated as a by-product of fermentative processes offers great potential for adopting an economical metal-recovery system. The purpose of this paper is to review the available information on various attributes of utilization of microbial and plant derived biomass and explores the possibility of exploiting them for heavy metal remediation.     

Sorption and precipitation of metals in activated sludge

A conceptual model describing the relative roles of sorption and precipitation processes for metals in solid-solution suspensions is presented. The model performance is demonstrated using experimental data on sorption and precipitation of metals in samples of activated sludge mixed liquor. Based on the experimental results presented here, it appears that, at total metal and mixed liquor suspended solids concentrations and pH values generally encountered in full-scale municipal (or combined municipal/industrial) activated sludge systems, metals are primarily removed by sorption processes.     

Siderophores mediate reduced and increased uptake of cadmium by Streptomyces tendae F4 and sunflower (Helianthus annuus), respectively

Aims: As a toxic metal, cadmium (Cd) affects microbial and plant metabolic processes, thereby potentially reducing the efficiency of microbe or plant‐mediated remediation of Cd‐polluted soil. The role of siderophores produced by Streptomyces tendae F4 in the uptake of Cd by bacteria and plant was investigated to gain insight into the influence of siderophores on Cd availability to micro‐organisms and plants. Methods and Results: The bacterium was cultured under siderophore‐inducing conditions in the presence of Cd. The kinetics of siderophore production and identification of the siderophores and their metal‐bound forms were performed using electrospray ionization mass spectrometry. Inductively coupled plasma spectroscopy was used to measure iron (Fe) and Cd contents in the bacterium and in sunflower plant grown in Cd‐amended soil. Siderophores significantly reduced the Cd uptake by the bacterium, while supplying it with iron. Bacterial culture filtrates containing three hydroxamate siderophores secreted by S. tendae F4 significantly promoted plant growth and enhanced uptake of Cd and Fe by the plant, relative to the control. Furthermore, application of siderophores caused slightly more Cd, but similar Fe uptake, compared with EDTA. Bioinoculation with Streptomyces caused a dramatic increase in plant Fe content, but resulted only in slight increase in plant Cd content. Conclusion: It is concluded that siderophores can help reduce toxic metal uptake in bacteria, while simultaneously facilitating the uptake of such metals by plants. Also, EDTA is not superior to hydroxamate siderophores in terms of metal solubilization for plant uptake. Significance and Impact of the Study: The study showed that microbial processes could indirectly influence the availability and amount of toxic metals taken up from the rhizosphere of plants. Furthermore, although EDTA is used for chelator‐enhanced phytoremediation, microbial siderophores would be ideal for this purpose.     

湿地植物根表的铁锰氧化物膜

湿地植物根系具有泌氧能力 ,使其根表及根际微环境呈氧化状态。因而 ,土壤溶液中一些还原性物质被氧化 ,如 Fe2 ,Mn2 ,形成的氧化物呈红色或红棕色胶膜状包裹在根表 ,称为铁锰氧化物膜。铁锰氧化物膜及其根际微环境是湿地植物根系吸收养分和污染物的门户 ,势必会影响这些物质的吸收。主要综述了铁锰氧化物膜的形成和组成 ,以及根表形成的氧化物膜的生态效应 ,也就是氧化物胶膜对植物根系吸收外部介质中的养分及污染物质——重金属离子的影响     

大型浅水湖泊鄱阳湖湿地微生物的研究现状

鄱阳湖是我国第一大淡水湖泊,同时也是一个典型的季节性通江浅水湖泊,独特的水文特征和多样的湿地景观类型形成了复杂多样的微生物群落。本文综述了鄱阳湖水文节律、营养盐及重金属含量对湖泊微生物群落组成的影响,以及水位高程和湿地围垦对鄱阳湖湿地土壤微生物分布特征的影响,同时还探讨了未来湖泊湿地微生物的研究方向和鄱阳湖所拥有的独特研究条件,以期为未来湖泊微生物研究提供重要参考。     

Microbial communities of ultramafic soils in maquis and rainforest at Mont Do,New Caledonia

We analysed variation in microbial community richness and function in soils associated with a fire‐induced vegetation successional gradient from low maquis (shrubland) through tall maquis to rainforest on metal‐rich ultramafic soils at Mt Do, New Caledonia. Random amplified polymorphic DNA fingerprinting was used to determine the extent of genetic relatedness among the microbial communities and indicated that the open and tall maquis microbial communities were more similar to each other than they were to the rainforest community. Sole‐source carbon utilization indicated variation in the microbial communities, again with greater diversity in rainforest soils. Plate counts showed that both rainforest and maquis soils contained bacteria that can grow in the presence of up to 20 mmol L^?1 nickel and 10 mmol L^?1 chromium. Understanding microbial community composition and dynamics in these ultramafic soils may lead to a better understanding of the processes facilitating vegetation succession from shrubland to forest on these high‐metal substrates, and of approaches to successful revegetation following mining for metals including nickel, chromium and cobalt.