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Interplay between arsenic and selenium biomineralization in Shewanella sp. O23S

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Abstract

Bacteria play crucial roles in the biogeochemical cycle of arsenic (As) and selenium (Se) as these elements are metabolized via detoxification, energy generation (anaerobic respiration) and biosynthesis (e.g. selenocysteine) strategies. To date, arsenic and selenium biomineralization in bacteria were studied separately. In this study, the anaerobic metabolism of As and Se in Shewanella sp. O23S was investigated separately and mixed, with an emphasis put on the biomineralization products of this process. Multiple analytical techniques including ICP-MS, TEM-EDS, XRD, Micro-Raman, spectrophotometry and surface charge (zeta potential) were employed. Shewanella sp. O23S is capable of reducing selenate (SeO42-) and selenite (SeO32-) to red Se(-S)0, and arsenate (AsO43-) to arsenite (AsO33-). The release of H2S from cysteine led to the precipitation of AsS minerals: nanorod AsS and granular As2S3. When As and Se oxyanions were mixed, both As-S and Se(-S)0 biominerals were synthesized. All biominerals were extracellular, amorphous and presented a negative surface charge (-24 to -38 mV). Kinetic analysis indicated the following reduction yields: SeO32- (90%), AsO43- (60%), and SeO42- (<10%). The mix of SeO32- with AsO43- led to a decrease in As removal to 30%, while Se reduction yield was unaffected (88%). Interestingly, SeO42- incubated with AsO43- boosted the Se removal (71%). The exclusive extracellular formation of As and Se biominerals might indicate an extracellular respiratory process characteristic of various Shewanella species and strains. This is the first study documenting a complex interplay between As and Se oxyanions: selenite decreased arsenate reduction, whereas arsenate stimulated selenate reduction. Further investigation needs to clarify whether Shewanella sp. O23S employs multi-substrate respiratory enzymes or separate, high affinity enzymes for As and Se oxyanion respiration.

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Severe effects of selenium (Se) occurred among birds feeding and nesting at Kesterson Reservoir (San Joaquin Valley, California) in 1983‐1985. This paper describes the integration of site monitoring, risk assessment, and management actions conducted after the effects of Se were discovered. Selenium contamination of the site occurred over just a few years, but actions to resolve the contamination issues required >20 years. The Reservoir, a series of 12 ponds totaling about 1,280 acres (518 hectares), served for storage and evaporation of subsurface agricultural drainage. Selenium concentrations in Reservoir inflow in 1983 were about 300 µg/L, primarily as selenate; within the ponds it was biogeochemically reduced to other inorganic and organic forms and bioaccumulated by biota or deposited to sediments. An estimated 9000 kg of Se were delivered to Kesterson in 1981‐1986. A 1985 order required cleanup and abatement of the Reservoir, so Reclamation and the US Department of the Interior undertook actions and studies to reduce hazards to birds. In 1988, about one million cubic yards (764,500 cubic meters) of soil were used to fill portions of the Reservoir, transforming it into terrestrial habitat. Intensive monitoring began in 1989 to assess the impact of the Reservoir on wildlife, provide a basis for adjusting site management, verify the effectiveness of cleanup actions, and provide a basis for modifying future monitoring. Monitoring continued until 2014, with modifications and management actions based on results of two risk assessments (1993 and 2000). Monitoring results in 2013‐2014 showed that Se concentrations were relatively stable over time and risks to wildlife were low. From the initial problem discovery to the conclusion of actions taken to remediate the site, combining responsive, reactive, and adaptive monitoring; modeling; risk assessment, and mitigation actions proved effective in solving the problem so that risks to wildlife were reduced to minimal levels. This article is protected by copyright. All rights reserved. Because severe effects of selenium (Se) occurred in birds at Kesterson Reservoir, portions of the Reservoir were filled with soil, transforming it into terrestrial habitat; we describe the integration of subsequent site monitoring, ecological risk assessment, and management actions. Monitoring in 1989-2014 and two risk assessments (1993 and 2000) assessed impacts on wildlife and provided a basis for adjusting site management and modifying future monitoring; final results showed that Se concentrations were relatively stable over time and risks to wildlife were low. From the initial problem discovery to the conclusion of actions taken to remediate the site, combining responsive, reactive, and adaptive monitoring; modeling; and mitigation actions proved effective in solving the problem so that risks to wildlife were reduced to minimal levels. Selenium contamination of the site occurred over just a few years, but actions to resolve the contamination issues required more than 20 years.
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Selenium is an essential element for life, with Se(IV) reduction a key step in its biogeochemical cycle. This report identifies for the first time a dissimilatory Se(IV) reductase, Srr, from a known selenite-respiring bacterium, the haloalkalophilic Bacillus selenitireducens strain MLS10. The work extends the versatility of the complex iron-sulfur molybdoenzyme (CISM) superfamily in electron transfer involving chalcogen substrates with different redox potentials. Further, it underscores the importance of biochemical and enzymological approaches in establishing the functionality of these enzymes.
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This paper reports the dry and wet synthetic procedures and characterization by Raman spectroscopy of amorphous arsenic sulfide reference pigments. Reference spectra of two amorphous materials obtained by wet process methods and four dry process references of amorphous arsenic sulfide pigments of known composition are presented and discussed. While all materials present a main band characteristic for the amorphous pigment centered on 341 cm⁻¹, additional small contributions indicate the presence of sulfur, arsenic oxide, and crystalline nano phases embedded in the amorphous matrix. Although only the broad 341‐cm⁻¹ peak is necessary to identify the arsenic sulfide as an amorphous material, the smaller additional features allow for the characterization of the various manufacturing processes and initial materials used. In ideal conditions, these small features also enable to assess the As/S ratio of the studied amorphous arsenic sulfide pigments based on their relative intensity. In this context, the latter reference spectra were used to characterize the amorphous arsenic sulfide pigments and their arsenic to sulfur elemental composition in four 18th‐ to 20th‐century historical samples and compared with scanning electron microscopy with energy dispersive X‐ray semiquantitative analyses. The identification of the amorphous arsenic sulfide used in these historical samples was compared with the description of the manufacturing processes reported in historical sources of the time, allowing for a better understanding of the evolution of the amorphous arsenic sulfide pigments manufacturing methods.
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This study combines the interaction between the toxic oxyanions selenite and selenate and the plant growth promoting bacterium Azospirillum brasilense with a comprehensive characterization of the formed selenium particles. As selenium is an essential trace element, but also toxic in high concentrations, its state of occurrence in nature is of major concern. Growth of the bacterium was affected by selenite (1-5mM) only, observable as a prolonged growth lag-phase of 3days. Subsequently, selenite reduction occurred under aerobic conditions resulting in extracellularly formed insoluble Se(0) particles. Complementary studies by microscopic and spectroscopic techniques revealed the particles to be homogeneous and stable Se8-nSn structured spheres with an average size of 400nm and highly negative surface charge of -18mV in the neutral pH range. As this is the first study showing Azospirillum brasilense being able to biotransform selenite to selenium particles containing a certain amount of sulfur, even if environmental waters supplemented with selenite were used, they may significantly contribute to the biogeochemical cycling of both elements in soil as well as to their soil-plant transfer. Therefore, microbial biotransformation of selenite under certain circumstances may be used for various bio-remediation and bio-technological applications.
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Arsenic and mercury are potentially toxic elements of concern for soil, surficial and ground waters, and sediments. In this work various geochemical and hydrogeological tools were used to study a paradigmatic case of the combined effects of the abandonment of Hg- and As-rich waste on these environmental compartments. Continuous weathering of over 40years has promoted As and Hg soil pollution (thousands of ppm) in the surroundings of a former Hg mining-metallurgy site and affected the water quality of a nearby river and shallow groundwater. In particular, the high availability of As both in soils and waste was identified as one of the main determinants of contaminant distribution, whereas the impact of Hg was found to be minor, which is explained by lower mobility. Furthermore, potential additional sources of pollution (coal mining, high natural backgrounds, etc.) discharging into the study river were revealed less significant than the contaminants generated in the Hg-mining area. The transport and deposition of pollutants within the water cycle has also affected several kilometres downstream of the release areas and the chemistry of stream sediments. Overall, the environmental compartments studies held considerable concentrations of Hg and As, as remarkably revealed by the average contaminant load released in the river (several tons of As per year) and the accumulation of toxic elements in sediments (enrichment factors of As and Hg above 35).
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Selenium (Se) removal from synthetic solutions and from real Flue Gas Desulfurization (FGD) wastewater generated by a coal-fired power plant was studied for the first time using a commercial iron oxide impregnated strong base anion exchange resin, Purolite® FerrIX A33E. In synthetic solutions, the resin showed high affinity for selenate and selenite, while sulfate exhibited a strong competition for both oxyanions. The FGD wastewater investigated is a complex system that contains Se (~1200 µg L-1), SO42- (~1.1 g L-1), Cl¯ (~9.5 g L-1), and Ca2+ (~5 g L-1), alongside a broad spectrum of toxic trace metals including Cd, Cr, Hg, Ni, and Zn. The resin performed poorly against Se in the raw FGD wastewater and showed moderate to good removal of several trace elements such as Cd, Cr, Hg, and Zn. In FGD effluent, sulfate was identified as a powerful competing anion for Se, having high affinity for the exchange active sites of the resin. The desulfurization of the FGD effluent using BaCl2 led to the increase in Se removal from 3% (non-desulfurized effluent) to 80% (desulfurized effluent) by combined precipitation and ion exchange treatment. However, complete desulfurization using equimolar BaCl2 could not be achieved due to the presence of bicarbonate that acts as a sulfate competitor for barium. In addition to selenium and sulfate removal, several toxic metals were efficiently removed (Cd: 91%; Cr: 100%; Zn: 99%) by the combined (desulfurization and ion exchange) treatment.
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Oxyanions of arsenic and selenium call be used in microbial anaerobic respiration as terminal electron accepters. The detection of arsenate and selenate respiring bacteria in numerous pristine and contaminated environments and their rapid appearance in enrichment culture suggest that they are widespread and metabolically active in nature. Although the bacterial species that have been isolated and characterized are still few in number, they are scattered throughout the bacterial domain and include Gram-positive bacteria, beta, gamma and epsilon Proteobacteria and the sole member of a deeply branching lineage of the bacteria, Chrysiogenes arsenatus. The oxidation of a number of organic substrates (i.e. acetate, lactate, pyruvate, glycerol, ethanol) or hydrogen can be coupled to the reduction of arsenate and selenate, but the actual donor used Varies from species to species. Both periplasmic and membrane-associated arsenate and selenate reductases have been characterized. Although the number of subunits and molecular masses differs, they all contain molybdenum. The extent of the environmental impact on the transformation and mobilization of arsenic and selenium by microbial dissimilatory processes is only now being fully appreciated.
Chapter
The chapter considers basic aspects of chemical thermodynamics as relevant for understanding microbial metabolisms in nature and for defining the chemical environments of the microbial world. The chapter describes enthalpy, entropy, and Gibbs free energy. All thermodynamically favorable chemical reactions proceed, barring kinetic barriers, until the distribution of reacting components in the system reaches equilibrium. The chapter discusses influence of temperature on thermodynamic properties, activity coefficient calculations, gas solubility and Henry's law, oxidation-reduction reactions. Cellular architecture and its relationship to show how organisms gain energy for their growth and metabolism are discussed. The chapter examines how catabolic (also called dissimilatory) processes and light provide the energy for the anabolic (also called assimilatory) synthesis of cellular material. It discusses some of the basic aspects of cellular metabolism and explains how different metabolisms are named. A vast array of different energy-providing metabolisms exist in nature, and a common nomenclature is adopted whereby these metabolisms are named based on their (1) energy source, (2) electron source, and (3) carbon source.
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The abandonment of Hg-As mining and metallurgy sites, together with long-term weathering, can dramatically degrade the environment. In this work it is exemplified the complex legacy of contamination that afflicts Hg-As brownfields through the detailed study of a paradigmatic site. Firstly, an in-depth study of the former industrial process was performed to identify sources of different types of waste. Subsequently, the composition and reactivity of As- and Hg-rich wastes (calcines, As-rich soot, stupp, and flue dust) was analyzed by means of multielemental analysis, mineralogical characterization (X-ray diffraction, electronic, and optical microscopy, microbrobe), chemical speciation, and sequential extractions. As-rich soot in the form of arsenolite, a relatively mobile by-product of the pyrometallurgical process, and stupp, a residue originated in the former condensing system, were determined to be the main risk at the site. In addition, the screening of organic pollution was also aimed, as shown by the outcome of benzo(a) pyrene and other PAHs, and by the identification of unexpected Hg organo-compounds (phenylmercury propionate). The approach followed unravels evidence from waste from the mining and metallurgy industry that may be present in other similar sites, and identifies unexpected contaminants overlooked by conventional analyses. Copyright © 2015 Elsevier B.V. All rights reserved.
Article
Arsenic (As) is an important water contaminant due to its high toxicity and widespread occurrence. Arsenic-sulfide minerals (ASM) are formed during microbial reduction of arsenate (AsV) and sulfate (SO42-). The objective of this research is to study the effect of the pH on the removal of As due to the formation of ASM in an iron-poor system. A series of batch experiments was used to study the reduction of SO42- and AsV by an anaerobic biofilm mixed culture in a range of pH conditions (6.1-7.2), using ethanol as the electron donor. Total soluble concentrations and speciation of S and As were monitored. Solid phase speciation of arsenic was characterized by x-ray adsorption spectroscopy (XAS). A marked decrease of the total aqueous concentrations of As and S was observed in the inoculated treatments amended with ethanol, but not in the non-inoculated controls, indicating that the As-removal was biologically mediated. The pH dramatically affected the extent and rate of As removal, as well as the stoichiometric composition of the precipitate. The amount of As removed was 2-fold higher and the rate of the As removal was up to 17-fold greater at pH 6.1 than at pH 7.2. Stoichiometric analysis and XAS results confirmed the precipitate was composed of a mixture of orpiment and realgar, and the proportion of orpiment in the sample increased with increasing pH. The results taken as a whole suggest that ASM formation is greatly enhanced at mildly acidic pH conditions.
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Microbial selenium (Se) bioremediation is based on conversion of water soluble, toxic Se oxyanions to water insoluble, elemental Se. Formed biogenic elemental Se is of nanometer size, hampering straightforward separation from the aqueous phase. This study represents the first systematic investigation on colloidal properties of pure biogenic Se suspensions, linking electrophoretic mobility (ζ-potential) to column settling behavior. It was demonstrated that circumneutral pH, commonly applied in bioremediation, is not appropriate for gravitational separation due to the negative ζ-potential preventing agglomeration. Mono-/di-/trivalent counter cations and acidity (protons) were used to screen efficiently the intrinsic negative charge of biogenic Se suspensions at circumneutral pH. Fast settling was induced by La3+ addition in the micromolar range (86.2 ± 3.5% within 0.5 h), whereas considerably higher concentrations were needed when Ca2+ or Na+ was used. Colloidal stability was furthermore studied in different model waters. It was demonstrated that surface waters as such represent a fragile system regarding colloidal stability of biogenic Se suspensions (ζ-potential ~ -30 mV), whereas dissolved organic matter increases colloidal stability. In marine waters, biogenic Se is colloidally destabilized and is thus expected to settle, representing a potential sink for Se during transport in the aquatic environment.
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A crystallization pathway describes the movement of ions from their source to the final product. Cells are intimately involved in biological crystallization pathways. In many pathways the cells utilize a unique strategy: They temporarily concentrate ions in intracellular membrane-bound vesicles in the form of a highly disordered solid phase. This phase is then transported to the final mineralization site, where it is destabilized and crystallizes. We present four case studies, each of which demonstrates specific aspects of biological crystallization pathways: seawater uptake by foraminifera, calcite spicule formation by sea urchin larvae, goethite formation in the teeth of limpets, and guanine crystal formation in fish skin and spider cuticles. Three representative crystallization pathways are described, and aspects of the different stages of crystallization are discussed. An in-depth understanding of these complex processes can lead to new ideas for synthetic crystallization processes of interest to mate...
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Selenium is usually known as the ‘double-edged sword element’ for its dual toxic and beneficial character to health. Since the pioneer works by Schwarz and Foltz on the relationships between selenium deficiency and liver, muscle and heart diseases, many efforts have been undertaken to better understand the role of selenium in health. At the same time, an increasing number of publications have appeared during these last years on the selenium physico–chemical interactions within the environment. Both types of research represent ongoing efforts to correctly estimate the bioavailability of selenium species for health and the environment. Redox reactions, diffusion, adsorption and precipitation processes or interactions with organic matter and biota govern the speciation and mobility of selenium in the environment. This review intends to emphasize and collect the important advances made during these last years in the mechanistic understanding of processes which govern selenium cycling and bioavailability, like adsorption at the mineral/water interface, precipitation of elemental selenium, or bioavailability of nanoscaled precipitates. The advent of powerful spectroscopic techniques, like X-ray absorption spectroscopy, has allowed the structural description of adsorption and substitution processes that selenium undergoes in a variety of minerals. These and other structural details about selenium precipitates are reviewed here, together with their relationships to the bioavailability of the element in the environment.
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A newly discovered arsenate-reducing bacterium, strain OREX-4, differed significantly from strains MIT-13 and SES-3, the previously described arsenate-reducing isolates, which grew on nitrate but not on sulfate. In contrast, strain OREX-4 did not respire nitrate but grew on lactate, with either arsenate or sulfate serving as the electron acceptor, and even preferred arsenate. Both arsenate and sulfate reduction were inhibited by molybdate. Strain OREX-4, a gram-positive bacterium with a hexagonal S-layer on its cell wall, metabolized compounds commonly used by sulfate reducers. Scorodite (FeAsO42. H2O) an arsenate-containing mineral, provided micromolar concentrations of arsenate that supported cell growth. Physiologically and phylogenetically, strain OREX-4 was far-removed from strains MIT-13 and SES-3: strain OREX-4 grew on different electron donors and electron acceptors, and fell within the gram-positive group of the Bacteria, whereas MIT-13 and SES-3 fell together in the epsilon-subdivision of the Proteobacteria. Together, these results suggest that organisms spread among diverse bacterial phyla can use arsenate as a terminal electron acceptor, and that dissimilatory arsenate reduction might occur in the sulfidogenic zone at arsenate concentrations of environmental interest. 16S rRNA sequence analysis indicated that strain OREX-4 is a new species of the genus Desulfotomaculum, and accordingly, the name Desulfotomaculum auripigmentum is proposed.
Article
Washed-cell suspensions of Sulfurospirillum barnesii reduced selenate [Se(VI)] when cells were cultured with nitrate, thiosulfate, arsenate, or fumarate as the electron acceptor. When the concentration of the electron donor was limiting, Se(VI) reduction in whole cells was approximately fourfold greater in Se(VI)-grown cells than was observed in nitrate-grown cells; correspondingly, nitrate reduction was approximately 11-fold higher in nitrate-grown cells than in Se(VI)-grown cells. However, a simultaneous reduction of nitrate and Se(VI) was observed in both cases. At nonlimiting electron donor concentrations, nitrate-grown cells suspended with equimolar nitrate and selenate achieved a complete reductive removal of nitrogen and selenium oxyanions, with the bulk of nitrate reduction preceding that of selenate reduction. Chloramphenicol did not inhibit these reductions. The Se(VI)-respiring haloalkaliphile Bacillus arsenicoselenatis gave similar results, but its Se(VI) reductase was not constitutive in nitrate-grown cells. No reduction of Se(VI) was noted for Bacillus selenitireducens, which respires selenite. The results of kinetic experiments with cell membrane preparations of S. barnesii suggest the presence of constitutive selenate and nitrate reduction, as well as an inducible, high-affinity nitrate reductase in nitrate-grown cells which also has a low affinity for selenate. The simultaneous reduction of micromolar Se(VI) in the presence of millimolar nitrate indicates that these organisms may have a functional use in bioremediating nitrate-rich, seleniferous agricultural wastewaters. Results with (75)Se-selenate tracer show that these organisms can lower ambient Se(VI) concentrations to levels in compliance with new regulations proposed for release of selenium oxyanions into the environment.
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Selenium pollution is a worldwide phenomenon and is associated with a broad spectrum of human activities, ranging from the most basic agricultural practices to the most high-tech industrial processes. Consequently, selenium contamination of aquatic habitats can take place in urban, suburban, and rural settings alike--from mountains to plains, from deserts to rainforests, and from the Arctic to the tropics. Human activities that increase waterborne concentrations of selenium are on the rise and the threat of widespread impacts to aquatic life is greater than ever before. Important sources of selenium contamination in aquatic habitats are often overlooked by environmental biologists and ecological risk assessors due to preoccupation with other, higher priority pollutants, yet selenium may pose the most serious long-term risk to aquatic habitats and fishery resources. Failure to include selenium in the list of constituents measured in contaminant screening/monitoring programs is a major mistake, both from the hazard assessment aspect and from the pollution control aspect. Once selenium contamination begins, a cascade of bioaccumulation events is set into motion which makes meaningful intervention nearly impossible. However, this cascade of events need not happen if adequate foresight and planning are exercised. Early evaluation and action are key. Prudent risk management based on environmentally sound hazard assessment and water quality goals can prevent biological impacts.
Article
We report on a detailed, temperature-dependent, off-resonant Raman scattering study of glassy and supercooled selenium. Raman spectra in the frequency regime of the first-order scattering (5-450 cm(-1)) have been recorded over a wide temperature range, i.e., 143-353 K. To facilitate the analysis, the spectra have intuitively been divided in three spectral regions. The analysis of the high frequency region (bond-stretching vibrational modes) yielded information on the rings-chains equilibrium. In particular, the polymer content was found to amount to more than 85% around the glass transition temperature, exhibiting a weak temperature dependence, which extrapolates nicely to the high-temperature dissolution data. The intermediate frequency range (representative of the medium-range structural order) was treated together with the low frequency regime (where low-energy excitations, i.e., the quasielastic line and the Boson peak are the dominant contributions) owing to their strong overlap. The study of the bond-bending regime revealed information which made it possible to clarify the role of ringlike and chainlike fragments incorporated in polymeric molecules. The temperature evolution of the Boson peak and the frequency dependence of the Raman coupling coefficient Comega were also determined. An attempt to decompose the partial contribution of the pure Boson peak to Comega revealed valuable information concerning the limiting (omega-->0) behavior of the coupling coefficient.
Article
Although it has long been known that microbes can generate energy using diverse strategies, only recently has it become clear that a growing number involve electron transfer to or from extracellular substrates. The best-known example of what we will term 'extracellular respiration' is electron transfer between microbes and minerals, such as iron and manganese (hydr)oxides. This makes sense, given that these minerals are sparingly soluble. What is perhaps surprising, however, is that a number of substrates that might typically be classified as 'soluble' are also respired at the cell surface. There are several reasons why this might be the case: the substrate, in its ecological context, might be associated with a solid surface and thus effectively insoluble; the substrate, while soluble, might simply be too large to transport inside the cell; or the substrate, while benign in one redox state, might become toxic after it is metabolized. In this review, we discuss various examples of extracellular respiration, paying particular attention to what is known about the molecular mechanisms underlying these processes. As will become clear, much remains to be learned about the biochemistry, cell biology and regulation of extracellular respiration, making it a rich field of study for molecular microbiologists.