X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-bearing minerals

The long-lived radionuclide ⁷⁹Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these Fe^II systems is controlled by the concentration of HSe⁻; Se⁰ forms only at lower HSe⁻ concentrations related to slower HSeO₃⁻ reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe²⁺-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product ⁷⁹Se may be much lower than previously assumed.     

Selenite reduction in Boom clay: Effect of FeS(2), clay minerals and dissolved organic matter

Several experiments were set up to study Se speciation and solubility in the reducing Boom clay environment, starting from oxidized Se species which were added in oversaturation with respect to the thermodynamic solubility of reduced Se solid phases. Upon introduction of SeO3(2-) to FeS(2)-containing samples, adsorption of SeO3(2-) occurred at the FeS2 surface, and led to a reduction and precipitation of a Se0 solid phase with a solubility of 3x10(-9) M (after 60 days). In the presence of humic substances, an association of Se with these humic substances was observed and the 3x10(-9) M solubility limit was not reached in the same time delay. Upon introduction of SeO3(2-) to Boom clay suspensions (equilibration up to 9 months), the initial adsorption of SeO3(2-) on the solid phase was increased with respect to systems containing only FeS2, due to the presence of (illite) clay minerals. This competing adsorption process, and the presence of humic substances, again decreased the kinetics of reduction with respect to FeS2 samples. Also, an association of Se with Boom clay humic substances was observed, and amounted up to approximately 10(-7) M in some samples after 9 months equilibration.     

Selenium speciation in acidic environmental samples: application to acid rain-soil interaction at Mount Etna volcano

Speciation plays a crucial role in elemental mobility. However, trace level selenium (Se) speciation analyses in aqueous samples from acidic environments are hampered due to adsorption of the analytes (i.e. selenate, selenite) on precipitates. Such solid phases can form during pH adaptation up till now necessary for chromatographic separation. Thermodynamic calculations in this study predicted that a pH < 4 is needed to prevent precipitation of Al and Fe phases. Therefore, a speciation method with a low pH eluent that matches the natural sample pH of acid rain-soil interaction samples from Etna volcano was developed. With a mobile phase containing 20 mM ammonium citrate at pH 3, selenate and selenite could be separated in different acidic media (spiked water, rain, soil leachates) in <10 min with a LOQ of 0.2 μg L⁻¹ using ⁷⁸Se for detection. Applying this speciation analysis to study acid rain-soil interaction using synthetic rain based on H₂SO₄ and soil samples collected at the flanks of Etna volcano demonstrated the dominance of selenate over selenite in leachates from samples collected close to the volcanic craters. This suggests that competitive behavior with sulfate present in acid rain might be a key factor in Se mobilization. The developed speciation method can significantly contribute to understand Se cycling in acidic, Al/Fe rich environments.     

Characterizing kinetics of transport and transformation of selenium in water-sediment microcosm free from selenium contamination using a simple mathematical model

This study developed a seven-compartment model for predicting the fate of selenium (Se) in an aquatic environment containing a water-sediment boundary. Speciation of Se in water-sediment microcosms under microaerobic conditions was measured to evaluate first-order kinetics of Se transportation and transformation. The microcosm consisted of a 10-ml solution containing 1mM soluble Se as selenate (Se6+) or selenite (Se4+) and 8 g wet sediment that was free from Se contamination, sampled from the Senri, Yamato, or Yodo Rivers in Osaka, Japan. Stepwise reaction coefficients describing transportation and transformation were determined using an inverse method on this model which includes: selenate (Se(W)6+) and selenite (Se(W)4+) in ponded water; selenate (Se(S)6+) and selenite (Se(S)4+), elemental Se (Se0), organic Se (Se2-) in sediment; and gaseous Se (DMSe). During this 1-month experiment, soluble Se was transported from ponded water to the sediment and Se was transformed sequentially to other Se species through biochemical reactions. Experimental and kinetic analyses indicated quantitatively that the Yamato River microcosm, with its high organic matter content, had a high adsorption rate of soluble Se. The Yodo River microcosm had a low adsorption rate for Se6+ and a low Se reduction rate. The Senri River microcosm had an apparent high volatilization rate of DMSe. The model developed in this study is extremely useful for predicting fate of Se in aquatic environment in the field.     

Differences in uptake and translocation of selenate and selenite by the weeping willow and hybrid willow

BACKGROUND, AIM, AND SCOPE: Due to its essentiality, deficiency, and toxicity to living organisms and the extensive use in industrial activities, selenium (Se) has become an element of global environmental and health concern. Se removal from contaminated sites using physical, chemical, and engineering techniques is quite complicated and expensive. The goal of this study was to investigate uptake and translocation of Se in willows and to provide quantitative information for field application whether Se phytoremediation is feasible and ecologically safe. MATERIALS AND METHODS: Intact pre-rooted plants of hybrid willows (Salix matsudana Koidz x alba L.) and weeping willows (Salix babylonica L.) were grown hydroponically and treated with selenite or selenate at 24.0 +/- 1 degrees C for 144 h. Removal of leaves was also performed as a treatment to quantify the effect of transpiration on translocation and volatilization of Se. At the end of the study, total Se in the hydroponic solution and in different parts of plant tissues was analyzed quantitatively by hydride generation-atomic fluorescence spectrometry. The capacity of willows to assimilate both chemical forms of Se was also evaluated using detached leaves and roots in sealed glass vessels in vivo. Translocation efficiency of Se in both plants was estimated. RESULTS: Significant amounts of the applied selenite and selenate were eliminated from plant growth media by willows during the period of incubation. Both willows showed a significantly higher removal rate for selenate than for selenite (p < 0.05). Substantial differences existed in the distribution of both chemical forms of Se in plant materials: lower stems and roots were the major sites for accumulation of selenite and selenate, respectively. Translocation efficiency for selenite was significantly higher than that for selenate in both willow species (p < 0.01). Compared to the intact trees, remarkable decrease in the removal rate of both chemical forms of Se was found for willows without any leaves (p < 0.01). Volatilization of Se by plant leaves was estimated to be approximately 10% of the total applied selenite or selenate. Significant reduction (>20%) of selenate was observed in the sealed vessel with excised roots of willows, whereas trace amounts of selenite were eliminated from the hydroponic solution in the presence of roots. Detached leaves from neither of them reduced the concentration of selenite or selenate in the solution. DISCUSSION: Due to the significant difference in the removal rate and the distribution of the two chemical forms of Se in plant materials, the conversion of selenate to selenite in hydroponic solution prior to uptake and within plant tissues is unlikely. An independent uptake and translocation mechanisms are likely to exist for each Se chemical species. Uptake of selenate is mediated possibly through an active transport mechanism, whereas that of selenite may possibly depend on plant transpiration. Uptake velocities of selenite are linear (zero-order kinetics), while selenate removal processes obey first-order kinetics. In experiments with detached leaves in closed bottles, the cuticle of leaves was the major obstacle to extract both chemical forms of Se from the hydroponic solution. Phytovolatilization is a biological process playing an important role in Se removal. CONCLUSIONS: Although faster removal rates of selenate than selenite from plant growth media were observed by both willow species, selenite in plant materials was more mobile than selenate. Significant decrease in removal rates of both chemical forms of Se was detected for willows without any leaves. Significant differences in extraction, assimilation and transport pathways for selenite and selenate exist in willow trees. RECOMMENDATIONS AND PERSPECTIVES: Phytoremediation of Se is an attractive approach of cleaning up Se contaminated environmental sites. More detailed investigation on the assimilation of Se in plant roots and transport in tissues will provide further biochemical evidence to explain the differences in uptake and translocation mechanisms between selenite and selenate in willows. A relevant phytoremediation scheme can then be designed to clean up Se contaminated sites. Willows show a great potential for uptake, assimilation and translocation of both selenite and selenate. Phytotreatment of Se is potentially an efficient and practical technology for cleaning up contaminated environmental sites.     

The digestibility of waste activated sludges.

Laboratory digestion studies using waste activated sludges (WAS) were conducted to compare the digestion performance between anaerobic and aerobic processes. Nine samples of WAS from seven wastewater treatment plants were collected and batch-digested under both anaerobic and aerobic conditions for 30 days at 25 degrees C. The cation content of wastewater (both floc and solution phases) and solution biopolymer (protein and polysaccharide) was measured before and after digestion and compared with volatile solids destruction data. The study revealed that each digestion process was associated with a distinct biopolymer fraction, which accounted for differences in volatile solids reduction under anaerobic and aerobic conditions. The anaerobic digestion data showed strong correlations between soluble protein generation, ammonium production, percent volatile solids reduction, and floc iron (Fe). These data suggest that the amount of volatile solids destroyed by anaerobic digestion depends on the Fe content of floc. In aerobic digestion, polysaccharide accumulated in solution along with calcium and magnesium. For aerobic digestion, correlations between divalent cation release and the production of inorganic nitrogen were found. This implies that divalent cation-bound biopolymer, thought to be lectin-like protein, was the primary organic fraction degraded under aerobic conditions. The results of the study show that the cation content in wastewater is an important indicator of the material that will digest under anaerobic or aerobic conditions and that some of the volatile solids will digest only under either anaerobic or aerobic conditions.     

Effects of temperature and dissolved oxygen on Se(IV) removal and Se(0) precipitation by Shewanella sp. HN-41

Facultative anaerobic Shewanella sp. strain HN-41 was able to utilize selenite (Se(IV)) as a sole electron acceptor for respiration in anaerobic condition, resulting in reduction of Se(IV) and then precipitation of elemental Se nano-sized spherical particles, which were identified using energy-dispersive X-ray spectroscopy and X-ray absorption near-edge structure spectroscopy. When the effects on Se(IV) reduction to elemental Se were studied by varying incubation temperatures and dissolved oxygen contents, Se(IV) reduction occurred more actively with higher removal rate of Se(IV) in aqueous phase and well-shaped spherical Se(0) nanoparticles were formed from the incubations under N(2) (100%) or N(2):O(2) (80%:20%) at 30 degrees C with average diameter values of 181+/-40 nm and 164+/-24 nm, respectively, while relatively less amounts of irregular-shaped Se(0) nanoparticles were produced with negligible amount of Se(IV) reduction and removal under 100% of O(2). The Se particle size distributions based on scanning electron microscopy also showed a general tendency towards decreased Se particle size as oxygen content increased, whereas the particle size seemed uncorrelated to the change in the incubation temperature. These results also suggest that the size-controlled biological Se(0) nanospheres production may be achieved simply by changing the culture conditions.     

Distribution and bioaccumulation of selenium in aquatic microcosms

Closed-system microcosms were used to study factors affecting the fate of selenium (Se) in aquatic systems. Distribution and bioaccumulation of Se varied among sediment types and Se species. A mixture of dissolved (75)Se species (selenate, selenite and selenomethionine) was sorbed more rapidly to fine-textured, highly organic pond sediments than to sandy riverine sediments. Sulfate did not affect the distribution and bioaccumulation of (75)Se over the range 80-180 mg SO(4) liter(-1). When each Se species was labeled separately, selenomethionine was lost from the water column more rapidly than selenate or selenite. Selenium lost from the water column accumulated primarily in sediments, but volatilization was also an important pathway for loss of Se added as selenomethionine. Loss rates of dissolved Se residues were more rapid than rates reported from mesocosm and field studies, suggesting that sediment: water interactions are more important in microcosms than in larger test systems. Daphnids accumulated highest concentrations of Se, followed by periphyton and macrophytes. Selenium added as selenomethionine was bioaccumulated preferentially compared to that added as selenite or selenate. Organoselenium compounds such as selenomethione may thus contribute disproportionately to Se bioaccumulation and toxicity in aquatic organisms.     

Arsenic release from iron rich mineral processing waste: Influence of pH and redox potential

This paper presents the effect of pH and redox potential on the potential mobility of arsenic (As) from a contaminated mineral processing waste. The selected waste contained about 0.47 g kg(-1) of As and 66.2 g kg(-1) of iron (Fe). The characteristic of the waste was identified by acid digestion, X-ray diffraction and sequential extraction procedures. Less than 2% of the total As was acid extractable with the remaining 98% associated with Fe-oxyhydroxides and oxides. Batch leaching tests at different pH conditions showed a strong pH dependence on arsenic and iron leaching. Arsenic leaching followed a "V" shaped profiles with significant leaching in the acidic and alkaline pH region. Acid extractable phases dissolved at acidic pH, while desorption of arsenic due to increase in pH resulted in high arsenic concentration at alkaline pH. Under aerobic conditions and pH 7, As solubility was low, probably due to its precipitation on Fe-oxyhydroxides. Maximum As solubilization occurred at pH 11 (3.59 mg l(-1)). Similarity in the As and Fe leaching profiles suggested that the release of As was related to the dissolution of Fe in the low pH region. In general, redox potential did not play a significant role in arsenic or iron solubilization. It was thus concluded that for this solid waste, desorption was the predominant mechanism in arsenic leaching. A simple thermodynamic model based on arsenic and iron redox reactions was developed to identify the more sensitive redox couple.     

Distribution coefficient of selenium in Japanese agricultural soils

In order to evaluate the selenium (Se) sorption level in Japanese soils, soil/soil solution distribution coefficients (K(d)s) were obtained for 58 agricultural soil samples (seven soil classification groups) using 75Se as a tracer. Although several chemical forms of Se are present in agricultural fields, selenite was used, because it is the major inorganic Se form in acid soils such as found in Japan. The Kd values obtained covered a wide range, from 12 to 1060l/kg, and their arithmetic mean was 315l/kg. Among the soil groups, Andosols had higher Kd values. The Kd values for all samples were highly correlated with soil active-aluminum (Al) and active-iron (Fe) contents. Thus, active-Al and active-Fe were considered to be the major adsorbents of Se. Then, a new sequential extraction procedure was applied to 12 soil samples in order to quantify the effect of soil components on Se adsorption. The sequential extraction results showed that 80-100% of the adsorbed Se was recovered as Al-bound Se and Fe-bound Se. The amount of Al-bound Se was the highest in the soils that showed high Kd values, though the relative contribution of Fe-bound Se tended to increase with decreasing Kd values. The high values of Kd seemed to be caused mainly by the adsorption of Se onto active-Al in Japanese soils.     

Uptake kinetics and interaction of selenium species in tomato (Solanum lycopersicum L.) seedlings

Environmental Science and Pollution Research - Selenite and selenate are two main selenium (Se) forms absorbed by plants. The comparative effects of selenite and/or selenate on Se uptake and...     

Modes of selenium occurrence and LCD modeling of selenite desorption/adsorption in soils around the selenium-rich core,Ziyang County,China

Studying the modes of selenium occurrence in high-Se soils and its behaviors can improve understanding and evaluating its cycling, flux, and balance in geo-ecosystems and its influence on health. In this paper, using a modified sequential chemical extraction technique, seven operationally defined selenium fractions and Se valence distribution were determined about five soils in which paddy was planted (W1, W2, W3, W4, W5) and five soils in which maize was planted (H1, H2, H3, H4, H5) around the selenium-rich core, Ziyang County, Shaanxi Province, China. The results show that selenium fractions in the soils mainly include sulfide/selenide and base-soluble Se, and ligand-exchangeable Se is also high for five soils in which paddy was planted. For water-soluble Se, Se (IV) is main Se valence and almost no Se (VI) was determined about five soils in which paddy was planted, while almost 1:1 of Se (IV) and Se (VI) coexist about five soils in which maize was planted. For exchangeable Se, similar results were found. For the first time, two typical high-Se soils (W1 soil and H1 soil) were chosen to measure the pH-dependent solid-solution distribution of selenite in the pH range 3–9, and the results were explained using LCD (ligand and charge distribution) adsorption modeling. The desorbed selenite concentrations from the two soils are in general underestimated by the model due to a comparable binding affinity of phosphate and selenite on goethite and much lower amount of total selenite than total reactively adsorbed phosphate. The pH dependency of adsorption of selenite added to the soil can be successfully described with the LCD model for W1 soil. Whereas considering the influence of Al-oxides, by lowering selenite adsorption affinity constant K of Se adsorption on goethite by 16 times, the LCD model can describe the adsorption much better. The results can help to understand selenium cycling, flux, and balance in typical high-Se soils.

     

Phosphorus and sulfur in a tropical soil and their effects on growth and selenium accumulation in Leucaena leucocephala (Lam.) de Wit

Selenium (Se) is an essential metalloid element for mammals. Nonetheless, both deficiency and excess of Se in the environment are associated with several diseases in animals and humans. Here, we investigated the interaction of Se, supplied as selenate (Se⁺⁶) and selenite (Se⁺⁴), with phosphorus (P) and sulfur (S) in a weathered tropical soil and their effects on growth and Se accumulation in Leucaena leucocephala (Lam.) de Wit. The P-Se interaction effects on L. leucocephala growth differed between the Se forms (selenate and selenite) supplied in the soil. Selenate was prejudicial to plants grown in the soil with low P dose, while selenite was harmful to plants grown in soil with high P dose. The decreasing soil S dose increased the toxic effect of Se in L. leucocephala plants. Se tissue concentration and total Se accumulation in L. leucocephala shoot were higher with selenate supply in the soil when compared with selenite. Therefore, selenite proved to be less phytoavailable in the weathered tropical soil and, at the same time, more toxic to L. leucocephala plants than selenate. Thus, it is expected that L. leucocephala plants are more efficient to phytoextract and accumulate Se as selenate than Se as selenite from weathered tropical soils, for either strategy of phytoremediation (decontamination of Se-polluted soils) or purposes of biofortification for animal feed (fertilization of Se-poor soils).

     

Oxidative dissolution of uraninite precipitated on Navajo sandstone

Column and batch experiments were conducted with sandstone and ground water samples to investigate oxidation of uraninite precipitated by microbially mediated reduction of U(VI), a contaminant in ground water beneath a uranium mill tailings site near Tuba City, AZ, USA. Uraninite precipitated together with mackinawite (FeS_0.9) because Fe(III) from the sandstone and sulfate, another contaminant in the water were reduced together with U(VI). After completion of U(VI) reduction, experiments were conducted to find out whether uraninite is protected by mackinawite against reoxidation. Uncontaminated ground water from the same site, containing 7 mg/l of dissolved oxygen, was passed through the columns or mixed with sandstone in batch experiments. The results showed that small masses of uraninite, 0.1 μg/g of sandstone, are protected by mackinawite from reoxidation. Uraninite masses on the order of 0.1 μg/g correspond to U(VI) concentrations of 0.5 mg/l, typically encountered in uranium contaminated ground waters. Mackinawite is an effective buffer and is formed in sufficient quantity to provide long-term protection of uraninite. Uranium concentrations in ground water passed through the columns are too low (4 μg/l) to distinguish between dissolution and oxidative dissolution of uraninite. However, batch experiments showed that uraninite oxidation takes place.     

Nitrate reduction by green rusts modified with trace metals

A kinetic study of nitrate reduction by green rust (GR), a group of layered Fe(II)-Fe(III) hydroxide solids, was performed using a batch reactor system. The reduction rate of nitrate by GRs was affected by the anion content in the interlayer of GRs. GR containing F^- (GR-F) showed the fastest reduction rate while GR-SO₄ showed 9 times slower reaction rate than GR-F. The addition of 1 mM Pt or Cu to GR that contained 85 mM Fe(II) improved the reduction kinetics of nitrate by up to 200 times. Pt was an effective activating agent for all GRs. The sequential step reaction model that we proposed appropriately simulated the experimental data. The fastest nitrate reduction by GR-F with Pt was achieved at pH 9 among 7.5 to 11. At that condition, 1 mM nitrate transformed completely into ammonium within 23 min.     

The use of a high-FeO olivine rock as a redox buffer in a nuclear waste repository

Due to the higher stability of the spent nuclear fuel (mainly composed of UO2) under reducing conditions, and in order to enhance the retention/retardation of some key radionuclides, the olivine rock from the Lovasj?rvi intrusion has been proposed as a potential redox-active backfill-additive in deep high-level nuclear waste (HLNW) repositories. In this work, two different approaches have been undertaken in order to establish the redox buffer capacity of olivine rock: (1) The capacity of the rock to respond to changes in pH or pe has been demonstrated and the final (pH, pe) coordinates agree with the control exerted by the system Fe(II)/Fe(III). (2) The rate of consumption of oxygen has been determined at different pH values. These rates are higher than the ones reported in the literature for other solids, what would point to the possibility of using this rock as an additive to the backfill material in a HLNW.     

Absorption of selenium by Lactuca sativa as affected by carboxymethylcellulose

Several organic compounds of high molecular weight present in soil interact with selenium and may act as active binding agents affecting its availability in soil, and, consequently, selenium uptake by plants. This study is aimed at investigating the effects of polysaccharides on selenium speciation in soil and on selenium absorption by Lactuca sativa L. plants. Three-week-old seedlings were transplanted into pots filled with soil, and sodium selenite at rates of 1.5 and 5mgSekg(-1) of soil, or sodium selenate at a rate of 1.5mgSekg(-1) of soil were applied. Carboxymethylcellulose (CMC) was added to the soil at rates of 0, 3 and 30mgkg(-1) of soil. After 48 and 110d from transplanting plants were harvested, separated into root and shoot, and fresh and dry matter weights were recorded. Total selenium was determined in both soil and plant samples. A sequential extraction was used to investigate the different Se oxidation states and assess the availability of Se in soil after the final harvesting. Both selenite and selenate were absorbed by roots, but plants amended with Se(VI+) showed higher selenium concentration than plants amended with Se(IV+). Selenite appears to be less mobile than selenate both in soil and plants. The addition of carboxymethylcellulose to soil decreased the amount of selenium absorbed by plants. CMC interacted with Se, making it less mobile as evidenced by the increase in the insoluble fractions. The insoluble Se forms in soil may represent environmental Se sinks potentially available for plants if the substrate is re-used for subsequent growth cycles and selenium species are mobilized as a result of biological and chemical processes.     

Influence of form and quantity of selenium on the development and survival of an insect herbivore

Even plants classified as 'nonaccumulators' can sequester concentrations of sodium selenate, sodium selenite, selenocystine and selenomethionine that can strongly influence insect development and survival. These forms of selenium (Se), tested in diet-incorporation bioassays, proved toxic to larvae of a generalist insect herbivore at relatively low levels. Sodium selenite was the most toxic form tested against Spodoptera exigua (Hübner), with an LC(50) of 9.14 microg g(-1) wet wt (21.11 microg g(-1) dry wt). Selenocystine was intermediate with an LC(50) of 15.2 microg g(-1) wet wt. The least toxic forms, sodium selenate and selenomethionine, had LC(50)s below 50 microg g(-1) dry wt, the upper level for tissues of plants classified as nonaccumulators. Ingestion of some forms of Se also affected growth and development. Increasing concentrations of sodium selenate and sodium selenite decreased pupal weight and added significantly to the time needed for development to the pupal and adult stages. The time required to complete the larval stage increased by over 25% and the time from egg to adult emergence was extended by 22% to nearly 30%. Selenocystine and selenomethionine did not significantly increase developmental times, even at concentrations that killed 90% or more of the test populations. Analyses of relative growth rate, relative growth index, and an analysis of covariance technique for measuring growth indicated that the form of Se affected growth rates, growth inhibition responses of the larvae, and toxicological effects. Thus, quantity and the form of Se accumulating in plants grown on Se-contaminated sites are likely to influence the population dynamics of insect herbivores. The implications of these results for the ecology of contaminated sites are discussed.     

Mobile fission and activation products in nuclear waste disposal

When disposing nuclear waste in clay formations it is expected that the most radiotoxic elements like Pu, Np or Am move only a few centimetres to meters before they decay. Only a few radionuclides are able to reach the biosphere and contribute to their long-term exposure risks, mainly anionic species like I129, Cl36, Se79 and in some cases C14 and Tc99, whatever the scenario considered. The recent OECD/NEA cosponsored international MOFAP workshop focussed on transport and chemical behaviour of these less toxic radionuclides. New research themes have been addressed, such as how to make use of molecular level information for the understanding of the problem of migration at large distances. Diffusion studies need to face mineralogical heterogeneities over tens to hundreds of meters. Diffusion rates are very low since the clay rock pores are so small (few nm) that electrostatic repulsion limits the space available for anion diffusion (anion exclusion). The large volume of traversed rock will provide so many retention sites that despite weak retention, even certain of these “mobile” nuclides may show significant retardation. However, the question how to measure reliably very low retention parameters has been posed. An important issue is whether redox states or organic/inorganic speciation change from their initial state at the moment of release from the waste during long term contact with surfaces, hydrogen saturated environments, etc.     

Reduction of selenite to red elemental selenium by moderately halotolerant Bacillus megaterium strains isolated from Bhitarkanika mangrove soil and characterization of reduced product

Two Gram (+) bacterial strains, BSB6 and BSB12, showing resistance and potential for Se(IV) reduction among 26 moderately halotolerant isolates from the Bhitarkanika mangrove soil were characterized by biochemical and 16S rDNA sequence analyses. Both of them were strictly aerobic and able to grow in a wide range of pH (4-11), temperature (4-40 °C) and salt concentration (4-12%) having an optimum growth at 37 °C, pH ∼7.5 and 7% salt (NaCl). The biochemical characteristics and 16S rDNA sequence analysis of BSB6 and BSB12 showed the closest phylogenetic similarity with the species Bacillus megaterium. Both the strains effectively reduced Se(IV) and complete reduction of selenite (up to 0.25 mM) was achieved within 40 h. SEM with energy dispersive X-ray and TEM analyses revealed the formation of nano size spherical selenium particles in and around the bacterial cells which were also supported by the confocal micrograph study. The UV-Vis diffuse reflectance spectra and XRD of selenium precipitates revealed that the selenium particles are in the nanometric range and crystalline in nature. These bacterial strains may be exploited further for bioremediation process of Se(IV) at relatively high salt concentrations and green synthesis of selenium nanoparticles.