Toxicity of copper to acetoclastic and hydrogenotrophic activities of methanogens and sulfate reducers in anaerobic sludge

Heavy metals could potentially negatively impact microorganisms in anaerobic sulfate reducing bioreactors. The objective of this is study was to evaluate the inhibitory effect of copper to acetoclastic and hydrogenotrophic activities of methanogens and sulfate reducers in sludge obtained from a full-scale sulfate reducing bioreactor. The 50% inhibiting concentration (50%IC) of Cu(2+) to acetoclastic and hydrogenotrophic methanogens was 20.7 and 8.9 mg l(-1), respectively. The 50%IC of Cu(2+) to acetoclastic sulfate reduction was 32.3 mg l(-1). The hydrogenotrophic sulfate reducers were only inhibited by 27% at the highest concentration of Cu(2+) tested, 200 mg l(-1), indicating a high level of tolerance. The soluble Cu(2+) was observed to decrease rapidly in both the methanogenic and sulfate reducing assays. The highest level of decrease was observed in the hydrogenotrophic sulfate reducing assay which was over 99% in 5h. The results of this study indicate that sulfate reducing biotechnologies would be robust at relatively high inlet concentrations of Cu(2+).     

Quantification of the inhibitory effect of methyl fluoride on methanogenesis in mesophilic anaerobic granular systems

The inhibitory effect of CH₃F on methanogenesis in mesophilic anaerobic granules was tested at different concentrations (0-10% v/v, in the gas phase) and verified by the stable carbon isotopic signatures of CH₄ and CO₂. The results showed that the inhibitory effect increased with the initial CH₃F concentration up to 5%. The CH₃F concentration causing 50% metabolic inhibition was 0.32%. Complete inhibition of acetoclastic methanogenesis with a 91% reduction in total methanogenic activity was achieved when 5% CH₃F was initially added to the headspace, which resulted in 870 μM dissolved CH₃F in the liquid. It was much higher than that applied in other natural anoxic non-granular systems, indicating that the layered granular structure influenced the inhibitory effect. The obvious increase in hydrogen content indicated that high concentrations of CH₃F (?5%) suppressed hydrogenotrophic methanogenesis as well. The stable inhibition lasted for at least 6 d as the CH₃F concentration decreased slowly with incubation time. These results suggested that CH₃F could be used for investigating methanogenic processes in anaerobic granular systems after the CH₃F concentration and incubation time for specific inhibition of acetoclastic methanogenesis were carefully determined. In the present system, CH₃F concentration of 5% was suggested to be optimal.     

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...     

Toxic effect of surfactants and probable products of their biodegradation on methanogenesis in an anaerobic microbial community.

Surfactants used in household and various industries, are rather toxic; therefore, the accumulation of these compounds in the environment through wastewaters has challenged the problem of their biodegradation. In this research, an attempt was made to assess the toxic effect of various surfactants and the likely products of their biodegradation on the acetoclastic methanogens of an anaerobic microbial community. Among the substances investigated, cationic surfactants were found to be most toxic to methanogens: 154 mg/l alkamon DS and 345 mg/l catamin AB induced a 50% inhibition of methanogenesis. Toxicity studies of some aromatic and cyclic compounds, as the probable products of biodegradation of alkylbenzene sulfonate surfactants, showed that methanogenesis in the microbial community under study are rather tolerant to high concentrations of these compounds.     

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.     

Effects of oxygen exposure on anaerobic digester sludge.

Recuperative thickening of anaerobic digester sludge (thickening with solids return) yields increased digester capacity. Common thickening methods cause oxygen exposure to the digester sludge. This study evaluated the effects of various levels of oxygen exposure on the acetoclastic methanogens. Gravity belt thickening had no detrimental effect on the acetoclastic activity. From a 7-day batch test with continuous oxygen exposure of digester sludge, a 12% loss in acetoclastic activity was predicted for a digester with a 20-day solids retention time (SRT) and 100% recycle with recuperative thickening via dissolved air flotation thickening. However, a greater loss (27%) was found from a long-term, bench-scale digester operated under similar conditions. This loss did not affect the digester performance, as measured by volatile solids destruction. This research suggests that recuperative thickening may not affect digester performance at a long SRT with constant operation, but may change the reserve capacity of the anaerobic community.     

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.     

Ammonia inhibition on thermophilic anaerobic digestion

This study evaluated both chronic and acute toxicity of ammonia in thermophilic anaerobic digestion of synthetic wastewater over a range of acclimation concentrations. The inhibition effects of ammonia, in terms of total ammonia nitrogen (TAN), under various pH values and acclimation conditions on thermophilic aceticlastic methanogens were investigated. Completely mixed thermophilic anaerobic reactors operated at a chemical oxygen demand (COD) loading rate of 4 g/lday and a solid retention time (SRT) of 7 days were subjected to TAN concentrations of 0.40, 1.20, 3.05, 4.92, and 5.77 g/l. The reactor operations presented a case of chronic inhibition and it was observed that TAN concentrations of 4.92 and 5.77 g/l caused a drop in methane production by as much as 39% and 64%, respectively with respect to control. Batch anaerobic toxicity assays (ATA) were also performed to evaluate the acute toxicity effects of TAN and pH on methanogenesis at thermophilic condition. Modeling based on the results of ATA indicated that aceticlastic methanogens acclimated to high concentrations of TAN were less sensitive to increase in TAN and could tolerate wider pH ranges. TAN concentration causing 100% inhibition occurred in the range of 8-13 g/l, depending on acclimation condition and system pH.     

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.     

Influence of particle size distribution on anaerobic degradation of phenol and analysis of methanogenic microbial community

Sludge morphology considerably affects the mechanism underlying microbial anaerobic degradation of phenol. Here, we assessed the phenol degradation rate, specific methanogenic activity, electron transport activity, coenzyme F420 concentration, and microbial community structure of five phenol-degrading sludge of varying particle sizes (i.e., < 20, 20–50, 50–100, 100–200, and > 200 μm). The results indicated an increase in phenol degradation rate and microbial community structure that distinctly correlated with an increase in sludge particle size. Although the sludge with the smallest particle size (< 20 μm) showed the lowest phenol degradation rate (9.3 mg COD·gVSS−1 day−1), its methanogenic activity with propionic acid, butyric acid, and H2/CO2 as substrates was the best, and the concentration of coenzyme F420 was the highest. The small particle size sludge did not contain abundant syntrophic bacteria or hydrogenotrophic methanogens, but contained abundant acetoclastic methanogens. Moreover, the floc sizes of the different sludge varied in important phenol-degrading bacteria and archaea, which may dominate the synergistic mechanism. This study provides a new perspective on the role of sludge floc size on the anaerobic digestion of phenol.     

Overexpressing both ATP sulfurylase and selenocysteine methyltransferase enhances selenium phytoremediation traits in Indian mustard

A major goal of our selenium (Se) phytoremediation research is to use genetic engineering to develop fast-growing plants with an increased ability to tolerate, accumulate, and volatilize Se. To this end we incorporated a gene (encoding selenocysteine methyltransferase, SMT) from the Se hyperaccumulator, Astragalus bisulcatus, into Indian mustard (LeDuc, D.L., Tarun, A.S., Montes-Bayón, M., Meija, J., Malit, M.F., Wu, C.P., AbdelSamie, M., Chiang, C.-Y., Tagmount, A., deSouza, M., Neuhierl, B., B?ck, A., Caruso, J., Terry, N., 2004. Overexpression of selenocysteine methyltransferase in Arabidopsis and Indian mustard increases selenium tolerance and accumulation Plant Physiol. 135, 377-383.). The resulting transgenic plants successfully enhanced Se phytoremediation in that the plants tolerated and accumulated Se from selenite significantly better than wild type. However, the advantage conferred by the SMT enzyme was much less when Se was supplied as selenate. In order to enhance the phytoremediation of selenate, we developed double transgenic plants that overexpressed the gene encoding ATP sulfurylase (APS) in addition to SMT, i.e., APSxSMT. The results showed that there was a substantial improvement in Se accumulation from selenate (4 to 9 times increase) in transgenic plants overexpressing both APS and SMT.     

Effects of arsenic on blast transformation and DNA synthesis of human blood lymphocytes

Effects of inorganic arsenicals on DNA synthesis in unsensitized human blood lymphocytes were biphasic: the chemicals at very low concentrations enhanced blast transformation and DNA synthesis, whereas higher concentrations inhibited the transformation and DNA synthesis. The concentrations of arsenicals at which the maximum stimulating effect was found were 1 x 10(-5) M, 1 x 10(-6) M or 2 x 10(-6) M, and 0.8 x 10(-6) M or 1 x 10(-6) M for sodium arsenite exposure of 1 h, 3 days and 6 days, respectively; for sodium arsenate, 1 x 10(-5) M, 1 x 10(-5) M, and 2 x 10(-6) M or 5 x 10(-6) M, respectively. Arsenicals must be present for the entire 6 days culture period to produce maximum stimulation of blast transformation of human lymphocytes. The longer exposure of the lymphocytes to arsenicals, the lower the concentrations of arsenicals at which the maximum stimulating effect was found. The stimulating effect of trivalent arsenic (sodium arsenite) was stronger than pentavalent arsenic (sodium arsenate).     

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.     

Treatment of carbofuran-bearing synthetic wastewater using UASB process

In the present study, fate of carbofuran in anaerobic environments and the adverse effects of carbofuran on conventional anaerobic systems were evaluated. Carbofuran degradation studies were carried out in batch reactors with varying carbofuran concentrations of 0 to 270.73 mg/L corresponding to a sludge-loading rate (SLR) of 2.12 x 10(-6) to 3.83 x 10(-3) g of carbofuran/g of volatile suspended solids (VSS)/d. Carbofuran concentration was reduced to undetectable levels at the end of 8 and 13 days in the batch reactors operated with a SLR of 2.12 x 10(-6) and 3.33 x 10(-5) g of carbofuran/g of VSS/d, respectively. Performances of two anaerobic reactors i.e. upflow anaerobic sludge blanket (UASB) and modified UASB (with tube settlers) were evaluated in the presence and absence of carbofuran using synthetic wastewater. In the absence of carbofuran, the soluble chemical oxygen demand (COD) removal efficiency in the conventional UASB reactor at 8 h and 6 h hydraulic retention time (HRT) was nearly 88% and 76%, respectively, whereas in modified UASB reactor it was increased to 90% at 8 h HRT and 78% at 6 h HRT. When 28 mg/L (SLR of 1.19 x 10(-2) g of carbofuran/g of VSS/d) of carbofuran was introduced in the reactors, the COD removal efficiency was reduced to 41% and 44% in conventional and modified UASB reactors respectively. However, the reactor could maintain around 80% COD removal efficiency at a carbofuran concentration of 7.84 mg/L (SLR of 3.64 x 10(-3) g of carbofuran/g of VSS/d). The reactor efficiency was also measured in terms of specific acetoclastic methanogenic activity (SMA). The toxic effect of carbofuran was reversible to a certain extent. Carbofuran removal efficiency in the conventional UASB reactor at carbofuran concentrations of 7, 13 and 28 mg/L were 40 +/- 3%, 27 +/- 3%, and 11 +/- 3%, respectively. In modified UASB reactor, carbofuran removal efficiency was almost uniform at 7 and 13 mg/L but it was reduced nearly by 56% at 28 mg/L. The major metabolite of carbofuran i.e. 3-keto carbofuran was found in all the reactors.     

Anaerobic treatment of high-saline wastewater using halophilic methanogens in laboratory-scale anaerobic filters.

The presence of a high concentration of sodium in wastewater is considered inhibitory for anaerobic biological treatment. This research was designed to investigate the potential use of halophilic methanogens and a mixed culture of halophilic methanogens and digester sludge, in anaerobic filters, for treatment of organic pollutants in high-saline wastewater at 35 degrees C. Data related to startup of the filters are presented. Both halophilic and mixed-culture anaerobic filters were able to operate at a sodium chloride concentration of 35 g/L, at organic loading rates (OLRs) of 6.2 and 5 kg chemical oxygen demand (COD)/m(3) x d, respectively. The COD removal efficiency was as high as 80%, and the systems were able to maintain a low volatile fatty acids concentration of 500 mg/L. No significant difference in COD removal was observed between the halophilic filter and the mixed-culture filter. Increasing the salt concentration to 37 g/L at an OLR of 3 kg/m(3) x d caused system failure.     

Forms and distribution of selenium at different depths and among particle size fractions of three Taiwan soils

The bioavailability of selenium in soils for plants depends more on its forms than on its total concentration. The purpose of the present study was to examine the solid-phase forms of selenium at different depths of three soil series representing major farming soil groups in Taiwan as well as the amounts of selenium in sand, silt and clay fractions of the soils. The study was conducted by means of sequential extraction to obtain the amounts of selenium and the distribution of various solid-phase forms of selenium at different depths of Pinchen (121 degrees 11(')E, 24 degrees 55(')N), Toulun-Sheto (120 degrees 55(')E, 24 degrees 50(')N), and Chunliao (120 degrees 25(')E, 23 degrees 57(')N) soil series. The amounts of metal oxide-bound form of selenium in the three soil series were the largest, with those of Pinchen and Toulun-Sheto soil series exceeding 50% of the total amounts of selenium and that of Chunliao soil series maintained at 30-40%. In the Pinchen and Toulun-Sheto soil series, the amounts of selenium in clay fractions were the largest, with a significant difference between the clays with and without metal oxides and organic matter removed. The amounts of selenium remained high in silt and/or sand fractions of the Chunliao soil series with metal oxides and organic matter removed. Metal oxide and organic matter contents of the three soil series mainly affect the amounts of various solid-phase forms of selenium and their distribution in different depths and particle size fractions of the soils. This observation of selenium associated with soil constituents was in good agreement with the results of the adsorption of selenite and selenate by the three soil series.     

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.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by FeII-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 (SeVIO4(2-)) and selenite (SeIVO3(2-)). Previous investigations have demonstrated, however, that SeIV and SeVI are reduced by surface-associated FeII, thereby forming insoluble Se0 and Fe selenides. Here we show that the mixed FeII/III (hydr)oxides green rust and magnetite, and the FeII sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the FeII carbonate siderite produces elemental Se. In the case of mackinawite, both S(-II) and FeII 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 FeII 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 x 10(-8) M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since FeII 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.     

Effects of copper on spore germination, growth and ultrastructure of Polypodium cambricum L. gametophytes

The effects of different concentrations (10(-5), 5x10(-5) and 10(-4)M) of copper bromide on spore germination, growth and ultrastructure were investigated in Polypodium cambricum L. gametophytes. The inhibitory effect of Cu was observed in spores cultured on medium supplemented with 10(-4)M CuBr(2): germination occurred about 40 days after sowing and was only 25%. Concentrations of 5x10(-5) and 10(-4)M CuBr(2) induced changes in gametophyte development, possibly by re-orientation of growth. Gametophytes treated with 10(-5) and 5x10(-5)M CuBr(2) took up and accumulated a large amount of copper and ultrastructural observations showed that cytoplasmic damage was limited to twisted swollen thylakoids. The ultrastructure of gametophytes treated with 10(-4)M CuBr(2) showed absence of a vacuolar compartment. The present observations suggest that P. cambricum gametophytes could be a suitable material for studying physiological and molecular alterations induced by excess copper.