A comprehensive review on environmental transformation of selenium: recent advances and research perspectives.

Selenium (Se) is an important micronutrient and essential trace element for both humans and animals, which exist in the environment ubiquitously. Selenium deficiency is an important issue worldwide, with various reported cases of its deficiency. Low selenium contents in some specific terrestrial environments have resulted in its deficiency in humans. However, high levels of selenium in the geochemical environment may have harmful influences and can cause a severe toxicity to living things. Due to its extremely narrow deficiency and toxicity limits, selenium is becoming a serious matter of discussion for the scientists who deals with selenium-related environmental and health issues. Based on available relevant literature, this review provides a comprehensive data about Se sources, levels, production and factors affecting selenium bioavailability/speciation in soil, characteristics of Se, biogeochemical cycling, deficiency and toxicity, and its environmental transformation to know the Se distribution in the environment. Further research should focus on thoroughly understanding the concentration, speciation, Se cycling in the environment and food chain to effectively utilize Se resources, remediate Se deficiency/toxicity, and evaluate the Se states and eco-effects on human health.

Deproteinization assessment using isotopically enriched compounds to trace the coprecipitation of low-molecular-weight selenium species with proteins.

Studies have shown that information related to the presence of low-molecular-weight metabolites is frequently lost after deproteinization of complex matrices, such as blood and plasma, during sample preparation. Therefore, the effect of several deproteinization reagents on low-molecular-weight selenium species has been compared by species-specific isotope labeling. Two isotopically enriched selenium tracers were used to mimic models of small inorganic anionic (77Se-selenite) and organic zwitterionic (76Se-selenomethionine) species. The results presented here show that the use of a methanol-acetonitrile-acetone (1:1:1 v/v/v) mixture provided approximately two times less tracer loss from plasma samples in comparison with the classic procedure using acetonitrile, which may not be optimal as it leads to important losses of low-molecular-weight selenium species. In addition, the possible interactions between selenium tracers and proteins were investigated, revealing that both coprecipitation phenomena and association with proteins were potentially responsible for selenite tracer losses during protein precipitation in blood samples. However, coprecipitation phenomena were found to be fully responsible for losses of both tracers observed in plasma samples and of the selenomethionine tracer in blood samples. This successfully applied strategy is anticipated to be useful for more extensive future studies in selenometabolomics.

A mathematical model for the behaviour of Se-79 in soils and plants that takes account of seasonal variations in soil hydrology.

Se-79 is a long-lived radionuclide of potential radiological significance in relation to the deep geological disposal of solid radioactive wastes. In the context of release to the terrestrial environment, its main radiological impact is delivered through food chain pathways. Therefore, its accumulation in soils and uptake by plants is an important consideration in post-closure safety assessment studies. However, representation of its behaviour in the soil-plant system requires consideration of the multiple valence states that it can exhibit under different redox conditions and its susceptibility to volatilisation. A simple model is described that includes seasonal variations in soil hydrology and their effects on the mobility and root uptake of Se-79. Illustrative calculations are undertaken with the model, to demonstrate its capabilities for interpreting experimental data on the behaviour of Se-79 in soils and plants, and for making projections on the long-term behaviour of Se-79 transported to soils.

Bayesian source reconstruction of an anomalous Selenium-75 release at a nuclear research institute.

Atmospheric transport and dispersion models are important tools in radiation protection as they help to estimate the impact of radionuclides released into the atmosphere. In particular, such models can be used in combination with radionuclide observations to estimate unknown source term parameters, or to improve source term estimates obtained through other methods. In this paper, a Bayesian inference system was used to determine the source term parameters and their corresponding credible intervals of a real-world anomalous 75Se release at a nuclear facility in Belgium. Furthermore, a formulation is proposed that not only takes into account true detections, but also true instrumental non-detections, false alarms and real misses. The Bayesian inference system is able to correctly determine the known source location. The Bayesian inference is then refined by fixing the release location and by making stronger assumptions about the release period.

Comparative accumulation of (109)Cd and (75)Se from water and food by an estuarine fish (Tetractenos glaber).

Few data are available on the comparative accumulation of metal(loid)s from water and food in estuarine/marine fish. Smooth toadfish (Tetractenos glaber), commonly found in estuaries in south-eastern Australia, were separately exposed to radio-labelled seawater (14kBqL(-1) of (109)Cd and 24kBqL(-1) of (75)Se) and food (ghost shrimps; Trypaea australiensis: 875Bqg(-1)(109)Cd and 1130Bqg(-1)(75)Se) for 25 days (uptake phase), followed by exposure to radionuclide-free water or food for 30 days (loss phase). Toadfish accumulated (109)Cd predominantly from water (85%) and (75)Se predominantly from food (62%), although the latter was lower than expected. For both the water and food exposures, (109)Cd was predominantly located in the gut lining (60-75%) at the end of the uptake phase, suggesting that the gut may be the primary pathway of (109)Cd uptake. This may be attributed to toadfish drinking large volumes of water to maintain osmoregulation. By the end of the loss phase, (109)Cd had predominantly shifted to the excretory organs - the liver (81%) in toadfish exposed to radio-labelled food, and in the liver, gills and kidney (82%) of toadfish exposed to radio-labelled water. In contrast, (75)Se was predominantly located in the excretory organs (gills, kidneys and liver; 66-76%) at the end of the uptake phase, irrespective of the exposure pathway, with minimal change in percentage distribution (76-83%) after the loss phase. This study emphasises the importance of differentiating accumulation pathways to better understand metal(loid) transfer dynamics and subsequent toxicity, in aquatic biota.

Effects of soil type, moisture content, redox potential and methyl bromide fumigation on Kd values of radio-selenium in soil.

Understanding the processes that determine the solid-liquid partitioning (K(d) value) of Se is of fundamental importance in assessing the risk associated with the disposal of radio-selenium-containing waste. Using a mini-column (rather than batch) approach, K(d) values for (75)Se were determined over time in relation to soil moisture content (field capacity or saturated), redox potential and methyl bromide fumigation (used to disrupt the soil microbial population) in three contrasting soil types: clay loam, organic and sandy loam. The K(d) values were generally in the range 50-500 L kg(-1), with mean soil K(d) increasing with increasing organic matter content. Saturation with water lowered the measured redox potentials in the soils. However, only in the sandy loam soil did redox potential become negative, and this led to an increase in (75)Se K(d) value in this soil. Comparison of the data with the Eh-pH stability diagram for Se suggested that such strong reduction may have been consistent with the formation of the insoluble Se species, selenide. These findings, coupled with the fact that methyl bromide fumigation had no discernible effect on (75)Se K(d) value in the sandy loam soil, suggest that geochemical, rather than microbial, processes controlled (75)Se partitioning. The inter-relations between soil moisture content, redox potential and Se speciation should be considered in the modelling and assessment of radioactive Se fate and transport in the environment.

Total Selenium Quantification in Biological Samples by Inductively Coupled Plasma Mass Spectrometry (ICP-MS).

Selenium (Se) is an element readily absorbed during the intestinal tract, distributed in the body by means of blood and excreted mainly by urine or feces. Here, we describe the method allowing the determination of the total Se content in biological tissues and fluids by Inductively Coupled Plasma Mass Spectrometry (ICP MS).

Soil migration, plant uptake and volatilisation of radio-selenium from a contaminated water table.

The properties of (79)Se make it of likely potential importance in safety studies for geological disposal of radioactive wastes. Despite a substantial literature on toxic and nutritional aspects of selenium in the environment little consideration has been given to the behaviour of radioactive selenium and its potential transfer from a radioactive waste repository to the biosphere. Column experiments (15 x 50 cm), using a sandy loam soil, indicated that the upwards migration of (75)Se (as a surrogate for (79)Se) from a contaminated water table was dependent upon the redox status of the soil. Low redox conditions within the water table strongly limited upwards (75)Se soil migration, presumably due to the immobilisation of reduced Se species. Under natural conditions, (79)Se from a radioactive waste repository is therefore likely to accumulate at considerable depth. As a consequence, its absence from the rooting zone is likely to limit its transfer into plants. Nevertheless, the column experiments indicated that when an overlap between roots and soil contamination occurs, uptake into the plant is observed. Quantification of (75)Se volatilisation from the column surfaces suggested that this is a significant pathway by which (79)Se may move either directly from soil to the atmosphere, or from soil to plants and then to the atmosphere.

Interaction of selenite with reduced Fe and/or S species: An XRD and XAS study.

In this study, we investigated the interaction between selenite and either Fe((II))aq or S((-II))aq in solution, and the results were used to investigate the interaction between Se((IV))aq and FeS in suspension. The reaction products were characterized by a combination of methods (SEM, XRD and XAS) and the reaction mechanisms were identified. In a first experiment, Se((IV))aq was reduced to Se((0)) by interaction with Fe((II))aq which was oxidized to Fe((III)), but the reaction was only partial. Subsequently, some Fe((III)) produced akaganeite (ß-FeOOH) and the release of proton during that reaction decreased the pH. The pH decrease changed the Se speciation in solution which hindered further Se((IV)) reduction by Fe((II))aq. In a second experiment, Se((IV))aq was quantitatively reduced to Se((0)) by S((-II))aq and the reaction was fast. Two sulfide species were needed to reduce one Se((IV)), and the observed pH increase was due to a proton consumption. For both experiments, experimental results are consistent with expectations based on the oxidation reduction potential of the various species. Upon interaction with FeS, Se((IV))aq was reduced to Se((0)) and minute amounts of pyrite were detected, a consequence of partial mackinawite oxidation at surface sulfur sites. These results are of prime importance with respect to safe deep disposal of nuclear waste which contains the long-lived radionuclide (79)Se. This study shows that after release of (79)Se((IV)) upon nuclear waste matrix corrosion, selenite can be reduced in the near field to low soluble Se((0)) by interaction with Fe((II))aq and/or S((-II))aq species. Because the solubility of Se((0)) species is significantly lower than that of Se((IV)), selenium will become much less (bio)available and its migration out of deep HLW repositories may be drastically hindered.

Sorption and desorption of radioselenium on calcareous soil and its solid components studied by batch and column experiments.

The effect of different calcareous soil solid components on the sorption and desorption of radioselenium was investigated by using a selective extraction method. The distribution coefficients, the breakthrough curves and the displacement curves were experimentally determined by batch and column experiments. The experiments were carried out at pH 7.8 +/- 0.2, T=20 +/- 1 degrees C and in the presence of 0.001 M CaCl2. It is found that all sorption isotherms are linear, the sorption-desorption hysteresis for untreated and treated soils to remove organic matter, CaCO3 and organic matter plus CaCO3 is obvious; and the retention of radioselenium can probably be attributed to clay and oxides. The contributions of organic matter and CaCO3 to the sorption of radioselenium are significant, and the interaction effects among organic matter, CaCO3 and other components play an important role in the sorption of radioselenium in calcareous soil. The content of interlaminary space of compacted soil plays an important role in the sorption of radioselenium in compacted soil. The presence of CaCO3 retards the transport of radioselenium in soils, CaCO3 is an important trap of radioselenium. It is very difficult for the effluent concentration to reach the influent concentration, although radioselenium is very quickly detected in the effluent solution. The breakthrough curves (BTCs) can be simulated by a one-dimensional convection-dispersion transport model.

Detection of small selenium-containing proteins in tissues of the rat.

The important role of selenium in the mammalian organism has been manifested by the detection of several selenoenzymes, and there are still numerous selenium-containing proteins to be identified. After in vivo labeling of rats with [75Se]-selenite, gel electrophoretic separation of the proteins in tissue homogenates and autoradiography of the labeled bands, information on the selenium-containing proteins present in the different tissues was obtained. In the separation by SDS-PAGE and two-dimensional IEF/SDS-PAGE a large number of selenium-containing proteins or protein subunits with apparent molecular masses in the range from 116 to 8 kDa could be distinguished. This range was extended by applying a modified Tricine-SDS-PAGE, which allows the determination of smaller proteins. Using this method in the separation of the homogenates of the adrenal, brain, diaphragm, epididymis, heart, kidney, liver, lung, pituitary, prostate, skeletal muscle, spleen, thymus and thyroid, four additional selenium-containing proteins with molecular masses of approximately 7 kDa, 5kDa, 4 kDa and 3kDa were detected. The 5 kDa protein and the 7 kDa protein were identified as selenocysteine-containing selenoproteins.

Application of short-lived radionuclides in neutron activation analysis of biological and environmental samples.

The application of short-lived nuclides, especially in connection with the 6LiD-converter, in biological and environmental samples is demonstrated on I and Br determination in human urine, on I in pet food, and on the analysis of all the halogens in volcanic gases in a single activation. Trace element determination in lichens indicates polluted and unpolluted areas. The use of the .74-s 38mCl enables the rapid screening of great number of samples.

Chemical forms of selenium present in rat and ram spermatozoa.

In vivo and in vitro studies were conducted to investigate the chemical forms by ion-exchange chromatography of selenium (Se) present in rat and ovine spermatozoa. After injection with 75Se-selenite, the form of 75Se in rat sperm was selenocysteine, but selenocysteine and selenomethionine (SeMet) were present in ovine sperm. Presumably, synthesis of SeMet by rumen microbes are responsible for its presence in ovine sperm. In vitro incubation of ram sperm with selenocysteine or SeMet produced no changes, but incubation with selenite produced a compound that eluted one fraction before SeMet from the ion-exchange column. After treatment of this fraction with mercaptoethanol, it eluted in a later fraction upon rechromatography, suggesting it to be selenodicysteine. This compound is apparently formed because of high levels of cysteine in semen. Cysteine, reduced glutathione, and oxidized glutathione were also found in semen. The significance of the results is discussed.

Kinetics of selenate sorption in soil as influenced by biotic and abiotic conditions: a stirred flow-through reactor study.

This study (i) quantified the kinetics of selenate sorption and (ii) measured the influence of biotic processes in soil selenate stabilisation. Stirred flow-through reactor experiments were conducted on samples of a silty clay soil (pH = 8, Eh = 240-300 mV) from Bure (France) in both non-sterile and sterile conditions. Parameters of the proposed two-site sorption model (EK), adapted from van Genuchten and Wagenet (1989), were estimated by nonlinear regression. Fast selenate sorption on type-1 sites was moderate, with an equilibrium constant of 25.5 and 39.1 L/kg for non-sterile and sterile conditions. Rate-limited sorption on type-2 sites increased with time, and was predominant for longer periods of time in non-sterile conditions. At equilibrium, it would represent over 96% of the sorbed inventory, with mean sorption times of 17 h and 191 h for non-sterile and sterile conditions. Our results showed for Bure soil that (i) selenate sorption in flowing and mildly-oxidising conditions was strongly kinetically controlled, especially in non-sterile conditions, (ii) selenate desorption was much slower than sorption, which suggests its pseudo-irreversible stabilisation, and (iii) microbial activity increased the contribution of rate-limited sorption on type-2 sites, for which it increased sorption rate by a factor 7 but also facilitated its reversibility. This work stresses the limits of the Kd approach to represent selenate sorption in flowing conditions and supports an alternative formulation like the EK model, but also points out that biotic conditions are significant sources of variability for sorption parameters.

Chromatographic separation of selenium and arsenic: A potential (72)Se/(72)As generator.

An anion exchange method was developed to separate selenium and arsenic for potential utility in a (72)Se/(72)As generator. The separation of the daughter (72)As from the (72)Se parent is based on the relative acid-base behavior of the two oxo-anions in their highest oxidation states. At pH 1.5, selenate is retained on strongly basic anion exchange resin as HSeO4(-) and SeO4(2-), while neutral arsenic acid, H3AsO4, is eluted.

Evaluating the performance of the ORTEC® Detective™ for emergency urine bioassay.

The performance of the ORTEC(®) Detective™ as a field deployable tool for emergency urine bioassay of (137)Cs, (60)Co, (192)Ir, (169)Yb and (75)Se was evaluated against ANSI N13.30. The tested activity levels represent 10 % RL (reference level) and 1 % RL defined by [Li C., Vlahovich S., Dai X., Richardson R. B., Daka J. N. and Kramer G. H. Requirements for radiation emergency urine bioassay techniques for the public and first responders. Health Phys (in press, 99(5), 702-707 (2010)]. The tests were conducted for both single radionuclide and mixed radionuclides at two geometries, one conventional geometry (CG) and one improved geometry (IG) which improved the MDAs (minimum detectable amounts) by a factor of 1.6-2.7. The most challenging radionuclide was (169)Yb. The measurement of the mixture radionuclides for (169)Yb at the CG did not satisfy the ANSI N13.30 requirements even at 10 % RL. At 1 % RL, (169)Yb and (192)Ir were not detectable at either geometry, while the measurement of (60)Co in the mixed radionuclides satisfied the ANSI N13.30 requirements only at the IG.

Sorption of selenate on soils and pure phases: kinetic parameters and stabilisation.

This study was conducted to identify the principle selenate carrier phases for two selected soils, by comparing their reactivity with selenate to that of pure phases of the solids. Silica, calcium carbonate, aluminium hydroxide, goethite, bentonite and humic acid were selected as the main soil carrier phases. Comparisons were made first on the parameter values obtained with the best fit of a kinetic sorption model which can discriminate instantaneous sorption from kinetically limited sorption. Then comparisons were made of the ability for each solid to stabilise selenate by measuring the ratio of the partition coefficient for sorption (Kd(sorption)) over that of the desorption (Kd(desorption)). Kinetics and stabilisation were used to help elucidate the nature of interactions with the test solid phases for a large range of selenate concentrations. The experiments were conducted over 165 h in batch reactors, the solid being isolated from the solution by dialysis tubing, at two pH (5.4 and 8) and three selenate concentrations (1 × 10(-3), 1 × 10(-6) and 1 × 10(-8) mol L(-1)). The results obtained showed that only aluminium hydroxide can sorb selenate throughout the studied pH range (pH 5.4 to 8.0). The sorption capacity on this mineral was high (Kd(sorption) > 100 to 1 × 10(4) L kg(-1)) and the selenate was mainly stabilized by the formation of inner sphere complexes. The sorption on goethite occurred at pH 5.4 (Kd(sorption) 52 L kg(-1)), mainly as outer sphere complexes, and was null at pH 8. On silica, a weak sorption was observed only at pH 5.4 and at 165 h (Kd(sorption) 4 L kg(-1)). On bentonite, calcium carbonate and humic acid no significant sorption was observed. Concerning the two soils studied, different behaviours were observed for selenate. For soil Ro (pH 5.4), Kd(sorption) was low (8 L kg(-1)) compared to soil Bu (pH 8) (70 L kg(-1)). The sorption behaviour of selenate on soil Ro was mainly due to outer sphere complexes, as for goethite, whereas for soil Bu the sorption was mainly attributed to inner sphere complexes followed by reduction mechanisms, probably initiated by microorganisms, in which no steady state was reached at the end of the 165 h experiments. The sorption of selenate decreased when concentrations reached 1 × 10(-3) mol L(-1), due to solid saturation, except for aluminium hydroxide. Reduction of selenate seemed also to occur on goethite and soil Ro, for the same concentration, but without preventing a decrease in sorption. Thus, this work shows that the comparison of selenate behaviour between soil and pure phases helps to elucidate the main carrier phases and sorption mechanisms in soil.

Extension of sensitivity and uncertainty analysis for long term dose assessment of high level nuclear waste disposal sites to uncertainties in the human behaviour.

Biosphere dose conversion factors are computed for the French high-level geological waste disposal concept and to illustrate the combined probabilistic and deterministic approach. Both (135)Cs and (79)Se are used as examples. Probabilistic analyses of the system considering all parameters, as well as physical and societal parameters independently, allow quantification of their mutual impact on overall uncertainty. As physical parameter uncertainties decreased, for example with the availability of further experimental and field data, the societal uncertainties, which are less easily constrained, particularly for the long term, become more and more significant. One also has to distinguish uncertainties impacting the low dose portion of a distribution from those impacting the high dose range, the latter having logically a greater impact in an assessment situation. The use of cumulative probability curves allows us to quantify probability variations as a function of the dose estimate, with the ratio of the probability variation (slope of the curve) indicative of uncertainties of different radionuclides. In the case of (135)Cs with better constrained physical parameters, the uncertainty in human behaviour is more significant, even in the high dose range, where they increase the probability of higher doses. For both radionuclides, uncertainties impact more strongly in the intermediate than in the high dose range. In an assessment context, the focus will be on probabilities of higher dose values. The probabilistic approach can furthermore be used to construct critical groups based on a predefined probability level and to ensure that critical groups cover the expected range of uncertainty.

New best estimates for radionuclide solid-liquid distribution coefficients in soils. Part 3: miscellany of radionuclides (Cd, Co, Ni, Zn, I, Se, Sb, Pu, Am, and others).

New best estimates for the solid-liquid distribution coefficient (K(d)) for a set of radionuclides are proposed, based on a selective data search and subsequent calculation of geometric means. The K(d) best estimates are calculated for soils grouped according to the texture and organic matter content. For a limited number of radionuclides this is extended to consider soil cofactors affecting soil-radionuclide interaction, such as pH, organic matter content, and radionuclide chemical speciation. Correlations between main soil properties and radionuclide K(d) are examined to complete the information derived from the best estimates with a rough prediction of K(d) based on soil parameters. Although there are still gaps for many radionuclides, new data from recent studies improve the calculation of K(d) best estimates for a number of radionuclides, such as selenium, antimony, and iodine.

Comparative performance study of different sample introduction techniques for rapid and precise selenium isotope ratio determination using multi-collector inductively coupled plasma mass spectrometry (MC-ICP/MS).

The analytical performance of five sample introduction systems, a cross flow nebulizer spray chamber, two different solvent desolvation systems, a multi-mode sample introduction system (MSIS), and a hydride generation (LI2) system were compared for the determination of Se isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP/MS). The optimal operating parameters for obtaining the highest Se signal-to-noise (S/N) ratios and isotope ratio precision for each sample introduction were determined. The hydride generation (LI2) system was identified as the most suitable sample introduction method yielding maximum sensitivity and precision for Se isotope ratio measurement. It provided five times higher S/N ratios for all Se isotopes compared to the MSIS, 20 times the S/N ratios of both desolvation units, and 100 times the S/N ratios produced by the conventional spray chamber sample introduction method. The internal precision achieved for the (78)Se/(82)Se ratio at 100 ng mL(-1) Se with the spray chamber, two desolvation, MSIS, and the LI2 systems coupled to MC-ICP/MS was 150, 125, 114, 13, and 7 ppm, respectively. Instrument mass bias factors (K) were calculated using an exponential law correction function. Among the five studied sample introduction systems the LI2 showed the lowest mass bias of -0.0265 and the desolvation system showed the largest bias with -0.0321.