Se Cycle Research Articles

Molecular-scale insight into selenium isotope fractionation caused by adsorption on Fe (oxyhydr)oxides

Selenium (Se) isotopes have recently emerged as a potential proxy for tracing biogeochemical processes and reconstructing the evolution of global Se cycle in the oceans. However, little is known about Se isotope fractionation mechanism during the sequestration of dissolved Se oxyanions by marine ferromanganese oxides that are mainly composed of Fe and Mn (oxyhydr)oxides. Here we elucidate the molecular mechanism governing equilibrium Se isotope fractionation during adsorption on 2-line ferrihydrite, by combining isotope ratio measurements, extended X-ray absorption fine structure (EXAFS) analyses, and high level quantum chemical calculations. Results show that Se isotopes can be fractionated 0.89‰ (Δ82/76Seaqueous-adsorbed) with enrichment of lighter isotopes in the solid phase during the adsorption of Se(IV) on 2-line ferrihydrite, which is primarily driven by the formation of bidentate-binuclear inner-sphere complexes. By contrast, little or no Se isotope fractionation (<0.2‰) was observed during Se(VI) adsorption due to the outer-sphere complexation. In combination with previous results, our findings would provide molecular-scale insights into Se isotope compositions in marine ferromanganese oxides and lead to an improved understanding of Se biogeochemical cycle in the ocean. Our study also has an implication for the systematical understanding of mechanisms governing isotope fractionations of other metal oxyanions like Mo, which highlights the controls of their proton dissociation constants, electronic configurations, and radius ratios. This would improve our understanding for isotope signatures of metals in the dissolved species and the adsorbed sinks in modern and ancient environments.

Selenite reduction and biogenesis of selenium-nanoparticles by different size groups of aerobic granular sludge under aerobic conditions

Microbial transformations play a vital role in Se cycle in the environment and decrease the solubility and toxicity of Se oxyanions by converting to elemental selenium (Se0) nanostructures. Aerobic granular sludge (AGS) has attracted interest due to efficient reduction of selenite to biogenic Se0 (Bio-Se0) and retention in bioreactors. Here, selenite removal, biogenesis of Bio-Se0 and entrapment of Bio-Se0 by different size groups of aerobic granules were investigated to optimize biological treatment process for Se-laden wastewaters. Furthermore, a bacterial strain showing high selenite tolerance and reduction was isolated and characterized. Removal of selenite and conversion to Bio-Se0 were achieved by all the size groups of granules ranging from 0.12 mm to 2 mm and above. However, selenite reduction and Bio-Se0 formation were rapid and more efficient with large aerobic granules (≥0.5 mm). The formed Bio-Se0 was majorly associated with the large granules, due to better entrapment capabilities. In contrast, the Bio-Se0 formed by the small granules (≤0.2 mm) was distributed both in the granules and aqueous phase because of ineffective entrapment. Scanning electron microscope and energy dispersive X-ray (SEM-EDX) analysis confirmed formation of Se0 spheres and association with the granules. Efficient selenite reduction and entrapment of Bio-Se0 was related to prevalent anoxic/anaerobic zones in the large granules. A bacterial strain showing efficient SeO32− reduction of up to 15 mM SeO32− under aerobic conditions was identified as Microbacterium azadirachtae. SEM-EDX analysis confirmed the formation and entrapment of Se0 nanospheres (size: 100 ± 5 nm) in the extracellular matrix. The cells immobilized in alginate beads showed effective SeO32− reduction and Bio-Se0 entrapment. Efficient reduction and immobilization of bio-transformed metalloids by large AGS and AGS-borne bacteria implicates prospective use in bioremediation of metal(loid) oxyanions and bio-recovery.

Pivotal biological processes and proteins for selenite reduction and methylation in Ganoderma lucidum.

Microbial transformations, especially the reduction and methylation of Se oxyanion, have gained significance in recent years as effective detoxification methods. Ganoderma lucidum is a typical Se enrichment resource that can reduce selenite to elemental Se and volatile Se metabolites under high selenite conditions. However, the detailed biological processes and reduction mechanisms are unclear. In this study, G. lucidum reduced selenite to elemental Se and further aggregated it into Se nanoparticles with a diameter of <200nm, simultaneously accompanied by the production of pungent, odorous, and volatile methyl-selenium metabolites. Tandem mass tag-based quantitative proteomic analysis revealed thioredoxin 1, thioredoxin reductase (NADPH), glutathione reductase, 5-methyltetrahydropteroyltriglutamate-homocysteine methyltransferase, and cystathionine gamma-lyase as proteins involved in selenite reduction and methylation. Furthermore, the high expression of proteins associated with cell structures that prompted cell lysis may have facilitated Se release. The upregulation of proteins involved in the defense reactions was also detected, reflecting their roles in the self-defense mechanism. This study provides novel insights into the vital role of G. lucidum in mediating Se transformation in the biogeochemical Se cycle and contributes to the application of fungi in Se bioremediation.

Selenium species transforming along soil-plant continuum and their beneficial roles for horticultural crops.

Selenium (Se) acquirement from daily diet can help reduce the risk of many diseases. The edible parts of crop plants are the main source of dietary Se, while the Se content in crops is determined by Se bioavailability in soil. We summarize recent research on the biogeochemical cycle of Se driven by specific microorganisms and emphasize the oxidizing process in the Se cycle. Moreover, we discuss how plant root exudates and rhizosphere microorganisms affect soil Se availability. Finally, we cover beneficial microorganisms, including endophytes, that promote crop quality and improve crop tolerance to environmental stresses. Se availability to plants depends on the balance between adsorption and desorption, reduction, methylation and oxidation, which are determined by interactions among soil properties, microbial communities and plants. Reduction and methylation processes governed by bacteria or fungi lead to declined Se availability, while Se oxidation regulated by Se-oxidizing microorganisms increases Se availability to plants. Despite a much lower rate of Se oxidization compared to reduction and methylation, the potential roles of microbial communities in increasing Se bioavailability are probably largely underestimated. Enhancing Se oxidation and Se desorption are crucial for the promotion of Se bioavailability and uptake, particularly in Se-deficient soils. Beneficial roles of Se are reported in terms of improved crop growth and quality, and enhanced protection against fungal diseases and abiotic stress through improved photosynthetic traits, increased sugar and amino acid contents, and promoted defense systems. Understanding Se transformation along the plant-soil continuum is crucial for agricultural production and even for human health.

Microbial oxidation of organic and elemental selenium to selenite

Selenium (Se) is an essential trace element for life. Se reduction has attracted much attention in the microbial Se cycle, but there is less evidence for Se oxidation. In particular, it is unknown whether microorganisms oxidise organic Se(-II). In this study, four strains of bacteria, namely Dyella spp. LX-1 and LX-66, and Rhodanobacter spp. LX-99 and LX-100, isolated from seleniferous soil, were involved in the oxidation of selenomethionine (SeMet), selenocystine (SeCys2), selenourea and Se(0) to selenite (Se(IV)) in pure cultures. The oxidation rates of organic Se were more rapidly than those of Se(0) in liquid media. Then Se(0) and SeMet were used as examples, microbial oxidation was the predominant process for both additional Se(0) and SeMet in sterilised alkaline or acidic soils. The Se(IV) concentrations were significantly higher at pH 8.56 than at pH 5.25. In addition, water-soluble Se (SOLSe) and exchangeable and carbonate-bound Se (EXC-Se) fractions increased dramatically with these four Se-oxidising bacteria in unsterilised seleniferous soil. To our knowledge, this is the first study to find that various bacteria are involved in the oxidation of organic Se to Se oxyanions, bridging the gap of Se redox in the Se biogeochemical cycle.

Biogeochemistry of selenium compounds in the water column of warm monomictic Lake Kinneret

The biogeochemistry of dissolved selenium (Se) was investigated over 3 years (2015–2017) in the subtropical, warm monomictic and meso-eutrophic Lake Kinneret (Sea of Galilee, Israel). We monitored seasonal variation and vertical distribution of dissolved total Se (T.Se), inorganic oxyanions (Se(IV) & Se(VI)), reduced Se fraction (Red.Se), organic (Org.Se) and volatile Se compounds. T.Se varied between ~ 100 and 160 ng L−1 with Red.Se comprising 40–80% of the Se inventory, and Se(VI) dominating over Se(IV) most of the time. The variation in T.Se and species correlated with winter holomixis vs. summer fall stratification periods. The annual cycle includes: (a) increase of T.Se from fall/winter to spring, representing increased allochthonous Se input flux, along with Se recycling via holomixis; (b) decrease of T.Se from spring to the end of the year, representing the diminishing Se inputs and the evolving output fluxes to the lake’s bottom and to the atmosphere. Org.Se variations are directly associated with Chlorophyll-a and primary production attesting for the significant role of phytoplankton activity in the Se cycle. An important Se output flux comprises spring to summer Se uptake by phytoplankton and further volatile compounds production and volatilization accounting for ~ 10% of estimated Se input. The similarity of total dissolved Se concentrations in this work and from mid 1990s attests for long-term stability of the Se inventory. The TVSe concentrations in lacustrine systems being similar to that of estuary systems, the biological role of phytoplankton and eventually the degradation of organic material may produce similar fluxes of volatile Se to the atmosphere.

Constraining Atmospheric Selenium Emissions Using Observations, Global Modeling, and Bayesian Inference.

Selenium (Se) is an essential dietary element for humans and animals, and the atmosphere is an important source of Se to soils. However, estimates of global atmospheric Se fluxes are highly uncertain. To constrain these uncertainties, we use a global model of atmospheric Se cycling and a database of more than 600 sites where Se in aerosol has been measured. Applying Bayesian inference techniques, we determine the probability distributions of global Se emissions from the four major sources: anthropogenic activities, volcanoes, marine biosphere, and terrestrial biosphere. Between 29 and 36 Gg of Se are emitted to the atmosphere every year, doubling previous estimates of emissions. Using emission parameters optimized by aerosol network measurements, our model shows good agreement with the aerosol Se observations (R2 = 0.66), as well as with independent aerosol (0.59) and wet deposition measurements (0.57). Both model and measurements show a decline in Se over North America in the last two decades because of changes in technology and energy policy. Our results highlight the role of the ocean as a net atmospheric Se sink, with around 7 Gg yr–1 of Se transferred from land through the atmosphere. The constrained Se emissions represent a substantial step forward in understanding the global Se cycle.

A Fungal-Mediated Cryptic Selenium Cycle Linked to Manganese Biogeochemistry.

Selenium (Se) redox chemistry is a determining factor for its environmental toxicity and mobility. Currently, millions of people are impacted by Se deficiency or toxicity, and in geologic history, several mass extinctions have been linked to extreme Se deficiency. Importantly, microbial activity and interactions with other biogeochemically active elements can drastically alter Se oxidation state and form, impacting its bioavailability. Here, we use wet geochemistry, spectroscopy, and electron microscopy to identify a cryptic, or hidden, Se cycle involving the reoxidation of biogenic volatile Se compounds in the presence of biogenic manganese [Mn(III, IV)] oxides and oxyhydroxides (hereafter referred to as "Mn oxides"). Using two common environmental Ascomycete fungi, Paraconiothyrium sporulosum and Stagonospora sp., we observed that aerobic Se(IV and VI) bioreduction to Se(0) and Se(-II) occurs simultaneously alongside the opposite redox biomineralization process of mycogenic Mn(II) oxidation to Mn oxides. Selenium bioreduction produced stable Se(0) nanoparticles and organoselenium compounds. However, mycogenic Mn oxides rapidly oxidized volatile Se products, recycling these compounds back to soluble forms. Given their abundance in natural systems, biogenic Mn oxides likely play an important role mediating Se biogeochemistry. Elucidating this cryptic Se cycle is essential for understanding and predicting Se behavior in diverse environmental systems.

Mapping the drivers of uncertainty in atmospheric selenium deposition with global sensitivity analysis

Abstract. An estimated 0.5–1 billion people globally have inadequate intakes of selenium (Se), due to a lack of bioavailable Se in agricultural soils. Deposition from the atmosphere, especially through precipitation, is an important source of Se to soils. However, very little is known about the atmospheric cycling of Se. It has therefore been difficult to predict how far Se travels in the atmosphere and where it deposits. To answer these questions, we have built the first global atmospheric Se model by implementing Se chemistry in an aerosol–chemistry–climate model, SOCOL-AER (modeling tools for studies of SOlar Climate Ozone Links – aerosol). In the model, we include information from the literature about the emissions, speciation, and chemical transformation of atmospheric Se. Natural processes and anthropogenic activities emit volatile Se compounds, which oxidize quickly and partition to the particulate phase. Our model tracks the transport and deposition of Se in seven gas-phase species and 41 aerosol tracers. However, there are large uncertainties associated with many of the model's input parameters. In order to identify which model uncertainties are the most important for understanding the atmospheric Se cycle, we conducted a global sensitivity analysis with 34 input parameters related to Se chemistry, Se emissions, and the interaction of Se with aerosols. In the first bottom-up estimate of its kind, we have calculated a median global atmospheric lifetime of 4.4 d (days), ranging from 2.9 to 6.4 d (2nd–98th percentile range) given the uncertainties of the input parameters. The uncertainty in the Se lifetime is mainly driven by the uncertainty in the carbonyl selenide (OCSe) oxidation rate and the lack of tropospheric aerosol species other than sulfate aerosols in SOCOL-AER. In contrast to uncertainties in Se lifetime, the uncertainty in deposition flux maps are governed by Se emission factors, with all four Se sources (volcanic, marine biosphere, terrestrial biosphere, and anthropogenic emissions) contributing equally to the uncertainty in deposition over agricultural areas. We evaluated the simulated Se wet deposition fluxes from SOCOL-AER with a compiled database of rainwater Se measurements, since wet deposition contributes around 80 % of total Se deposition. Despite difficulties in comparing a global, coarse-resolution model with local measurements from a range of time periods, past Se wet deposition measurements are within the range of the model's 2nd–98th percentiles at 79 % of background sites. This agreement validates the application of the SOCOL-AER model to identifying regions which are at risk of low atmospheric Se inputs. In order to constrain the uncertainty in Se deposition fluxes over agricultural soils, we should prioritize field campaigns measuring Se emissions, rather than laboratory measurements of Se rate constants.

Geological evolution of the marine selenium cycle: Insights from the bulk shale δ82/76Se record and isotope mass balance modeling

Abstract Bulk δ82/76Se values of representative marine shales from the Paleoarchean to the present day vary between approximately −3 and + 3 ‰ with only local deviations beyond this range. This muted Se isotope variability in the shale record contrasts with the relatively large fractionations associated with abiotic and microbial Se oxyanion reduction seen in experimental studies. Long-term temporal trends in the bulk shale data do not directly correlate with changes in redox conditions of the global ocean, although a minor but significant shift towards more negative formation-averaged δ82/76Se values appears to track oxygenation of the deep ocean at the end of the Proterozoic. We hypothesize that extensive δ82/76Se variability in the shale data was suppressed due to the early emergence of biological assimilatory uptake and the resulting persistence of low seawater Se concentrations, coupled with small authigenic Se outputs throughout most of geological time. In the modern ocean, Se is an essential micronutrient with a relatively short residence time of about 11,500 yrs. The marine Se cycle is dominated by assimilation into biomass and subsequent recycling in the water column and surface sediments, i.e. processes that result in only minimal isotopic fractionation. We suggest that similar processes dominated back through the geological record to Archean times. Our model shows that paleoceanographic information could in principle be extracted from proxy data on the Se isotopic composition of seawater, once isotopic differences can be readily discerned between individual sedimentary Se pools.

Fate of Selenium in Soils at a Seleniferous Site Recorded by High Precision Se Isotope Measurements.

Selenium poisoning is a significant health problem in parts of Punjab, India, which is an area of intense agricultural productivity. To determine the complex soil dynamics that control distribution of Se in this area, we measured concentrations and δ(82/76)Se of bulk Se and individual Se pools in four soil profiles. This was compared against δ(82/76)Se of crops and groundwater used for irrigation. The isotopic composition of bulk Se and component Se pools reveal spatial heterogeneity. The bulk δ(82/76)Se show progressively lower values with increasing soil depth indicating the preferential migration of isotopically lighter Se downward through the soil profile. The δ(82/76)Se of water-soluble Se is isotopically heavier than δ(82/76)Se of adsorbed Se, suggesting Se isotope fractionation by reduction prior to scavenging by reactive minerals in the soil. The organically bound Se is isotopically lighter than water-soluble Se and correlates with the C/N ratio at different soil depths. Thus, Se immobilization by redox cycling controls the biogeochemical Se cycle in the soil. Se isotope ratios help to trace biochemical processes of Se in agricultural seleniferous soils and provide an important assessment for better soil management mitigating Se concentrations of ecotoxicological levels.

The evolution of the global selenium cycle: Secular trends in Se isotopes and abundances

The Earth’s surface has undergone major transitions in its redox state over the past three billion years, which have affected the mobility and distribution of many elements. Here we use Se isotopic and abundance measurements of marine and non-marine mudrocks to reconstruct the evolution of the biogeochemical Se cycle from ∼3.2Gyr onwards. The six stable isotopes of Se are predominantly fractionated during redox reactions under suboxic conditions, which makes Se a potentially valuable new tool for identifying intermediate stages from an anoxic to a fully oxygenated world. δ82/78Se shows small fractionations of mostly less than 2‰ throughout Earth’s history and all are mass-dependent within error. In the Archean, especially after 2.7Gyr, we find an isotopic enrichment in marine (+0.37±0.27‰) relative to non-marine samples (−0.28±0.67‰), paired with increasing Se abundances. Student t-tests show that these trends are statistically significant. Although we cannot completely rule out the possibility of volcanic Se addition, these trends may indicate the onset of oxidative weathering on land, followed by non-quantitative reduction of Se oxyanions during fluvial transport. The Paleoproterozoic Great Oxidation Event (GOE) is not reflected in the marine δ82/78Se record. However, we find a major inflection in the secular δ82/78Se trend during the Neoproterozoic, from a Precambrian mean of +0.42±0.45‰ to a Phanerozoic mean of −0.19±0.59‰. This drop probably reflects the oxygenation of the deep ocean at this time, stabilizing Se oxyanions throughout the water column. Since then, reduction of Se oxyanions has likely been restricted to anoxic basins and diagenetic environments in sediments. In light of recent Cr isotope data, it is likely that oxidative weathering before the Neoproterozoic produced Se oxyanions in the intermediate redox state SeIV, whereas the fully oxidized species SeVI became more abundant after the Neoproterozoic rise of atmospheric oxygen.

Mercury levels assessment in hair of riverside inhabitants of the Tapajós River, Pará State, Amazon, Brazil: Fish consumption as a possible route of exposure

The study present evaluated the levels of mercury (Hg) and methylmercury (MeHg) in hair samples of people from Barreiras community, riverside inhabitants of the Tapajós River (Pará, Brazil), an area impacted by clandestine gold mining, as well as we analyzed the levels of Hg and Se (selenium) in nine fish species (carnivores and non-carnivorous) from the Tapajós River, which stand out as the main species consumed by riverside inhabitants, to evaluate a relationship between frequency of fish consumption and Hg concentration, and also to evaluate possible mechanisms of fish protection (or non-protection) to Hg exposure by Se. Furthermore we analyze the water quality to evaluate the environmental trophic state, fact responsible by creating conditions that can potentiate the effects of toxic mercury. Concentrations of Hg and MeHg were analyzed in hair samples of 141 volunteers in different age band. Of those, 84.40% of samples present values above the threshold for biological tolerance, which is 6.00μgg−1 of total Hg in hair. Total Hg, in men there was a variation of 2.07–24.93μgg−1, while for women the variation was 4.84–27.02μgg−1. Consequently, the level of MeHg in men presented a variation of 1.49–19.57μgg−1, with an average of 11.68μgg−1, while with women the variation was from 3.73 to 22.35μgg−1, with an average of 10.38μgg−1. In fish species, Hg concentrations in carnivorous species had an average of 0.66μgg−1, higher than that permitted by current legislation, ranging from 0.30 to 0.98μgg−1, while the non-carnivorous species have values below the recommended by the legislation averaging 0.09μgg−1, ranging between 0.02 and 0.44μgg−1. For Se in fish, show that among carnivores, the contents of Se ranged between 0.18 and 0.54μgg−1 with a mean of 0.34μgg−1, while for non-carnivores these values were of the order of 0.16–0.56μgg−1, with an average of 0.32μgg−1. In surface water quality variables at the sampling points all showed values in accordance with the range established by current legislation. In this regard, the results provided by this study, while not conclusive, are strong indicators that despite not having been shown the relationship between the concentration of mercury in hair and feeding habits along the Tapajós River basin communities showed that a plausible correlation exists between levels of mercury and selenium in fish. This fact may serve as a subsidy to research human health, because in the Amazon, there is still a lot to examine with regards to the full understanding of the Se cycle.

Selenium redox cycling during weathering of Se-rich shales: A selenium isotope study

Selenium isotopes are becoming an important paleoenvironmental proxy. However, few studies have focused on the behavior of Se isotopes during oxidative weathering. In this paper, a comprehensive set of Se isotopic composition and concentration data were collected from the weathering profiles of Se-rich shales of the Permian Maokou Formation in Yutangba and Shadi, China to investigate Se isotopic fractionation and Se enrichment during weathering processes. The δ82/76Se in fresh shales (148±118mg/kg Se, 1SD, n=40) from Shadi and Yutangba drill cores varies from −1.69‰ to 1.74‰ with an average of 0.40±0.71‰ (1SD, n=40), consistent with the range in other Phanerozoic shales, suggesting that Se isotopes are not strongly fractionated during Se sequestration in the primary sedimentary environment. However, the strongly weathered Se-rich shales from Shadi and Yutangba profiles are isotopically lighter with average δ82/76Se values of −1.96±1.08‰ (1SD, n=5) and −1.08±1.83‰ (1SD, n=23), respectively. These data suggest that Se isotopes can be fractionated during oxidation and reduction processes associated with weathering, with heavier isotopes removed preferentially during oxidative weathering of shales. Such a shift, if found to be a global phenomenon, would have implications for models of the global Se cycle and interpretation of Se isotope data from past biogeochemical regimes.Locally altered shales exposed in a quarry at Yutangba are extremely enriched in Se with 1642±1505mg/kg (1SD, n=45), approximately 10 times greater than that in unaltered drill core samples. These rocks display very strong variation in δ82/76Se over short distances, with a single 60cm transect showing the most strongly negative and positive δ82/76Se values (−14.20‰ to +11.37‰) observed to date in natural samples. This suggests that Se has undergone multiple cycles of oxidation, mobilization, and re-reduction, resulting in a Se-rich redox front that has migrated downward through the organic-rich shales over time. δ82/76Se values vary sharply over distances as small as 10cm, indicating that Se redox conditions change strongly with position and are controlled by fractures and rock layering. Our data and a simple conceptual model suggest that zones of increased permeability that are accessed first by infiltrating waters are isotopically light, whereas less accessible zones are heavy. Repeated redox cycling accentuates this pattern. Furthermore, the average δ82/76Se in Se-rich shales at the Yutangba weathering system is 0.45±5.77‰ (1SD, n=39), identical with that (0.40±0.71‰) in fresh shales from same locality, implying that Se released by weathering accumulates in the redox front with little loss. The strong Se isotopic fractionation occurring in the redox front implies that Se isotopes can be extensively used in tracing geochemical processes of Se in groundwater system, especially related to fractures.

The origin and geochemical cycle of soil selenium in a Se-rich area of China

Mianyang City, located in the Fujiang River Basin, Sichuan Province, is a Se-rich area of China. The distribution of Selenium (Se) in the Mianyang area was studied based on assay data obtained from soil, irrigation water, fertilizer, and rice (grain and stem) samples. The ratio between natural and anthropogenic sources in the area was derived by analyzing the concentrations and spatial distributions of multiple elements (such as Se, cadmium, arsenic, and mercury) in the soil. The controlling factors affecting Se concentration in the soil were also investigated. We established a geochemical model of the Se cycle among the different media (i.e., the atmosphere, water, soils, and plants). We then calculated the annual Se flux caused by various inputs' (such as precipitation, fertilization, and irrigation) and outputs' (such as infiltration, crop harvest, removal of straws from cropland, and volatilization) pathways in the topsoil. We discuss the contribution of different pathways to the Se cycle and provide evidence for exploring Se-rich land in the study area.

Formation of Se (0) Nanoparticles by Duganella sp. and Agrobacterium sp. isolated from Se-laden soil of North-East Punjab, India

BackgroundSelenium (Se) is an essential trace element, but is toxic at high concentrations. Depending upon the geological background, the land use or on anthropogenic pollution, different amounts of Se may be present in soil. Its toxicity is related to the oxyanions selenate and selenite as they are water soluble and bioavailable. Microorganisms play an important role in Se transformations in soil and its cycling in the environment by transforming water-soluble oxyanions into water insoluble, non-toxic elemental Se (0). For this study, soil samples were collected from selenium-contaminated agricultural soils of Punjab/India to enrich and isolate microbes that interacted with the Se cycle.ResultsA mixed microbial culture enriched from the arable soil of Punjab could reduce 230 mg/l of water soluble selenite to spherical Se (0) nanoparticles during aerobic growth as confirmed by SEM-EDX. Four pure cultures (C 1, C 4, C 6, C 7) of Gram negative, oxidase and catalase positive, aerobic bacteria were isolated from this mixed microbial consortium and identified by 16 S rDNA gene sequence alignment as two strains of Duganella sp. (C 1, C 4) and two strains of Agrobacterium sp.(C 6, C 7). SEM/TEM-EDX analyses of the culture broth of the four strains revealed excretion of uniformly round sharply contoured Se (0) nanoparticles by all cultures. Their size ranged from 140–200 nm in cultures of strains C 1 and C 4, and from 185–190 nm in cultures of strains C 6 and C 7. Both Duganella sp. revealed better selenite reduction efficiencies than the two Agrobacterium sp.ConclusionsThis is the first study reporting the capability of newly isolated, aerobically growing Duganella sp. and Agrobacterium sp. from soils of Punjab/India to form spherical, regularly formed Se (0) nanoparticles from water soluble selenite. Among others, the four strains may significantly contribute to the biogeochemical cycling of Se in soil. Bioconversion of toxic selenite to non-toxic Se (0) nanoparticles under aerobic conditions in general may be useful for detoxification of agricultural soil, since elemental Se may not be taken up by the roots of plants and thus allow non-dangerous fodder and food production on Se-containing soil.

Selenium in volcanic environments: A review

Abstract Selenium is a chemical element with major environmental implications, due to the extremely narrow range between essential and toxic concentrations. Volcanoes emit significant amounts of Se, which has an enormous impact on the Se cycle and potentially human and animal health. This paper presents a broad overview of the current state of knowledge of major aspects of volcanic derived Se, focussing on the processes in soils and aquifers. Volcanic soils, formed when volcanic products weather rapidly, display peculiar characteristics. Selenium contents can be relatively high (1–2 orders of magnitude higher) compared to the worldwide average (0.4 mg/kg), but often with low mobility. The soils can be impacted by local deposition of volcanic emissions, which are enriched in Se due to volatilization in the magma chamber. It seems that the chemical fate of Se in volcanic soils is controlled by sorption processes on poorly crystalline phases, which presence depends on the parental materials and weathering. These sorption processes also determine leaching to groundwaters. Some volcanic aquifers have Se concentrations above the WHO guideline of 10 μg/L. This might also be related to geothermal activity. In spite of the well documented interest on Se during the last decades a significant number of uncertainties exist on the behavior of this fascinating element. A preliminary model of the Se cycle around volcanoes can be constructed, but the well-known analytical problems associated with Se determinations have produced a lack of reliable information on some processes involved in the chemical interaction between soils and water. This review, therefore, also aims to identify the processes where new efforts are needed to produce good quality data to be compared and integrated in global models.

Plant availability of soil selenate additions and selenium distribution within wheat and ryegrass

Selenate fertilization is an effective way to secure selenium (Se) nutrition in Se-poor areas but the cycling of the added selenate in the soil-plant system requires further clarification. We examined the Se uptake efficiency of wheat and ryegrass and Se distribution within these plants in two pot experiments. The behaviour of added selenate in a sand soil under wheat was monitored by sequential extractions during a ten-week growing period. In addition, the relationship between Se uptake of ryegrass and the salt extractable and ligand exchangeable Se in a sand and silty clay soil were studied. The added selenate remained mainly salt soluble in the soil throughout the monitoring. Se uptake by wheat comprised 12% of the soluble Se pool in soil and extended over the whole period of growth. In wheat, over 50% of Se accumulated in grains. The Se uptake of ryegrass comprised, on average, 40% of the soil salt soluble Se. In ryegrass, over 80% of the Se accumulated in roots. The distribution pattern of Se in plants can clearly have a major influence on both the Se cycle in soil and the nutritional efficiency of Se fertilization. The simple salt extraction showed fertilization-induced changes in the soluble soil Se pool, whereas the ligand exchangeable Se fraction reflected the difference in the nonlabile Se status between the two soils.

Transformations of volatile methylated selenium in soil

Microbial volatilization of selenium as dimethylselenide (DMSe) and dimethyldiselenide (DMDSe) from soil is an important part of the Se cycle in nature, but little is known about the stability and transformations of these gases during residence in the soil environment before dissipation to the atmosphere. Experiments monitored by gas chromatography and atomic absorption spectroscopy were made with various clay mineral standards, charcoal, commercial humic substances and soils to determine the sorption and transformations of DMSe and DMDSe injected into the headspace or passed through soil materials. Batch experiments conducted with 2–5 g materials placed into 40 mL Teflon centrifuge tubes equipped with Mininert ™ gas sampling valves showed that DMSe was slowly sorbed by soil materials and most of the DMSe deficit in the headspace was recovered as SeO = 3 and SeO = 4. In contrast, DMDSe was rapidly partitioned from the gas phase and resulted in an increased recovery of less soluble elemental and selenide-Se forms. These results were confirmed during flow-through soil column studies with both little DMSe sorption and sorption of the majority of DMDSe addition. Additions of selenomethionine (SeMet) to soil to produce DMSe and DMDSe in sealed flasks resulted in an increased partitioning of Se into inorganic Se when compared with a flow-through system designed to limit the contact of Se gases with soil. These results suggest that soil Se volatilization as DMSe and DMDSe results in Se loss to the atmosphere as DMSe with concomitant soil Se immobilization due to the instability of DMDSe.

Assessing Se cycling and toxicity in aquatic ecosystems

Toxic substances exert impacts on ecosystems at several levels: biogeochemical, toxicological, and populations/communities. Integrating exposure (biogeochemistry) and effects (toxicology) into an ecological context requires models as a necessary step to prediction and assessment of effects on populations and their interactions. To this end, research is being conducted to develop techniques for predicting the effects of Se on aquatic ecosystems. The objective is to develop mechanistic models to predict biogeochemical cycling, toxicological processes, and toxic effects on population and community dynamics. Earlier research demonstrated that different chemical forms of Se have different toxicological properties. Biogeochemical research culminated with a dynamic model of the Se cycle. In ongoing research, experiments are being conducted on microorganisms, phytoplankton, microzooplankton, zooplankton, benthic invertebrates, and fish to measure uptake, biotransformation, and depuration kinetics of different chemical forms of Se, transfer through the food web, and effects on growth, reproduction, community interactions, and survival. This information will provide the basis for the ecosystem effects model.