Se Species Research Articles

Selenomethionine supplementation and expression of selenosugars, selenocysteine, and other selenometabolites in rat liver.

Selenomethionine (SeMet) as a methionine analog can be incorporated into protein. In turkeys, we recently found that selenium (Se) as selenite is not metabolized to SeMet but rather to selenosugars (seleno-N-acetyl galactosamine) bound to protein as well as to selenocysteine (Sec) in selenoproteins. To characterize the metabolism of SeMet, we fed rats graded levels of SeMet from 0 to 5µg Se/g in a Se-deficient diet for 4 wk, and investigated the fate and accumulation of liver Se using high pressure liquid chromatography (HPLC) coupled with Se-specific inductively coupled plasma mass spectrometry (ICP-MS) and molecule specific (Orbitrap MS/MS) detection. Up to 0.24µg Se/g (Se requirement for maximal glutathione peroxidase activity), Sec accounted for ∼40% of total liver Se whereas SeMet only accounted for 3-11%. Analysis of water-soluble extracts found negligible low molecular weight (LMW) Se species in rats fed 0 and 0.08µg Se/g, including no SeMet. At 0.24µg Se/g and above, SeMet accounted for only 10% of LMW Se species, whereas methyl- and glutathionyl-selenosugars accounted for 70% of LMW Se species. Above the Se requirement, SeMet was ∼30% of the proteinaceous amino acids, whereas Sec levels fell to 5% in rats fed 5µg Se/g as SeMet. Last, considerably less inorganic Se was bound to liver protein with high SeMet as compared to selenite in a parallel study. SeMet is efficiently metabolized and mixes with the common Se metabolite pool, where Se is preferentially incorporated into Sec and Sec-selenoproteins until selenoproteins plateau; with high SeMet intake, Se is increasingly accumulated as LMW selenosugars and as selenosugar-decorated proteins.

Effect of graded levels of selenium supplementation as selenite on expression of selenosugars, selenocysteine, and other selenometabolites in rat liver.

Using high pressure liquid chromatography (HPLC) coupled with selenium-specific inductively coupled plasma mass spectrometry (ICP-MS) and molecule specific (Orbitrap MS/MS) detection, we previously found that far more selenium (Se) is present as selenosugar (seleno-N-acetyl galactosamine) in Se-adequate turkey liver than is present as selenocysteine (Sec) in true selenoproteins, and that selenosugars account for half of the Se in high-Se turkey liver. To expand these observations to mammals, we studied Se metabolism in rats fed graded levels of selenite from 0 to 5μg Se/g for 4 wk. In Se-adequate (0.24μg Se/g) rats, 43% of liver Se was present as Sec, 32% was present as selenosugars, and 22% as inorganic Se bound to protein. In liver of rats fed 5μg Se/g as selenite, the quantity of Sec remained at the Se-adequate plateau (11% of total Se), 22% was present as low molecular weight (LMW) selenosugars with substantial additional selenosugars linked to protein, but 64% was present as inorganic Se bound to protein. No selenomethionine was found at any level of selenite supplementation. Below the Se requirement, Se is preferentially incorporated into Sec-selenoproteins. Above the dietary Se requirement, selenosugars become by far the major LMW water soluble Se species in liver, and levels of selenosugar-decorated proteins are far higher than Sec-selenoproteins, making these selenosugar-decorated proteins the major Se-containing protein species in liver with high Se supplementation. This accumulation of selenosugars linked to cysteines on proteins or the build-up of inorganic Se bound to protein may underlie Se toxicity at the molecular level.

Biotransformation of se-methylselenocysteine into volatile selenocompounds by bacteria isolated from rat gut microflora

Selenium (Se) is an essential micronutrient that exists in various chemical forms in nature. Because of this property, animals must metabolize diverse Se species to utilize them as selenoproteins. Although gut microflora is suggested to play a role in Se metabolism in host animal, the biotransformation of Se by gut microflora in animal gut is not fully understood. In this study, we isolated Morganella morganii from rat feces under the condition that Se-methylseleno-L-cysteine (MeSeCys), one of the major Se sources in vegetables, was present in excess. Then, we examined the biotransformation of MeSeCys by M. morganii. Two volatile selenocompounds, dimethyldiselenide (DMDSe) and dimethylselenide (DMSe), were detected by GC–MS in the headspace of M. morganii culture. We speculate that M. morganii cleaved off the methylselenyl group from MeSeCys. Taken together, we conclude that gut microflora plays a role in the biotransformation of MeSeCys, and seems to support efficient metabolism in animals.

Mechanistic Insight into the Abiotic Interactions of Selenate and Selenite with Natural Organic Matter.

Natural organic matter (NOM) decreases the selenium (Se) mobility in soil and sediment. Biotic dissimilatory reduction of selenate and selenite and assimilation of the reduced Se species into biomolecules are thought to be primarily responsible for this decreased Se mobility. However, the possibility of Se immobilization due to the abiotic interaction of Se species with NOM is still poorly understood. Equilibrating selenate and selenite with a model NOM (Pahokee peat soil), followed by X-ray absorption spectroscopic analysis, this study shows that the NOM can abiotically reduce highly mobile selenate into relatively less mobile selenite. NOM can sorb Se species, especially selenite, considerably. Preloading of the NOM with Fe(III) increases the sorption of selenite and selenate by several orders of magnitude. Modeling of the Se and Fe K-edge EXAFS data revealed that Se species are sorbed to NOM due to indirect complexation with the organically complexed Fe(O,OH)6 octahedra through the corner- (2C) and edge-sharing (1E) and direct complexation with the oxygen-containing functional groups of the NOM. This study concludes that the abiotic reduction and complexation of the Se species with NOM can be the additional or alternative route of Se immobilization in the NOM-rich soil and sediment.

Simultaneous speciation analysis of Hg and Se in fish by high-performance liquid chromatography and inductively coupled plasma-mass spectrometry following microwave-assisted enzymatic hydrolysis.

This study reports the development and validation of a new analytical method for simultaneous speciation analysis of Se and Hg in fish muscle. For this purpose, four Se species (selenite/Se(IV), selenate/Se(VI), selenomethionine/SeMet, and selenocysteine/SeCys) and two Hg species (inorganic mercury/iHg and methylmercury/MeHg) were extracted simultaneously by microwave-assisted enzymatic hydrolysis and then separated by HPLC in less than 15min by using a column with both anion and cation exchange mechanisms and a mobile phase consisting of a mixture of methanol 5% (v/v), 45mM HNO3, 0.015% 2-mercaptoethanol, and 1.5mM sodium 3-mercapto-1-propanesulfonate. The separated species of Hg and Se were detected online by inductively coupled plasma-mass spectrometry (ICP-MS). The speciation analysis method was validated by means of the accuracy profile approach by carrying out three series of measurements in duplicate on three different days over a time-span of 3weeks. The limits of quantification (LOQ) are in the range of 0.010-0.013mg/kg wet weight (ww) for all selenium species, except for Se(IV) (0.15mg/kg ww), while the coefficient of variation in terms of intermediate reproducibility (CVR) was < 7%. The LOQ for MeHg was 0.006mg/kg ww, while the CVR was 3%. The method was successfully applied to the analysis of muscle samples from four different fish species: rainbow trout, tuna, swordfish, and dogfish.

Multifactorial interaction of selenium, iron, xylose, and glycine on cordycepin metabolism in Cordyceps militaris.

Cordycepin, a nucleoside analog, is the main antioxidative and antimicrobial substance in Cordyceps militaris. Toimprove the metabolism of cordycepin, carbon sources, nitrogen sources, trace elements, and precursors were studied by single factor, Plackett-Burman, and central composite designs in C. militaris mycelial fermentation. Under the regulation of the multifactorial interactions of selenite, ferrous chloride, xylose, and glycine, cordycepin production was increased by 5.2-fold compared with the control. The gene expression of hexokinase, ATP phosphoribosyltransferase, adenylosuccinate synthetase, and cns1-3 in the glycolysis, pentose phosphate, and adenosine synthesis pathways were increased by 3.2-7.5 times due to multifactorial interactions, while the gene expression of histidine biosynthesis trifunctional protein and histidinol-phosphate aminotransferase in histidine synthesis pathway were decreased by 23.4%-56.2%. Increasing with cordycepin production, glucose uptake was accelerated, mycelia growth was inhibited, and the cell wall was damaged. Selenomethionine (SeMet), selenocysteine (SeCys), and selenium nanoparticles (SeNPs) were the major Se species in C. militaris mycelia. This study provides a new insight for promoting cordycepin production by regulating glycolysis, pentose phosphate, and histidine metabolism. KEY POINTS: • Cordycepin production in the CCDmax group was 5.2-fold than that of the control. •Glucose uptake of the CCDmax group was accelerated and cell wall was damaged. •The metabolic flux was concentrated to the cordycepin synthesis pathway.

Effects of Sodium Selenite on the Rhizosphere Environment, Growth, and Physiological Traits of Oilseed Rape (Brassica napus L.)

Soil selenium (Se) speciation characteristics and their influence on the Se enrichment pattern and physiological characteristics of oilseed rape are poorly understood. We investigated dynamic changes in rhizosphere soil physicochemical properties, Se uptake and partitioning, biomass, and physiological indices in oilseed rape under five exogenous Se condition levels (0, 1.0, 2.5, 5.0, and 10.0 mg kg−1 Se in sodium selenite) using soil cultivation experiments. The rhizosphere pH and dissolved organic carbon in the soil solution were higher than those of the non-rhizosphere soil solution. The total Se, water-soluble Se, exchangeable Se, and organic Se contents in soils, as well as rapeseed root/leaf Se contents, significantly increased with increasing exogenous Se. Under 2.5 mg kg−1 Se, the biomass of rapeseed roots and leaves increased at the sixth week (82% and 58%) and eighth week (48% and 32%), respectively, reaching the highest level. Applications of 5.0 mg kg−1 Se at 6 and 8 weeks significantly increased the glutathione peroxidase activity (49%/82%), and decreased malondialdehyde content (23%/39%). Canonical correlation and ridge regression analyses showed that Se in the rapeseed roots/leaves significantly and positively correlated with water-soluble Se, exchangeable Se, and organic Se in rhizosphere soil. Overall, moderate-concentration Se soil application benefited oilseed rape growth (optimum = 2.5 mg kg−1 Se). Our findings reveal the response of oilseed rape to soil Se application based on plant growth and physiological traits, rhizospheric soil solution properties, and Se speciation transformation.

Selenium Health Benefit Values and Hg and Se speciation studies for elucidating the quality and safety of highly consumed fish species and fish-derived products

Nowadays, there has been an increase in the consumption of fish-derived products that constitute alternative ways of introducing fish into the diet, such as fish roe and products made from fish (crab sticks andsurimi-derived products). However, there is no data available considering selenium and mercury total contents along with speciation studies in these kinds of samples, which are mandatory for a proper safety and quality assessment. In this study,Selenium Health Benefit Values (HBVSe) in fish and fish-derived products were evaluated, resulting inpositivein all cases. Selenium speciation studies performed by HPLC-ICP-MS and confirmed by HPLC-ESI-MS/MS revealed that SeMet and SeMeSeCys are present in fish and fish-derived products. Finally, Hg speciation studiesshow that the percentage of Hg2+ increases in fishes lower in the food chain as well as in fish-derived products.

Sensitive analysis of selenium speciation in natural seawater by isotope-dilution and large volume injection using PTV-GC-ICP-MS

Although oceans play a key role in the global selenium (Se) cycle, there is currently very little quantitative information available on the distribution of Se concentrations and Se speciation in marine environments. In general, determining Se concentration and speciation in seawater is highly challenging due to very low Se levels ((sub)ng⋅L−1), whereas matrix elements interfering Se pre-concentration and detection are up to the g⋅L−1 levels. In this study, we established a sensitive method for the determination of the various Se chemical fractions present in natural seawater, i.e. selenite (SeIV), selenate (SeVI), organic Se-II + Se0 and total Se, using species-specific isotope dilution gas chromatography coupled to inductively coupled plasma mass spectrometry (ID-GC-ICP-MS). We compared different derivatization reagents and optimized specific pre-treatment protocols, including a microwave assisted oxidation protocol for the determination of total Se and organic Se-II + Se0 using H2O2. To increase sensitivity, we developed an online pre-concentration method based on large volume injection (LVI) using a programmed temperature vaporization (PTV) inlet. Eventually, the developed method achieved low absolute and methodological detection limits, i.e., respectively, 0.1–0.3 pg and 0.9–3.1 ng.L-1 for the different fractions. The accuracy of our method was of 2% for a certified reference material (CRM) diluted in artificial seawater while the precision was better than 4% for a freshwater CRM in artificial seawater matrix as well as two common seawater CRMs certified for trace elements excluding Se. As a proof-of-concept, we quantified the various Se fractions in a large number of natural water samples from the Baltic and North Seas, encompassing a wide range of salinity (7–35 psu), which shows that its detection limits are sufficient to determine total Se, SeIV, SeVI and organic Se-II + Se0 concentrations in brackish and marine systems.

A long-running in situ experiment in clay: 12 years of the Bitumen–Nitrate–Clay interaction experiment at Mont Terri rock laboratory

Abstract. In various countries such as Belgium and Germany, deep clay formations are investigated as potential host rock to dispose of radioactive waste. Intermediate-level long-lived bituminised waste, produced from spent fuel reprocessing, is currently foreseen to be disposed of in such a deep repository. This type of waste typically contains large amounts of salts embedded in an organic matrix, of which NaNO3 is the most prevalent. NaNO3, along with radionuclides immobilised in the bitumen matrix, will slowly dissolve and leach out into the surrounding host rock. The transport and reactivity of nitrate in a deep clay formation, in the presence and absence of electron donors coming from bituminised waste (i.e. acetate, H2), has been studied extensively inside anoxic and water-saturated chambers in the clay in the Bitumen–Nitrate–Clay interaction (BN) experiment. This in situ experiment in Opalinus clay is located in the Mont Terri rock laboratory (Switzerland). The effect of a nitrate plume on redox-sensitive radionuclides is also studied with stable selenium in selenate form as a proxy for 79Se, an important fission product for the long-term dose to humans. The BN experiment consists of a vertical borehole containing three packed-off intervals, in contact with the surrounding clay through cylindrical sintered stainless steel filter screens. The intervals are saturated with artificial Opalinus clay pore water at a pH between 7.5 and 8, containing all major ions at concentrations specific to the location of the BN experiment but without natural organic matter. Each interval is connected to a water circulation system with a gear pump, a flow meter and water sampling containers. This ensures a chemically well-mixed solution, constant water flow and easy sampling of the interval solutions under anoxic conditions. Water samples are regularly taken to assess the chemical composition and the microbial population in the intervals. An online UV spectrophotometer and pH and redox electrodes are installed in the water circuit of the intervals, to continuously monitor the nitrate and nitrite concentrations, pH and Eh. A given solution can be injected into the intervals to follow up redox reactions affecting nitrate and selenate in situ, in the presence or absence of additional electron donors. From 2011 to 2019, several injections with nitrate were performed in the intervals to investigate the biogeochemical reactivity of nitrate in the borehole and clay. These tests showed microbial reduction of nitrate, using electron donors from Opalinus clay (e.g. dissolved organic matter or pyrite). Nitrite and nitrogenous gases were formed. Pulses of electron donors (acetate or H2) boosted the microbial activity and nitrate reduction rate. From 2019 until now, injection tests with selenate, with and without nitrate, have been performed. These tests showed clearly that the presence of nitrate, a stronger oxidiser, inhibited the microbial reduction of selenate. In the absence of nitrate, the microbial population was able to reduce selenate to selenite and more reduced Se species. The results obtained in this in situ experiment will be summarised in this work, addressing questions concerning the effect of biogeochemical perturbations of the clay on the migration of redox-sensitive radionuclides.

Bifunctional tracer-mediated sandwich ELISA: A novel and promising approach for highly selective and ultrasensitive detection of selenium

Our current work involves developing a sandwich enzyme-linked immunosorbent assay (ELISA) that utilizes biotinylated long-chain o-phenylenediamine dihydrochloride (Bio-lc-OPD·2 HCl) as a bifunctional ligand for highly selective and ultra-sensitive quantitative analysis of selenium (Se) in food samples. The approach has successfully achieved a remarkable limit of detection (LOD) at the femtomolar level, while also exhibiting a substantial enhancement in sensitivity, up to 32.7-fold higher than that of the traditional indirect competitive ELISA (ic-ELISA). We demonstrated the reliability and accuracy of our approach by assessing overall recoveries, ranging from 75.4% to 104.1% across four different Se species. To validate our proposed method, we conducted the Se detection in Se-rich food samples. The results exhibited high consistency with atomic absorption spectrometry (AAS) analysis, reaffirming the robustness of our sandwich ELISA. This purposed detection strategy emerges as a compelling alternative, offering simplicity, accuracy, and high sensitivity for Se detection.

Selenium bioaccessibility in rice grains biofortified via soil or foliar application of inorganic Se

Selenium (Se) is a micronutrient for humans, and its deficiency is related to various diseases. Recent studies have proposed strategies to increase Se intake, especially using selenium biofortification in staple foods. However, few investigations shed light on the chemical species and the bioavailability of Se in cereal grains, including rice, one of the most important staple foods worldwide. This study aimed to determine the bioaccessible fractions of Se in rice grains biofortified with inorganic Se species using an in vitro sequential extraction method to simulate human digestion. Samples and extracts were submitted to microwave-assisted acid digestion, and total/bioaccessible Se levels were determined by DRC-ICP-MS. Accurate Se quantification was achieved using matrix-matching calibration. Rice biofortification via foliar application increased Se levels in the bioaccessible fraction more effectively than soil applications. Bioaccessible Se represented, on average, 61 ± 5 % of the total levels. Of the total Se content in rice, 44 ± 4 % was extracted in the gastric step, which is where most protein-bound bioaccessible selenium is degraded. Biofortification with inorganic forms of Se effectively increases the bioaccessible content of this element in food. Still, the amount to be applied must be corrected based on the bioaccessible fraction of the nutrient in rice grains.

The Ozonolysis of Methylated Selenide Compounds in the Atmosphere: Isotopes, Kinetics, Products, and Mechanisms.

Selenium (Se) is an essential micronutrient with an important atmospheric component in its biogeochemical cycle. In this cycle, phytoplankton form volatile organic Se species, such as dimethyl selenide (CH3SeCH3) and dimethyl diselenide (CH3SeSeCH3), which are emitted into the atmosphere. To predict the atmospheric fate of these methylated Se compounds, we investigated their ozonolysis reaction. We used proton-transfer-reaction time-of-flight mass spectrometry to quantify atmospheric Se and its isotopes, and used this method in kinetic and product studies. The ozonolysis of CH3SeCH3 proceeded with a rate constant of (7.4 ± 2.2) × 10-17 cm3 molec-1 s-1 at 26 ± 1 °C with an activation energy of 50 ± 14 kJ mol-1 forming dimethyl selenoxide (CH3Se(O)CH3). Comparatively, CH3SeSeCH3 reacted with O3 at (2.6 ± 0.9) × 10-17 cm3 molec-1 s-1 at 27 ± 1 °C with an activation energy of 56 ± 5 kJ mol-1 forming methylselinic acid (CH3Se(O)OH). At 20 ppbv of O3, the atmospheric lifetimes of CH3SeCH3 and CH3SeSeCH3 are 7.6 and 22 h, respectively. The Se oxidation products were confirmed by synthesis and can serve as new atmospheric tracers of methylated Se compounds. Overall, we measured Se isotopes in real time and determined the rate constants, activation energies, and oxidation products. These mechanisms can now be used to determine the quantitative atmospheric fate of Se toward O3, and thus its distribution within a changing climate.

Achieving long-cycling life rechargeable aluminum batteries with a Cu2Se cathode enabled by a carbon-functionalized separator

Transition metal selenides (TMSs) become one of the most promising cathode materials for rechargeable aluminum batteries (RABs) due to the advantages of high specific capacity, low cost, and simple preparation process. However, TMSs are soluble in the acidic chloroaluminate ionic liquid electrolyte during cycling, leading to undesirable electrochemical performance. Herein, rechargeable Al-Cu2Se batteries are fabricated with acetylene black modified separator (AB/GF/A) showing excellent electrochemical performance with capacity retention of 95 mAh g−1 after 5000 cycles at 0.5 A g−1 and 166.1 mAh g−1 at 1.0 A g−1. By combining electrochemical tests and ex situ spectroscopy and electronic microscope characterizations, it is revealed that the dissolved Cu and Se species adsorbed on the surface of AB/GF/A still remain electroactivity, which transforms the diffusion-controlled mechanism of Cu2Se to surface pseudocapacitance-controlled behavior, thus suppressing the shuttle effects and boosting the reaction kinetics. The in-depth understanding of the functionalized separator in energy storage mechanism of TMSs could provide reference for further progress of RABs in the future work.

Selenium contents, speciation and bioaccessibility of Se-enriched rice grains from Chinese markets

Diet intake accounts for >90% of selenium (Se) exposure in humans, with rice being the main source of Se intake for >60% of the Chinese population. In this study, 48 rice grain samples labeled Se-enriched were obtained from 22 major rice producing areas in China through online sources. Their total Se contents, Se speciation, and Se bioaccessibility were evaluated to provide a holistic view of Se-enriched rice in the market. The total Se contents were 0.006–0.951 ​μg ​g−1 (average 0.249 ​μg ​g−1), which showed great regional variations, with 73% of the samples satisfying the Se-enriched standard based on GB/T22499-2008 (0.04–0.30 ​mg ​kg−1). Over 80% of Se in the rice samples was organic Se species including selenomethionine, selenocysteine and methylselenocysteine, with selenomethionine being the main Se species, accounting for 61–98%. Based on a modified physiologically-based extraction test (MPBET), the Se bioaccessibility in 33 selected samples was 8.05–49.6% (28.6%) in the gastric phase and 18.1–117% (82.5%) in the intestinal phase. Further, Se bioaccessibility was positively correlated with organic Se (r ​= ​0.89–0.93), but not with inorganic Se (selenite and selenate), suggesting that Se bioaccessibility depended on organic Se in these rice grains. The data call for re-evaluation of Se-enriched rice in the market. Further, the potential risk of long-term consumption of Se-enriched rice in the market towards human health should be studied.

Transfer of Se from sediments to the western mosquitofish Gambusia affinis: Tissue distribution, accumulation, and effects on the antioxidant physiology

Selenium (Se) has been shown to cause various toxicities in predatory species (i.e., fish and birds) in Se-contaminated aquatic environments. However, trophic transfer of Se from abiotic environments to freshwater fish has been relatively less addressed. In this study, 2-month-old mosquitofish (Gambusia affinis) were fed Se-enriched oligochaete (Lumbriculus variegatus, exposed to different concentrations of Se(IV) at 0.0, 3.0, 10.0, and 30.0 µg/g dry weight for 7 days) for 45 days. Tissue distribution, Se speciation, and effects on the antioxidant physiology in G. affinis were assessed. The results showed Se was rapidly accumulated in the oligochaete, with 6.30 ± 1.20, 16.20 ± 2.10, and 34.50 ± 2.40 µg/g dw of total Se levels in the worms exposed to 3.0, 10.0, and 30.0 µg/g of Se(IV), respectively. Total Se levels were increased in a dose-dependent manner in fish tissues and Se(IV) from sediments was maternally transferred to the fish embryos. Se-Met-and Se-Cys-were the predominant Se species in the worm and fish tissues, accounting for a minimum of 91.01% of the total Se. Furthermore, increased lipid peroxidation and altered the activities of antioxidant enzymes and levels of GSH were noticed in G. affinis fed the Se-enriched L. variegatus. This study has demonstrated that Se(IV) is transferred from an abiotic vector to freshwater organisms, disturbing the antioxidant physiology in G. affinis and potentially their offspring. This study highlights the importance of dietary exposure on the accumulation and toxicity of Se in aquatic organisms.

Assessment of Membrane and Electrochemical Technologies for the Treatment of a Selenium-Bearing Mine water: Technology Performance and Effect on Toxicity and Bioaccumulation

Nanofiltration (NF), reverse osmosis (RO), electrodialysis (ED), and electrocoagulation (EC), were all tested at the bench scale for removing selenium (Se) from mine water. All of these technologies reduced the concentration of total Se from 216 µg/L (i.e. 120.1 µg/L of selenate; 59.1 µg/L of selenite, and 0.6 µg/L methyl-selenic acid) in the raw mine water to about 2 µg/L or less in the treated water, equivalent to more than 99% removal. Electrodialysis was found to be the most effective, removing more than 99.5% of the Se. The untreated mine water was toxic to algae. In contrast, RO and NF reduced the toxicity of the mine water, allowing algae to grow between 15,000 to 25,000 cells/mL, while ED and EC did not allow algal growth, likely due to complete removal of essential minerals (ED) or the presence of other contaminants (EC), such as copper. The Se speciation did not change as a result of membrane filtration; however, selenite in the effluent was almost fully transformed to selenate in the brines from the ED and EC treatment processes. The effluent treated by NF and EC generated seleno-cyanate at 0.37 and 1.01 µg/L, respectively. Further testing is recommended at the pilot-scale with the same mine water as well as different mine water.

Se-doped Nb2O5–Al2O3 composite-ceramic nanoarrays via the anodizing of Al/Nb bilayer in selenic acid

Novel arrays of Nb2O5-based ceramic nanostructures of various sizes (9–210 nm) and morphologies (dots, goblets, rods) aligned on substrates are fabricated via the anodizing of a thin Nb film through the initially formed porous anodic alumina (PAA) film in 1.5 M selenic acid (H2SeO4) – a new aqueous electrolyte generating extraordinarily thinner PAA pores than any other solutions. Accordingly, the nanostructures formed in the selenic acid are 1.3-fold thinner and better self-ordered than their counterparts formed from the same Al/Nb precursor bilayer in a reference oxalic-acid electrolyte. The nanostructures have a dual (core/shell) composition: the inner material (the core) is stoichiometric Nb2O5, whereas the outer layer (the shell) is a few nm-thick substoichiometric NbOx mixed with Al2O3. The composite-ceramic nanoarrays grow doped with selenium species such as selenate (SeO42−) and selenide (Se2−) anions originating from the electrolyte and migrating inward under the high electric field. The incorporated Se species do not contribute to photoluminescence emission nor hinder the Raman signal from the nanoarrays, which makes them highly promising as Nb2O5-based SERS biosensing substrates. The planar PAA-inbuilt Se-doped Nb2O5–Al2O3 nanostructured ceramic film performs like a high-k low-loss low-leakage-current dielectric promising for on-chip integration. More potential applications of the Se-doped ceramic nanoarrays developed here include biomedical antibacterial coatings, advanced superhydrophobic surfaces, gas-sensing, and catalytic layers.

Effect of inorganic arsenic in paddy soil on the migration and transformation of selenium species in rice plants

Selenium (Se) in paddy rice is one of the significant sources of human Se nutrition. However, the effect of arsenic (As) pollution in soil on the translocation of Se species in rice plants is unclear. In this research, a pot experiment was designed to examine the effect of the addition of 50 mg As/kg soil as arsenite or arsenate on the migration of Se species from soil to indica Minghui 63 and Luyoumingzhan. The results showed that the antagonism between inorganic As and Se was closely related to the rice cultivar and Se oxidation state in soil. Relative to the standalone selenate treatment, arsenite significantly (p < 0.05) decreased the accumulation of selenocystine, selenomethionine and selenate in the roots, stems, sheaths, leaves, brans and kernels of both cultivars by 21.4%-100.0%, 40.0%-100.0%, 41.0%-100%, 5.4%-96.3%, 11.3%-100.0% and 26.2%-39.7% respectively, except for selenocystine in the kernels of indica Minghui 63 and selenomethionine in the leaves of indica Minghui 63 and the stems of indica Luyoumingzhan. Arsenate also decreased (p < 0.05) the accumulation of selenocystine, selenomethionine and selenate in the roots, stems, brans and kernels of both cultivars by 34.9%-100.0%, 30.2%-100.0%, 11.3%-100.0% and 5.6%-39.6% respectively, except for selenate in the stems of indica Minghui 63. However, relative to the standalone selenite treatment, arsenite and arsenate decreased (p < 0.05) the accumulation of selenocystine, selenomethionine and selenite only in the roots of indica Minghui 63 by 45.5%-100.0%. Our results suggested that arsenite and arsenate had better antagonism toward Se species in selenate-added soil than that in selenite-added soil; moreover, arsenite had a higher inhibiting effect on the accumulation of Se species than arsenate.

Sulfur levels regulate the absorption and utilization of selenite in rapeseed (Brassica napus)

Selenium (Se) is a necessary trace element that contributes to the health of humans and animals alike. Humans rely on the consumption of Se-rich plants to achieve adequate levels of the nutrient, but many crop-growing regions are unable to keep up with demand through conventional agriculture alone. Hydroponic cultivation with inorganic Se sources such as selenate or selenite represents a valid opportunity for biofortification in plants. This method is largely free from dependence on local Se resources, and the appropriate optimizations of hydroponic ingredients have previously demonstrated improved plant Se. However, effective strategies to improve the absorption and utilization efficiency of selenite at physiological levels remain scarce. In this study, we manipulated sulfate levels in a selenite-containing hydroponic solution and found that a decreased supply was able to elevate Se contents more than 6-fold in the shoots of rapeseed seedlings, but only had a slight effect in the roots. Additionally, this low sulfur environment increased the root-to-shoot Se translocation efficiency by more than 6 times. Our Se speciation analysis showed that a large proportion of the root-absorbed selenite was transformed into organic forms under a normal sulfate supply, and that selenate and SeMeCys represent the main Se species involved in root-to-shoot translocation. A reduction in sulfate supply was also found to induce the upregulation of genes related to selenate distribution and a key rate-limiting step for organic Se biosynthesis. These findings are consistent with the dramatically enhanced accumulation of SeMet and selenate in both roots and shoots. Taken together, our results demonstrate that the regulation of sulfur levels has a great potential for the improvement of the Se enrichment efficiency in economically valuable aboveground organs of selenite-treated plants.