Selenium Biofortification: Roles, Mechanisms, Responses and Prospects.

The trace element selenium (Se) is a crucial element for many living organisms, including soil microorganisms, plants and animals, including humans. Generally, in Nature Se is taken up in the living cells of microorganisms, plants, animals and humans in several inorganic forms such as selenate, selenite, elemental Se and selenide. These forms are converted to organic forms by biological process, mostly as the two selenoamino acids selenocysteine (SeCys) and selenomethionine (SeMet). The biological systems of plants, animals and humans can fix these amino acids into Se-containing proteins by a modest replacement of methionine with SeMet. While the form SeCys is usually present in the active site of enzymes, which is essential for catalytic activity. Within human cells, organic forms of Se are significant for the accurate functioning of the immune and reproductive systems, the thyroid and the brain, and to enzyme activity within cells. Humans ingest Se through plant and animal foods rich in the element. The concentration of Se in foodstuffs depends on the presence of available forms of Se in soils and its uptake and accumulation by plants and herbivorous animals. Therefore, improving the availability of Se to plants is, therefore, a potential pathway to overcoming human Se deficiencies. Among these prospective pathways, the Se-biofortification of plants has already been established as a pioneering approach for producing Se-enriched agricultural products. To achieve this desirable aim of Se-biofortification, molecular breeding and genetic engineering in combination with novel agronomic and edaphic management approaches should be combined. This current review summarizes the roles, responses, prospects and mechanisms of Se in human nutrition. It also elaborates how biofortification is a plausible approach to resolving Se-deficiency in humans and other animals.

Comparative efficacy of selenate and selenium nanoparticles for improving growth, productivity, fruit quality, and postharvest longevity through modifying nutrition, metabolism, and gene expression in tomato; potential benefits and risk assessment.

This study attempted to address molecular, developmental, and physiological responses of tomato plants to foliar applications of selenium nanoparticles (nSe) at 0, 3, and 10 mgl-1 or corresponding doses of sodium selenate (BSe). The BSe/nSe treatment at 3 mgl-1 increased shoot and root biomass, while at 10 mgl-1 moderately reduced biomass accumulation. Foliar application of BSe/nSe, especially the latter, at the lower dose enhanced fruit production, and postharvest longevity, while at the higher dose induced moderate toxicity and restricted fruit production. In leaves, the BSe/nSe treatments transcriptionally upregulated miR172 (mean = 3.5-folds). The Se treatments stimulated the expression of the bZIP transcription factor (mean = 9.7-folds). Carotene isomerase (CRTISO) gene was transcriptionally induced in both leaves and fruits of the nSe-treated seedlings by an average of 5.5 folds. Both BSe or nSe at the higher concentration increased proline concentrations, H2O2 accumulation, and lipid peroxidation levels, suggesting oxidative stress and impaired membrane integrity. Both BSe or nSe treatments also led to the induction of enzymatic antioxidants (catalase and peroxidase), an increase in concentrations of ascorbate, non-protein thiols, and soluble phenols, as well as a rise in the activity of phenylalanine ammonia-lyase enzyme. Supplementation at 3 mgl-1 improved the concentration of mineral nutrients (Mg, Fe, and Zn) in fruits. The bioaccumulated Se contents in the nSe-treated plants were much higher than the corresponding concentration of selenate, implying a higher efficacy of the nanoform towards biofortification programs. Se at 10 mgl-1, especially in selenate form, reduced both size and density of pollen grains, indicating its potential toxicity at the higher doses. This study provides novel molecular and physiological insights into the nSe efficacy for improving plant productivity, fruit quality, and fruit post-harvest longevity.

Systematic study on the reduction efficiency of ascorbic acid and thiourea on selenate and selenite at high and trace concentrations.

Selenate (Se(VI)) and selenite (Se(IV)) are common soluble wastewater pollutants in natural and anthropogenic systems. We evaluated the reduction efficiency and removal of low (0.02 and 2 mg/L) and high (20 and 200 mg/L) Se(IV)(aq) and Se(VI)(aq) concentrations to elemental (Se0) via the use of ascorbic acid (AA), thiourea (TH), and a 50-50% mixture. The reduction efficiency of AA with Se(IV)(aq) to nano- and micro-crystalline Se0 was ≥ 95%, but ≤ 5% of Se(VI)(aq) was reduced to Se(IV)(aq) with no Se0. Thiourea was able to reduce ≤ 75% of Se(IV)(aq) to bulk Se0 at lower concentrations but was more effective (≥ 90%) at higher concentrations. Reduction of Se(VI)(aq)→Se (IV)(aq) with TH was ≤ 75% at trace concentrations which steadily declined as the concentrations increased, and the products formed were elemental sulfur (S0) and SnSe8-n phases. The reduction efficiency of Se(IV)(aq) to bulk Se0 upon the addition of AA+TH was ≤ 81% at low concentrations and ≥ 90% at higher concentrations. An inverse relation to what was observed with Se(IV)(aq) was found upon the addition of AA+TH with Se(VI)(aq). At low Se(VI)(aq) concentrations, AA+TH was able to reduce more effectively (≤ 61%) Se(VI)(aq)→Se(IV)(aq)→Se0, while at higher concentrations, it was ineffective (≤ 11%) and Se0, S0, and SnSe8-n formed. This work helps to guide the removal, reduction effectiveness, and products formed from AA, TH, and a 50-50% mixture on Se(IV)(aq) and Se(VI)(aq) to Se0 under acidic conditions and environmentally relevant concentrations possibly found in acidic natural waters, hydrometallurgical chloride processing operations, and acid mine drainage/acid rock drainage tailings. Graphical Abstract ᅟ.

Effects of straw amendment on selenium aging in soils: Mechanism and influential factors.

Soil dissolved organic matter (DOM) alters heavy metal availability, but whether straw amendment can manipulate soil selenium (Se) speciation and availability through DOM mineralization remains unclear. In this study, allochthonous maize straw and selenate were incubated together in four different soils for 1 y. The transformation and availability of DOM associated Se (DOM-Se) was investigated during aging. Results indicated that soil solution and soil particle surfaces were dominated by hexavalent hydrophilic acid-bound Se (Hy-Se). The amount of fulvic acid bound Se in soil solution (SOL-FA-Se) was higher than humic acid bound Se in soil solution (SOL-HA-Se), except in krasnozems, and mainly existed as hexavalent Se (Se(VI)). Tetravalent Se (Se(IV)) was the main valence state of FA-Se adsorbed on soil particle surfaces (EX-FA-Se) after 5 w of aging. The proportion of soil-available Se (SOL + EX-Se) decreased with increasing straw rate. However, under an application rate of 7500 kg·hm-2, soluble Se fraction (SOL-Se) reduction was minimal in acidic soils (18.7%-34.7%), and the organic bound Se fraction (OM-Se) was maximally promoted in alkaline soils (18.2%-39.1%). FA and HON could enhance the availability of Se in the soil solution and on particle surfaces of acidic soil with high organic matter content. While Se incorporation with HA could accelerate the fixation of Se into the solid phase of soil. Three mechanisms were involved in DOM-Se aging: (1) Reduction, ligand adsorption, and inner/outer-sphere complexation associated with the functional groups of straw-derived DOM, including hydroxyls, carboxyl, methyl, and aromatic phenolic compounds; (2) interconnection of EX-FA-Se between non-residual and residual Se pools; and (3) promotion by soil electrical conductivity (EC), clay, OM, and straw application. The dual effect of DOM on Se aging was highly reliant on the characteristics of the materials and soil properties. In conclusion, straw amendment could return selenium in soil and reduce soluble Se loss.

Generating cellulose-agar composite hydrogels for uptake-release kinetic studies of selenate and selenomethionine.

Cellulose-agar (CAB) composite hydrogel beads were generated for the uptake-release kinetics studies of Se(VI) and selenomethionine (SeMt) from water medium. The objective of this work is to analyze the surface structure, gel properties, thermal stability and chemical functionalities responsible for the adsorption of Se(VI) and SeMt. We propose here a possible mechanism for the adsorptions. Adsorption isotherms are in good agreement with the Freundlich model, yielding a high adsorption capacity for the CAB composite. Maximum adsorption capacity of Se(VI) and SeMt were found to be 7.083 mg g-1 and 34.639 mg g-1 respectively. The mean free energy of adsorption (E*) value was found to be 0.0423 kJ mol-1 and 0.329 kJ mol-1 of Se(VI) and SeMt respectively. 1 M HCl and 0.1 M HCl were able to desorb Se(VI) and SeMt respectively from CAB. The adsorption of Se(VI) was significantly reduced if As(III), Cr(III) and Hg(II) were present as complementary ions in the medium. Similar studies with pristine cellulose beads (CB) yielded insignificant uptake properties.

Nutritional quality and organic matter degradability of Brachiaria spp. agronomically biofortified with selenium.

Selenium (Se) fertilisation in grazing systems can improve the quality of animal forage, but there are few studies addressing the influence of Se fertilisation on the chemical composition and ruminal degradability of forage fertilised with Se. The aim of this study was to evaluate the chemical composition and in vitro assays of truly degraded organic matter (TDOM), short-chain fatty acids (SCFA) total gas (GP) and methane (CH4 ) production of two harvests of Brachiaria brizantha cv. Marandu fertilised with urea coated with B, Cu and sodium selenate for 0, 10, 20, 40, 80 and 160 g/ha of Se. Selenium content in forage increased linearly with the different doses at 30 and 60 days after fertilisation. However, doses of 20 and 80 g/ha Se fertilisation yielded positive effects increasing Se content and truly degraded organic matter in vitro of Brachiaria brizantha cv. Marandu.

Effects of a foliar spray of selenite or selenate at different growth stages on selenium distribution and quality of blueberries.

BACKGROUND: Foliar spraying of selenium (Se) has increasingly been applied to improve Se concentrations in grain crops, although little information is available about the properties of Se-enriched fruits. In the present study, selenium distribution in blueberry and Se effect on blueberry quality were investigated by foliar spraying selenite or selenate (200 g ha-1 ) on two blueberry cultivars (Bluecrop and Northland) during the young fruit or coloring stage. RESULTS: Selenium concentration in blueberry was mainly affected by cultivar and spray stage relative to the Se source. Northland was 1.3- to 1.5-fold higher than Bluecrop with respect to Se enrichment. Se treatment at the young fruit stage induced a 1.5- to 2.3-fold increase compared to that at the coloring stage with respect to the Se concentration of blueberry. Additionally, selenium was mainly stored in pomace, with an accumulative distribution ratio of 89.3-94.9%. The proportion of organic Se reached up to 77.0% in blueberry. Furthermore, the foliar application of Se significantly increased the anthocyanin concentration and the intact fruit rate of blueberry. CONCLUSION: Se-enriched blueberry can be used as a 'functional food'. Because Se was mainly accumulated in the pomace, the consumption of blueberries as fresh fruit, dried fruit and jam can improve the efficiency of Se supplement. © 2018 Society of Chemical Industry.

Selenate redistribution during aging in different Chinese soils and the dominant influential factors.

To date, few works have attempted to determine the effect of soil types on Selenium aging process and the possible influential factors. In this study, the differences in Se speciation distribution and availability in 15 Chinese typical agricultural soils were investigated using spiked selenate for the entire year. Results evidenced that after one year of incubation, Se transformed from soluble fraction to Fe/Mn oxides and organic matter bound fractions in neutral or alkaline soils (pH 7.09-8.51) and from exchangeable fraction to residual fraction in acidic soils (pH 4.89-6.82). The available Se content in all soils declined rapidly at the initial stage of aging, with most of the neutral or alkaline soils reaching equilibrium after 109 d, whereas the acidic soils reached equilibrium after only 33-56 d. The available Se content in soil decreased constantly during the entire aging process in S4 (Xinjiang Gray desert soil), S12 (Anhui Yellow brown earths), and S15 (Hunan Krasnozems). Elovich model was the best model (R2 > 0.80) in describing the Se aging process. Estimated time for exogenous Se reaching the distribution of available Se in corresponding native soils extended from 9.7 y to 50.2 y, indicating a much longer time was required for spiked soil to reach equilibrium. Soil pH was the most significant factor directly and negatively influencing the aging process (p < 0.05), while organic matter played a dual role on Se speciation. Results could provide reference for the selection of unified equilibrium time on Se-spiked experiment.

Effect of temperature on selenium removal from wastewater by UASB reactors.

The effect of temperature on selenium (Se) removal by upflow anaerobic sludge blanket (UASB) reactors treating selenate and nitrate containing wastewater was investigated by comparing the performance of a thermophilic (55 °C) versus a mesophilic (30 °C) UASB reactor. When only selenate (50 µM) was fed to the UASB reactors (pH 7.3; hydraulic retention time 8 h) with excess electron donor (lactate at 1.38 mM corresponding to an organic loading rate of 0.5 g COD L(-1) d(-1)), the thermophilic UASB reactor achieved a higher total Se removal efficiency (94.4 ± 2.4%) than the mesophilic UASB reactor (82.0 ± 3.8%). When 5000 µM nitrate was further added to the influent, total Se removal was again better under thermophilic (70.1 ± 6.6%) when compared to mesophilic (43.6 ± 8.8%) conditions. The higher total effluent Se concentration in the mesophilic UASB reactor was due to the higher concentrations of biogenic elemental Se nanoparticles (BioSeNPs). The shape of the BioSeNPs observed in both UASB reactors was different: nanospheres and nanorods, respectively, in the mesophilic and thermophilic UASB reactors. Microbial community analysis showed the presence of selenate respirers as well as denitrifying microorganisms.

Hydrogen-fed biofilm reactors reducing selenate and sulfate: Community structure and capture of elemental selenium within the biofilm.

Remediation of selenate (SeO4 (2-) ) contamination through microbial reduction is often challenging due to the presence of sulfate (SO4 (2-) ), which can lead to competition for the electron donor and the co-production of toxic H2 S. Microbial reduction of SeO4 (2-) in the presence of SO4 (2-) was studied in two hydrogen-based membrane biofilm reactors (MBfRs). One MBfR was initiated with SO4 (2-) -reducing conditions and gradually shifted to SeO4 (2-) reduction. The second MBfR was developed with a SeO4 (2-) -reducing biofilm, followed by SO4 (2-) introduction. Biofilms within both MBfRs achieved greater than 90% SeO4 (2-) reduction, even though the SeO4 (2-) concentration ranged from 1,000-11,000 µg/L, more than 20-200 times the maximum contaminant level for drinking water (50 µg/L). Biofilm microbial community composition, assessed by 16S rRNA gene-based amplicon pyrosequencing, was distinct between the two MBfRs and was framed by alterations in SeO4 (2-) loading. Specifically, high SeO4 (2-) loading resulted in communities mainly composed of denitrifying bacteria (e.g., Denitratisoma and Dechloromonas). In contrast, low loading led to mostly sulfate-reducing bacteria (i.e., Desulfovibrio) and sulfur-oxidizing bacteria (i.e., Sulfuricurvum and Sulfurovum). SeO4 (2-) was reduced to elemental selenium (Se°), which was visualized within the biofilm as crystalloid aggregates, with its fate corresponding to that of biofilm solids. In conclusion, microbial biofilm communities initiated under either SeO4 (2-) or SO4 (2-) -reducing conditions attained high SeO4 (2-) removal rates even though their microbial community composition was quite distinct. Biotechnol. Bioeng. 2016;113: 1736-1744. © 2016 Wiley Periodicals, Inc.

Fractionation of Selenium during Selenate Reduction by Granular Zerovalent Iron.

Batch experiments were conducted using granular zerovalent iron (G-ZVI) with either ultrapure water or CaCO3 saturated simulated groundwater to assess the extent of Se isotope fractionation in solution under the anaerobic conditions characteristic of many aquifers. G-ZVI is a common remediation material in permeable reactive barriers (PRB) to treat Se-contaminated groundwater, and stable isotopes are a potential tool for assessing removal mechanisms. The solution composition, speciation of Se, and Se isotope ratios were determined during both sets of experiments. Dissolved Se concentrations decreased from 10 to <2 mg L(-1) after 3 d in the CaCO3 system and below 0.4 mg L(-1) after 2 d in the ultrapure water system. XANES analysis of the solid phase showed spectra consistent with the formation of Se(IV), Fe2(SeO3)3, FeSe, FeSe2, and Se(0) on the G-ZVI. Selenium isotope ratio measurements in solution in the CaCO3 and ultrapure water experiments showed enrichment of δ(82/76)Se values from -0.94 ± 0.07‰ and -1.93 ± 0.20‰ to maximum values of 6.85 ± 0.52‰ and 5.68 ± 0.20‰ over 72 and 36 h, respectively. The effective fractionations associated with the reduction of Se(VI) were 4.3‰ within the CaCO3 saturated water and 3.0‰ in ultrapure water.

Variations in the accumulation, localization and rate of metabolization of selenium in mature Zea mays plants supplied with selenite or selenate.

Quantification of selenium bioavailability from foods is a key challenge following the discovery of the antioxidant role of this micronutrient in human health. This study presents the uptake, accumulation and rate of metabolization in mature Zea mays plants grown in hydroponic solution supplemented with selenate or selenite. Selenium content was lower in plants supplemented with selenate and accumulated mainly in the leaves compared with selenite-treated plants where the selenium was retained in the roots. Selenite-treated grains accumulated more selenium. Selenate was metabolized less than selenite in whole plants, but in grains selenium was present exclusively as organic selenium compounds. For humans, the bioavailability of organic selenium was evaluated at 90% compared with only 50% for inorganic forms. Our results show that the potential for selenium bioavailability is increased with selenite treatment.

Selenate-enriched urea granules are a highly effective fertilizer for selenium biofortification of paddy rice grain.

This study examined the effects of applied selenium (Se) species, time of application, method of application, and soil water management regimen on the accumulation of Se in rice plants. Plants were grown to maturity in a temperature- and humidity-controlled growth chamber using three water management methods: field capacity (FC), submerged until harvest, and submerged and drained 2 weeks before harvest. Two Se species, selenate (SeO4(2-)) and selenite (SeO3(2-)), were applied at a rate equivalent to 30 g ha(-1). Four application methods were employed as follows: (i) Se applied at soil preparation, (ii) Se-enriched urea granules applied to floodwater at heading; (iii) foliar Se applied at heading; and (iv) fluid fertilizer Se applied to soil or floodwater at heading. Total Se concentrations in rice grains, husks, leaves, culms, and roots were measured, as well as Se speciation in grains from the Se-enriched urea granule treatment. Highest Se concentrations in the grain occurred with SeO4(2-) and with fertilizer applied at heading stage; SeO4(2-)-enriched urea granules applied at heading increased grain Se concentrations 5-6-fold (by 450-600 µg kg(-1)) compared to the control (no fertilizer Se applied) in all water treatments. Under paddy conditions other Se fertilization strategies were much less effective. Drainage before harvesting caused Se to accumulate in/on rice roots, possibly through adsorption onto iron plaque on roots. Rice grains contained Se mainly in the organic form as selenomethionine (SeM), which comprised >90% of the total grain Se in treatments fertilized with SeO4(2-)-enriched urea granules. The results of this study clearly show that of the fertilizer strategies tested biofortification of Se in rice grains can best be achieved in lowland rice by broadcast application of SeO4(2-)-enriched urea granules to floodwater at heading stage.