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.

Kinetics and equilibrium adsorption study of selenium oxyanions onto Al/Si and Fe/Si coprecipitates.

Inappropriate treatments for the effluents from semiconductor plants might cause the releases and wide distributions of selenium (Se) into the ecosystems. In this study, Al/Si and Fe/Si coprecipitates were selected as model adsorbents as they often formed during the wastewater coagulation process, and the removal efficiency of selenite (SeO3) and selenate (SeO4) onto the coprecipitates were systematically examined. The removal efficiency of SeO3 and SeO4 was highly related to surface properties of Al/Si and Fe/Si coprecipitates. The surface-attached Al shell of Al/Si coprecipitates shielded a portion of negative charges from the core SiO2, resulting in a higher point of zero charge than that of Fe/Si coprecipitates. Thus, adsorption of SeO3/SeO4 was favorable on the Al/Si coprecipitates. Adsorptions of both SeO3 and SeO4 on Al/Si coprecipitates were exothermic reactions. On Fe/Si coprecipitates, while SeO3 adsorption also showed the exothermic behavior, SeO4 adsorption occurred as an endothermic reaction. The kinetic adsorption data of SeO3/SeO4 on Al/Si and Fe/Si coprecipitates were described well by the pseudo-second-order kinetic model. SeO4 and SeO3 adsorption on Fe/Si or Al/Si were greatly inhibited by the strong PO4 ligand, whereas the weak ligand such as SO4 only significantly affected SeO4 adsorption. The weakest complex between SeO4 and Al was implied by the essentially SeO4 desorption as SeO4/PO4 molar ratios decreased from 0.5 to 0.2. These results were further confirmed by the less SeO4 desorption (41%) from Fe/Si coprecipitates than that from Al/Si coprecipitates (78%) while PO4 was added sequentially.

Biological removal of selenate and ammonium by activated sludge in a sequencing batch reactor.

Wastewaters contaminated by both selenium and ammonium need to be treated prior to discharge into natural water bodies, but there are no studies on the simultaneous removal of selenium and ammonium. A sequencing batch reactor (SBR) was inoculated with activated sludge and operated for 90days. The highest ammonium removal efficiency achieved was 98%, while the total nitrogen removal was 75%. Nearly a complete chemical oxygen demand removal efficiency was attained after 16days of operation, whereas complete selenate removal was achieved only after 66days. The highest total Se removal efficiency was 97%. Batch experiments showed that the total Se in the aqueous phase decreased by 21% with increasing initial ammonium concentration from 50 to 100mgL-1. This study showed that SBR can remove both selenate and ammonium via, respectively, bioreduction and partial nitrification-denitrification and thus offer possibilities for treating selenium and ammonium contaminated effluents.

Adsorption of selenite and selenate by nanocrystalline aluminum oxide, neat and impregnated in chitosan beads.

Nanocrystalline metal oxide impregnated chitosan beads (MICB) were successfully developed with nanocrystalline aluminum oxide (n-Al2O3) to form n-Al2O3 impregnated chitosan beads (AICB). AICB were able to simultaneously adsorb inorganic aqueous selenite and selenate more effectively than n-Al2O3 or chitosan alone. For completeness, adsorption performance was also compared to n-TiO2, a widely studied adsorbent for selenium, and n-TiO2 impregnated chitosan beads (TICB). For the selenite system, n-Al2O3 was the primary active adsorbent responsible for removal as chitosan has a low affinity for selenite. For selenate, however, chitosan was the primary active adsorbent. The association constants for the adsorbent/adsorbate complexes and the relative amounts in which they are present supported this hypothesis. The association constants for selenate binding on n-Al2O3 and chitosan were 1.215 × 10(-2) and 3.048 × 10(-3), respectively, and the association constants for selenite binding on n-Al2O3 and chitosan were 1.349 × 10(-2) and 1.990 × 10(-4), respectively. For systems with coexisting selenite and selenate, AICB is potentially the most robust option as it maintained the most consistent performance regardless of fractionation of the selenium species. Kinetic studies and equilibrium isotherms were completed and effectively modeled using pseudo-second order kinetics and Langmuir adsorption theory, making it the first comprehensive systematic study of neat n-Al2O3 and AICB for selenium adsorption. pH significantly impacted adsorption due to changes in the adsorbent surface charge; increasing pH corresponded with decreasing adsorbent performance, beginning at approximately pH 6.5-7 for AICB. The trend in performance due to the effect of pH indicated that selenate binds to the amine group in chitosan, as suggested by other studies. In addition, increasing background sulfate concentration was found to negatively impact adsorption efficacy for both selenite, and more significantly, selenate, as sulfate is known to compete with selenium oxyanions due to their similar structures. The results indicate that, in order to maintain consistent removal in more realistic systems, a pre-treatment process to manage sulfate will be necessary as indicated for other adsorbents implemented for selenium adsorption in aqueous systems.

Evaluation of selenium species in selenium-enriched pakchoi (Brassica chinensis Jusl var parachinensis (Bailey) Tsen & Lee) using mixed ion-pair reversed phase HPLC-ICP-MS.

HPLC-ICP-MS based on ion-paired reversed phase chromatography for the selenium speciation using the mixture of 1-butanesulfonic acid (BA) and trifluoroacetic acid (TFA) as the mixed ion-pairing reagents was developed and applied to selenium-enriched pakchoi (Brassica chinensis Jusl var parachinensis (Bailey) Tsen & Lee). Several conditions of ion-paired reversed phase HPLC-ICP-MS, such as pH of the mobile phase, concentration of ion pairing reagents, types and length of analytical column, and flow rate of the mobile phase, were optimised for five selenium species; selenate (Se(VI)), Selenite (se(IV)), selenocysteine (SeC), Se-methylselenocysteine (SeMC) and selenomethionine (SeM). The results showed that the optimum conditions for pH, BA and TFA condition, type of separating column and flow rate, were 4.5, 8mM, 4mM, C18 (250 mm length × 4.6mm I.D) and 1.2 mL min(-1), respectively. These conditions archived separation of the organic selenium species. The limits of detection (LOD) and quantitation (LOQ) of each selenium species were lower than 5 and 16 ng Se mL(-1), respectively. Furthermore, the recoveries of most selenium species were good, except for SeC. In this research, selenium-enriched pakchoi was cultivated by supplementing inorganic selenium from selenate into sand. The result showed that inorganic selenium, SeMC, SeM and several unknown species were found in selenium-enriched pakchoi sprouts by using the proposed method. Thereby, the biotransformation of selenate in pakchoi was similar to other Brassicaceae plants such as kale and broccoli.