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PubMed2002

Removal of selenocyanate from water using elemental iron.

Batch experiments were conducted to investigate the removal of selenocyanate (SeCN-) from oil refinery wastewater and artificial wastewater with elemental iron [Fe(0)]. The chemical forms of selenium in the reacted solids were determined with X-ray photoelectron spectroscopy (XPS) and a sulfite extraction procedure. SeCN- was effectively removed from the wastewater with Fe(0) filings when the water pH was controlled at approximately 6. SeCN- was removed by Fe(0) through the formation of elemental selenium [Se(0)] and ferrous selenide. The possible chemical reactions between SeCN- and Fe(0) included deselenation of SeCN- and electrochemical reduction of Se(0) to selenide. A cost-effective process may be developed for the treatment of SeCN- in wastewater using Fe(0).

Cyanates↗
PubMed2003

Selective binding of chiral molecules of cinchona alkaloid by beta- and gamma-cyclodextrins and organoselenium-bridged bis(beta-cyclodextrin)s.

The inclusion complexation behavior of chiral members of cinchona alkaloid with beta- and gamma-cyclodextrins (1 and 2) and 6,6(')-trimethylenediseleno-bridged bis(beta-cyclodextrin) (3) was assessed by means of fluorescence and 2D-NMR spectroscopy. The spectrofluorometric titrations have been performed in aqueous buffer solution (pH 7.20) at 25.0 degrees C to determine the stability constants of the inclusion complexation of 1-3 with guest molecules (i.e., cinchonine, cinchonidine, quinine, and quinidine) in order to quantitatively investigate the molecular selective binding ability. The stability constants of the resulting complexes of 2 with guest molecules are larger than that of 1. As a result of cooperative binding, the stability constants of inclusion complexation of dimeric beta-cyclodextrin 3 with cinchonidine and cinchonine are higher than that of parent 1 by factor of 4.5 and 2.4, respectively. These results are discussed from the viewpoint of the size-fit and geometric complementary relationship between the host and guest.

Binding Sites↗
PubMed2000

A geometric approach to determine adsorption and desorption kinetic constants.

A geometric method based on Langmuir kinetics has been derived to determine adsorption and desorption kinetic constants. In the conventional procedure, either the adsorption kinetic constant (k(a)c) or desorption kinetic constant (k(d)c) is found from kinetic experiments and the other is calculated by their correlation with the equilibrium constant, i.e, k(d)c = Kcon/k(a)c, where Kcon has been known from equilibrium studies. The determined constants (Kcon, k(a)c, k(d)c), if based only on the conventional procedure, may not be accurate due to their mathematical dependence. Therefore, the objectives of this study are applying a geometric approach to directly determine Langmuir kinetic constants and describe adsorption behavior. In this approach, both adsorption kinetic constant (k(a)g) and desorption kinetic constant (k(d)g) are obtained only from data of kinetic experiments, and a geometric equilibrium constant (Kgeo) is calculated by Kgeo = k(a)g/k(d)g. The deviation between Kgeo and Kcon can prove the accuracy of k(a)g and k(d)g which were determined by this method. This approach was applicable to selenate, selenite and Mg2+ adsorption onto SiO2 regardless of whether the adsorbate formed inner- or outer-sphere complexes. However, this method showed some deviation between Kcon and Kgeo for Mn2+ adsorption because of the formation of surface Mn(II)-hydroxide clusters, which was inconsistent with the basic assumption of this method of monolayer adsorption.

Adsorption↗
PubMed2002

Modeling competitive adsorption of molybdate, sulfate, selenate, and selenite using a Freundlich-type multi-component isotherm.

This study examined the interactions of MoO4(2-) + SO4(2-), MoO4(2-) + SeO4(2-), and MoO4(2-) + SeO3(2-) systems on gamma-Al2O3 to better understand the competitive adsorption of these anions in the natural environment. The Freundlich isotherms of anionic adsorption onto gamma-Al2O3 in single and binary solutes were also investigated to estimate the competition between these anions. Experimental results indicate that a higher concentration of competitive solute yields a higher efficiency of the competitive solute's prevention of MoO4(2-) adsorption. The most significant result was found in the MoO4(2-) + SeO3(2-) system. The Freundlich isotherm constant (n) increases with the competitive solute concentration. The suitability of a Freundlich-type isotherm, the Sheindorf-Rebuhn-Sheintuch (SRS) equation, and the modified SRS equation in representing the competitive adsorption of MoO4(2-), SO4(2-), SeO4(2-), and SeO3(2-) on gamma-Al2O3 surface, was also examined. Each set of isotherm data was found to conform to linear SRS expressions, allowing competition coefficients to be derived on a concentration basis for each binary-solute system. The competition coefficient aij and relative affinity coefficients alphaij can be seen as a way to quantify competitive interactions. The proposed SRS and modified SRS equations are simple mathematical expressions accounting for competitive interactions of anions present in a mixture for the range of concentrations over which each individual component exhibits Freundlich behavior.

Adsorption↗
PubMed2003

Forms and distribution of selenium at different depths and among particle size fractions of three Taiwan soils.

The bioavailability of selenium in soils for plants depends more on its forms than on its total concentration. The purpose of the present study was to examine the solid-phase forms of selenium at different depths of three soil series representing major farming soil groups in Taiwan as well as the amounts of selenium in sand, silt and clay fractions of the soils. The study was conducted by means of sequential extraction to obtain the amounts of selenium and the distribution of various solid-phase forms of selenium at different depths of Pinchen (121 degrees 11(')E, 24 degrees 55(')N), Toulun-Sheto (120 degrees 55(')E, 24 degrees 50(')N), and Chunliao (120 degrees 25(')E, 23 degrees 57(')N) soil series. The amounts of metal oxide-bound form of selenium in the three soil series were the largest, with those of Pinchen and Toulun-Sheto soil series exceeding 50% of the total amounts of selenium and that of Chunliao soil series maintained at 30-40%. In the Pinchen and Toulun-Sheto soil series, the amounts of selenium in clay fractions were the largest, with a significant difference between the clays with and without metal oxides and organic matter removed. The amounts of selenium remained high in silt and/or sand fractions of the Chunliao soil series with metal oxides and organic matter removed. Metal oxide and organic matter contents of the three soil series mainly affect the amounts of various solid-phase forms of selenium and their distribution in different depths and particle size fractions of the soils. This observation of selenium associated with soil constituents was in good agreement with the results of the adsorption of selenite and selenate by the three soil series.

Adsorption↗
PubMed2003

Possible use of constructed wetland to remove selenocyanate, arsenic, and boron from electric utility wastewater.

Wetland microcosms were used to evaluate the ability of constructed wetlands to remove extremely high concentrations of selenocyanate (SeCN-), arsenic (As), and boron (B) from wastewater generated by a coal gasification plant in Indiana. The wetland microcosms significantly reduced the concentrations of selenium (Se), As, B, and cyanide (CN) in the wastewater by 64%, 47%, 31%, and 30%, respectively. In terms of the mass of each contaminant, 79%, 67%, 57%, and 54% of the Se, As, B, and CN, respectively, loaded into the microcosms were removed from the wastewater. The primary sink for the retention of contaminants within the microcosms was the sediment, which accounted for 63%, 51%, and 36% of the Se, As, and B, respectively. Accumulation in plant tissues accounted for only 2-4%, while 3% of the Se was removed by biological volatilization to the atmosphere. Of the 14 plant species tested, cattail, Thalia, and rabbitfoot grass were highly tolerant of the contaminants and exhibited no growth retardation. Environmental toxicity testing with fathead minnow (Pimephales promelas) larvae confirmed that the water treated by the wetland microcosms was less toxic than untreated water. The data from the wetland microcosms support the view that constructed wetlands could be used to successfully reduce the toxicity of aqueous effluent contaminated with extremely high concentrations of SeCN-, As, and B, and that a pilot-scale wetland should therefore be constructed to test this in the field. Cattail, Thalia, and rabbitfoot grass would be suitable plant species to establish in such wetlands.

Animals↗
PubMed2000

Effect of moisture and casein on demethylation of trimethylselenonium in soil.

Trimethylselenonium ion (TMSe+) is a major urinary selenium (Se) metabolite of animals. The effect of soil moisture and casein on the demethylation of TMSe+ were examined in three California soils [Tulare Basin (TL), Losthill (LH) and Five Points (FP) upland areas] treated with 20 microg/g TMSe+. Results showed that soil moisture positively affected the demethylation of TMSe+ to volatile dimethylselenide (DMSe). In the non-saline TL and FP soils, the highest demethylation rates were 0.169-0.454, 0.646-2.71, and 3.15-6.01 microg/g per day from a 10, 20, and 100% moisture soil, respectively. During 51 days of the experiment, approximately 75.4-80.2% of added TMSe+ was demethylated to volatile DMSe. In contrast, in a saline LH soil, the demethylation rate was < 0.2 microg/g per day, and only 7% of the added TMSe+ was demethylated to volatile DMSe. Addition of casein stimulated the demethylation of TMSe+ in a 10% moisture TL soil. Dissolved DMSe, dimethylselenoxide (DMSeO) and TMSe+, and adsorbed TMSe+ were found in the three experimental soils. Concentrations of dissolved and adsorbed TMSe+ were much higher in the LH soil than in the TL and FP soils. This study showed that demethylation of TMSe+ dominates in the FP and TL soils, and adsorption of TMSe+ is a more important process in the LH soil.

Animals↗
PubMed2002

Influence of various concentrations of selenic acid (IV) on the activity of soil enzymes.

The aim of this experiment was the assessment of the influence of various concentrations of H2SeO3 (0.05, 0.5 and 5 mM) on the activity of soil enzymes over 112 days. The lab experiment was performed using soil samples (dust-silt black soil of 1.92% organic C content, pH 7.7), 60% maximal water capacity. The soil samples were treated with a selenic acid water solution at the concentrations mentioned above. As a reference, natural soil was used (without the selenic acid). The activity of the following enzymes was tested: beta-glucosidase, nitrate reductase, urease, dehydrogenase, acid and alkaline phosphatases. The soil was sampled at days 0, 1, 3, 7, 14, 28, 56 and 112. The results of the study have shown that the selenic acid had no effect on the activity of the beta-glucosidase in soil. In the course of the whole experiment, the applied selenic acid inhibited activity of the nitrate reductase up to 70% at 5 mM, and the activity of dehydrogenase was also decreased--by up to 85% at 5 mM, similarly to urease (with the exception of days 14 and 28), and acid phosphatase (until day 56). The activity of alkaline phosphatase was increased by the lowest concentration of selenic acid and decreased by the highest, which was found in the course of the whole experiment. The 5-mM concentration of selenic acid inhibited the activity of all the enzymes tested in this experiment.

Biomass↗
PubMed2003

Factors affecting removal of selenate in agricultural drainage water utilizing rice straw.

Microbial reduction of selenate [Se(VI)] to elemental selenium [Se(0)] is a useful technique for removing Se from agricultural drainage water. A series of batch experiments were conducted in the laboratory to determine the effects of pH (5-10), NO(3)(-) (100-500 mg/l), and SO(4)(2-) (0-5000 mg/l) on the removal of Se(VI) from drainage water with 1000 microg/l of Se(VI) and different amounts (1-4 g) of rice straw. Results showed that rice straw was very effective in creating a reducing environment (Eh=-205 to -355 mV) in the first 3 days of the pH-effect experiments. The optimum conditions for rapid Se(VI) removal from drainage water were a pH range of 6-9, high amounts of SO(4)(2-) (1000-5000 mg/l), low amounts of NO(3)(-) (100 mg/l) and high amounts of rice straw (3-4 g). Under these conditions, it took 5-7 days to reduce 93-95% of the added Se(VI) to Se(0). This study indicates that rice straw may be an inexpensive reducing agent to remediate Se(VI)-dominant San Joaquin Valley drainage water in the field.

Adsorption↗
PubMed1996

Genotoxicity evaluation of selenium sulfide in in vivo and in vivo/in vitro micronucleus and chromosome aberration assays.

Selenium monosulfide (SeS) was reported to be carcinogenic to livers of male and female rats and livers and lungs of female mice. However, its genotoxicity profile in short-term assays is somewhat equivocal. A multiple endpoint/multiple tissue approach to short-term genetic toxicity testing has been developed in our laboratory. In the present paper, the effect of SeS in in vivo and in vivo/in vitro micronucleus and chromosome aberration assays in rat bone marrow and spleen are reported. In the in vivo assay, small but statistically significant increases in bone marrow micronucleated polychromatic erythrocytes (MNPCEs) were observed 24 h after treatment of rats with 50 mg/kg SeS and 48 h after treatment with 12.5 mg/kg. A significant decrease in the PCE/total erythrocyte (TE) ratio, indicative of cytotoxicity, was observed at the 50 mg/kg dose at the 24-h timepoint. In spleen, no increases in MNPCEs or decreases in the PCE/TE ratios were observed. No evidence of a significant increase in aberrations was observed in bone marrow or spleen. In the in vivo/in vitro assay, no increase in micronucleated binucleated cells or cells with aberrations was observed in SeS-treated rats. The small but statistically significant increases in MN observed in the in vivo study are considered likely not to be biologically significant since no dose-response was observed and all the values obtained were within historical control range in our laboratory. Given the overall genetic toxicity profile of SeS, it appears that SeS may be a weak mutagen and that differences between testing protocols may be very important in determining whether or not it is found to be negative or positive. Histological evidence was obtained in this study that suggests that the liver is the acute target organ of SeS in rats. Given the fact that SeS is selectively hepatocarcinogenic, we are currently testing the hypothesis that the genotoxicity of SeS in rats may be more readily detectable in liver than in bone marrow or spleen.

Administration, Oral↗
PubMed1984

Double-blind efficacy study of selenium sulfide in tinea versicolor.

Selenium sulfide (2.5%) lotion applied daily for 10 minutes for 7 consecutive days was found to be an effective therapeutic agent, significantly superior to the vehicle, in a double-blind study in the treatment of tinea versicolor. Mild transitory contact dermatitis of the primary irritant type occurred in all the treatment groups and was apparently due to the detergent base.

Administration, Topical↗
PubMed1984

Selenium sulfide in tinea versicolor: blood and urine levels.

The safety of topical selenium sulfide lotion in man has been demonstrated previously. Twenty male patients with a diagnosis of tinea versicolor were randomly assigned to two parallel groups who applied selenium sulfide lotion or the vehicle to the entire skin surface, excluding mucous membranes, for 10 minutes once daily for 7 consecutive days. Blood and urine selenium levels were determined before and after treatment and showed no significant differences between the active drug and vehicle groups on any study day. It would appear that no significant absorption of selenium took place as a result of this treatment regimen.

Administration, Topical↗
PubMed1985

Pityrosporum folliculitis: a common disease of the young and middle-aged.

Fifty-one patients, thirty-nine women and twelve men, with Pityrosporum folliculitis are described. This investigation clearly demonstrates that Pityrosporum folliculitis is a real entity. The diagnosis is based primarily on the clinical picture, direct microscopy, histopathology, and the effect of antimycotic treatment. The typical patient is a woman of 30 years with itching follicular papules and pustules localized to the upper trunk or upper arms. Direct microscopy reveals round yeast cells and sometimes even hyphae. In biopsy specimens, abundant round budding yeast cells and occasionally hyphae are seen in a dilated follicle. Yeast growth is obtained only on lipid-enriched media. Twenty-five patients were treated with selenium sulfide shampoo, twelve with 50% propylene glycol in water, and ten with topical econazole cream with good results. Cure or marked improvement was seen after 3 to 4 weeks, but symptoms and lesions recurred if treatment was not continued intermittently. Predisposing factors such as occlusion and greasy skin are probably important, and future studies should focus on fungal hypersensitivity, quantitative variations in the number of Pityrosporum orbiculare, lipid composition of the skin, and extended epidemiologic data.

Administration, Topical↗