none

The overall goal of this study is to evaluate the ability of novel nanostructured adsorbent media (NTAs, iron sulfides (FeS2 and FeS)) to remove arsenic, selenium and mercury from ash and scrubber pond effluents. The NTAs aim to enhance arsenic removal from solution compared to conventional adsorbents. The iron sulfides are expected to produce stable residuals for ultimate disposal after removing As, Se and Hg from solution, so that removal of these compounds from wastewaters will not result in contamination of soils and groundwaters. Methods for reliably and economically producing these materials were developed. The synthesized NTAs and iron sulfides were characterized by surface analysis techniques such as XRD, FT-IR, SEM-EDS, TEM, XPS, AFM and N2-adsorption. These analyses indicated that Ti(25)-SBA-15 has highly ordered hexagonal mesopores, MT has interparticle mesopores, pyrite (FeS2) forms crystalline, nonporous rectangular nanoparticles (<500 nm), and mackinawite (FeS) forms amorphous, nonporous nanoparticles (<100 nm). Kinetic and equilibrium tests for As(III, V) removal were conducted with NTAs over a range of pH (4, 7, 9.5). The rates of arsenic uptake were very fast and followed a bi-phasic sorption pattern, where sorption was fast for the first 10 minutes, and then slowed and was almost completed within 200 minutes. Distinct sorption maxima for As(III) removal were observed between pH 7 and pH 9.5 for MT and between pH 4 and pH 7 for Ti(25)-SBA-15. The amount of As(V) adsorbed generally decreased as pH increased. In addition, a surface complexation model (SCM) based on the diffuse layer model (DLM) was used to predict arsenic adsorption envelopes by NTAs under various environmental conditions. The SCM for As(III, V) adsorption by NTAs demonstrated the role of mono- and bidentate surface complexes in arsenic adsorption. A batch reactor system was employed in an anaerobic chamber to conduct experiments to characterize both the removal of As, Se, Hg from solution and their subsequent reactions with iron sulfides. Experiment variables for removal experiments included: contaminant valence state (As(V), As(III), Se(VI), Se(IV), Hg(II)); adsorbent/reactant type (FeS, FeS2); adsorbent/reactant concentration; pH (7, 8, 9, 10); and competing ion (SO42-) concentration (0, 1, 10 mM). Experimental variables for reaction experiments were reaction time (up to 30 days) at pH 8 and oxidation states of contaminants. In addition, the stability of iron sulfides (FeS2, FeS) combined with target compounds was investigated by measuring the ability of the target compounds to resist release to the aqueous phase after removal. These experiments showed that iron sulfides were good adsorbent/reactants for target contaminants in spite of the presence of sulfate. This was particularly true at intermediate concentrations of target compounds. The experiments also demonstrated that iron sulfides interacted with target contaminants in such a way to improve their resistance to being released back to solution as pH was changed. Therefore, this study demonstrates the ability of novel nanostructured adsorbent media to remove arsenic, selenium and mercury from ash and scrubber pond effluents and the ability of iron sulfides to produce residuals that are stable when disposed in landfills.

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (p. 116-127).

No description available.

Selenium, an essential trace mineral that becomes anticarcinogenic at supranutritional levels, is readily incorporated into milk proteins when cows are fed high levels of selenium. The objective of this study was to investigate the effects of selenized milk protein on human mammary tumor progression. Four isonitrogenous diets with Se levels of 0.16, 0.51, 0.85 and 1.15 ppm were formulated by mixing low- and high-selenium milk protein isolates with a rodent premix. MCF-7 human breast cancer cells were inoculated into the mammary fat pad of female BALB/c nude mice implanted with slow-release 17 β-estradiol pellets. Mice with palpable tumors were randomly assigned to one of four diets for 10 weeks. Increasing Se intake reduced final tumor volume and the number of tumors > 500 mm3 in volume. There was a two-fold higher proportion of apoptotic cells in tumors exposed to the highest Se level. / Financial support was provided by Dairy Farmers of Ontario, Alltech Canada, Inc., and NSERC Canada.

A general route to 1-chloro-1,2,4,6-selenatriazines with substuents on 3,5 positions has been developed by the reactions of N-imidoylamidines with selenium tetrachloride. The mechanism for these reactions is discussed according to the observed intermediates. At least two intermediates exist. One of the intermediates, 1,1-dichloro-3-trichloromethyl-4H-5-diisopropylphenyl-1,2,4,6-selenatriazine, was identified by 1HNMR, Mass spectroscopy and X-ray crystallography. 1-Chloro-1,2,4,6-selenatriazines were synthesized in high yield and fully characterized. Five 1-chloro-1,2,4,6-selenatriazine crystal structures were obtained. Reduction of 1-chloro-1,2,4,6-selenatriazines with triphenylamtimony immediately produced the corresponding selenatriazinyl radicals in hot acetonitrile. Pure radicals were obtained by in-situ crystallization as their dimers from reaction. Two crystal structures were obtained for 3-trifluoromethyl-5-p-tolyl-1,2,4,6-selenatriazinyl dimer and 3-trifluoromethyl-5-p-methyloxyphenyl-1,2,4,6-selenatriazinyl dimer. EPR spectroscopy measured all radicals coupling to three unique nitrogen atoms with 7 broad lines. There is no resolvable hyperfine coupling to 77Se, 37Cl/19F and phenyl protons. / xv, 172 leaves : ill. ; 29 cm.

No description available.

The complexes Cp(,2)M(SH)(,2), where M = Ti and Zr, have been prepared and treated with S(,8) and >N-S(,x)-NN = benzimidazolyl, phthalimidyl and x = 1, 2, to give the metallacyclohexasulfanes Cp(,2)MS(,5). Reaction of Cp(,2)TI(SH)(,2) with >N-SR, where >N = phthalimidyl, succinimidyl, gave the complexes Cp(,2)Ti(S(,2)R)(,2) (R = CHMe(,2)) and Cp(,2)Ti(SR)(S(,3)R) (R = Ph, 4-C(,6)H(,4)Me). The thiolates Cp(,2)Ti(Cl)SR and Cp(,2)Ti(SR)(,2) (R = CHMe(,2), CMe(,3), Ph, 4-C(,6)H(,4)Me) were prepared for comparison. Treatment of the complexes Cp(,2)MCl(,2) with anhydrous solutions of Li(,2)E(,x) gave the complexes Cp(,2)ME(,5), where M = Ti, Zr, Hf and E = S, Se. The compounds (RCp)(,2)TiS(,5) (R = Me, SiMe(,3)),CH(,2)Cp(,2)TiS(,5), and (Me(,5)Cp)CpTiS(,5) were prepared similarly. Reaction of Li(,2)S(,x) with (Me(,5)Cp)(,2)MCl(,2) gave the metallacyclotetrasulfanes (Me(,5)Cp)(,2)MS(,3). The complex Cp(,2)Ti{S(CH(,2))(,3)S} was synthesized. Variable temperature ('1)H NMR studies established the barriers ((DELTA)G('(NOT=))) for ME(,x) and TiS(,2)C(,3) ring reversal in the above complexes. The crystal structures of Cp(,2)Ti(SPh)(S(,3)Ph), Cp(,2)MS(,5), and (Me(,5)Cp)(,2)TiS(,3) are discussed.

No description available.

Runoff and effluent discharge from mining activities has resulted in elevated concentrations of selenium in aquatic ecosystems. Bioavailability is dependent on chemical speciation. Although dissolved inorganic Se species are not directly toxic to organisms, uptake by primary producers and subsequent biotransformation to organo-selenium species substantially increase risk and bioaccumulation potential, potentially impairing reproduction in high-order organisms. The effects of dietary selenium exposure were assessed in two aquatic invertebrates: Ceriodaphnia dubia and Chironomus dilutus. Two generations of these organisms were exposed to seleniferous algae grown in 0-40 μg L-1 selenate. Dissolved selenate was readily absorbed and concentrated by algal species Pseudokirchneriella subcapitata and Chlorella kesslerii. Se had no effect on survival at treated concentrations. Dietary selenium exposures had little effect on reproductive endpoints in either invertebrate species, suggesting that invertebrates have the ability to regulate chronic Se exposures from dietary sources. These results provide valuable information concerning the effects of dietary selenium in aquatic invertebrates.