published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

The beam-foil method was used to determine mean-lives of excited atomic states. Initial studies were done on states. Initial studies were done on states of the helium- and hydrogen-like ions B IV and B V, with the mean-lives determined by fitting the decay curves to sums of exponential terms. Since theoretical values of the mean-lives are very precise in these simple atomic systems, our results indicate the accuracy of the experimental method. A series of measurements was made of the low lying 2s 2p⁴ states in nitrogen-like Ne IV, Na V, Mg VI, Al VII, and Si VIII. The experimental results were compared to theoretical calculations of Fawcett and Sinanoglu, and showed excellent agreement with Sinanolu's nonclosed-shell many electron theory. The lifetimes of the 4p ²P₁/₂ and 4p ²P₃/₂ states in copper-like Br VII were determined by measuring decay curves for both the primary and cascade decays and then analyzing the curves jointly. Our resulting mean-life values are considerbly shorter than those of previous experiments which analyzed only the primary decay curve. Comparison with theoretical calculations showed excellent agreement with those which include core polarization effects.

A couple of processes for electrosynthetic production of expendable reagents, namely acids, bases, and oxidants, from the native salt content of raw waters and industrial wastes were investigated, and the composition of mixed acids and bases made of sodium sulfate or sodium chloride salts were predicted using a model predicated on conservation principles, mass action relations, and Pitzer equations. Electrodialysis with bipolar membranes (BMED) was used to produce acids and bases in a single pass. Product concentration was limited only by the salt content of the feed water. The current efficiency for acid production was slightly higher than that for base, but neither dropped below 75%. Acid and base current utilization showed the same trends with respect to feed salt content and flow velocity, with higher efficiency at higher feed salt concentrations and flow velocities. Operating the BMED stack near the limiting current density of the bipolar membrane (BLCD) or above the limiting current density of the diluate compartment (LCD) decreased current efficiency and increased electrical power dissipation. Electrodialytic acid and base production was approximately10 times cheaper than the chemicals' f.o.b. unit costs as quoted on Alibaba.com. The mechanism and cost of on site peroxodisulfuric acid production by electrolysis of sulfuric acid solutions with boron doped diamond film anodes was investigated experimentally and with molecular dynamics (MD) and density functional theory (DFT) simulations. The cost of on site peroxodisulfate production was approximately 4 times less expensive than purchasing a 25 lb bag. It was shown that direct discharge of sulfate species produces sulfate radicals, which subsequently combined to form peroxodisulfuric acid. The likely hood of these reactions was dependent on electrode surface condition. Sulfate radicals could also be produced in solution by reaction with hydroxyl radicals generated by water discharge.

This research investigated the mechanism, kinetics and feasibility of nitrate, arsenate, and trichloroethylene inactivation on zerovalent iron (ZVI), mixed-valent iron oxides, and boron doped diamond film electrode surfaces, respectively. Nitrate ( ) is a common co-contaminant at sites remediated using permeable reactive barriers (PRBs). Therefore, understanding nitrate reactions with ZVI is important for understanding the performance of PRBs. This study investigated the reaction mechanisms of with ZVI under conditions relevant to groundwater treatment. Tafel analysis and electrochemical impedance spectroscopy were used to probe the surface reactions. Batch experiments were used to study the reaction rate of with freely corroding and cathodically protected iron wires. The removal kinetics for the air formed oxide (AFO) were 2.5 times slower than that of water formed oxide (WFO).This research also investigated the use of slowly corroding magnetite (Fe3O4) and wustite (FeO) as reactive adsorbent media for removing As(V) from potable water. Observed corrosion rates for mixed valent iron oxides were found to be 15 times slower than that of zerovalent iron under similar conditions. Electrochemical and batch and column experiments were performed to study the corrosion behavior and gain a deeper understanding on the effects of water chemistry and operating parameters, such as, empty bed contact times, influent arsenic concentrations, dissolved oxygen levels and solution pH values and other competing ions. Reaction products were analyzed by X-Ray diffraction and XPS to determine the fate of the arsenic.This research also investigated use of boron doped diamond film electrodes for reductive dechlorination of trichloroethylene (TCE). TCE reduction resulted in nearly stoichiometric production of acetate. Rates of TCE reduction were found to be independent of the electrode potential at potentials below -1 V with respect to the standard hydrogen electrode (SHE). However, at smaller overpotentials, rates of TCE reduction were dependent on the electrode potential. Short lived species analysis and density functional simulations indicate that TCE reduction may occur by formation of a surface complex between TCE and carbonyl groups present on the surface.

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In the past 20 years, boron has been identified as an essential trace element for animals and humans but also as an increasingly important industrial pollutant. We examined first whether boron influenced survival of the gastrointestinal nematode Heligmosomoides bakeri. Female Balb/c mice were fed deficient (0.1 mug B/g), marginal (2.0 mug B/g) or control (12.0 mug B/g) diets, and infected with third-stage larvae. Although liver boron concentrations did not differ among diet groups, dietary boron deficiency impaired survival of the parasite and modulated a broad range of cytokines and chemokines. On the other hand, infection history altered liver mineral concentrations. Second, we examined whether elevated boron concentrations would exert toxic effects on H. bakeri in vitro. Boron toxicity was evidenced by reduced motility, fecundity, infectivity and survival. Feeding stages and free-living stages were more sensitive than non-feeding stages and parasitic stages respectively in a dose-dependent manner.

No description available.

Although fluoride is used at low concentrations in drinking water as a means of promoting dental health, it poses a danger at high exposure levels where it can lead to skeletal fluorosis or other adverse effects. Cyanide is notoriously toxic, and its large scale use in industrial processes warrants the need for close monitoring to remain aware of potential contamination of water sources and other environmental resources. Based on these considerations, it is critical to continue to develop improved methods of monitoring fluoride and cyanide concentrations in water. However, molecular recognition of these anions in water poses considerable challenges. For fluoride, this is due largely to its high hydration enthalpy (Ho = -504 kJ mol-1), which drastically reduces its reactivity in water. Additionally, the strong basicity of cyanide (pKa of (HCN) = 9.3) may obscure its detection in neutral water due to protonation. In addition to achieving detection of these anions in water, it is most desirable to have information of the detection event relayed in the form of a positive, rather than negative, response (i.e., turn-on vs turn-off). The general strategy of appending cationic groups to triarylboranes imparts beneficial Coulombic, inductive, and sometimes chelate effects that have allowed a number of these Lewis acidic receptors to sense fluoride and cyanide in aqueous environments. With the goal of developing new triarylborane-based receptors that show enhanced affinities for these anions, as well as turn-on responses to detection, a series of pyridinium boranes were synthesized and studied. Having recognized that the inherent Lewis acidity of antimony(V) species might be exploited for anion sensing, we also describe initial studies on the ability of tetraorganostibonium ions (R4Sb+) and cationic transition metal-triarylstibine complexes (R3SbM+) to complex fluoride. Finally, the electropositivity of antimony and its ability to form stable compounds in both the +3 and +5 oxidation states have led us to begin investigations into the bonding and redox reactivity of novel metal stibine/stiborane complexes.

The Bolivian Altiplano (BA) is a high plateau located in the western part of the country at an altitude of 3,600 to 3,900 meters above sea level and is bordered by the Eastern and Western Cordillera. Within the BA there is a large endorheic hydrologic system linking the Titicaca Lake in the north the Desaguadero River, lakes Uru-Uru and Poopó in the central part; and the Lacajahuira River and Coipasa and Uyuni salt pans in the south. Several mineralized areas, especially in the Eastern Cordillera, have been intensively exploited for centuries for the extraction of silver, gold, and tin from polymetallic sulfide ore deposits. Presently many urban centers are also contributing for an extensive contamination in localized areas; especially the Poopó Lake and some rivers are affected by high loads of wastewater and solid waste, in addition to the release of heavy metals and arsenic (As) due to acid mine drainage. The presence of As in the BA was known to be related to mining only, but recent studies revealed that As of geogenic origin also contributing to the elevated concentration of As in surface and groundwater. The Poopó Lake basin is characterized by a semiarid climate. Geologic formations predominantly are of volcanic origin and groundwater flow is sluggish in nature. These environmental settings have generated substantially elevated concen- trations of geogenic As and other trace elements in surface and groundwater. Both surface and groundwater used for drinking water have high concentrations of As that by far exceed the World Health Organization (WHO) guideline. The overall objective of the present study has been focused on the determination of the sources and principal mechanisms for mobilization of geogenic As into surface and groundwater of the Poopó Lake basin area. More specifically, this study has determined the spatial distribution and the extent of As contamination in surface and groundwater; chemical composition of surface and groundwater, rock and sediment; major geochemical mechanisms for As mobilization from solid phase to aqueous phases. This study also made an assessment of drinking water quality in rural areas within the Poopó Lake basin. Arsenic concentration exceeded the WHO guideline and national regulations for drinking water of 10 µg/L in 85% of the samples collected from the area around the Poopó Lake (n=27) and 90% of the samples from the southern part of the lake basin (n=42). Groundwater samples collected from drinking water wells had As concentrations up to 623 µg/L, while samples collected from piezometers had even higher up to 3,497 µg/L. Highest concentration in river water samples was observed 117 µg/L. Alkaline nature of water (median pH 8.3 for groundwater and 9.0 for surface water), predominance of Na-Cl-HCO3 water type and elevated Eh reflecting oxidized character has been revealed by As(V) as the major species in As speciation. Different rock types were analyzed for their As content and the highest concentration of 27 mg/kg was found in a coral limestone sample. In evaporate it was 13 mg and 11 mg As/kg was measured in calcareous sandstone. Elevated concentration of As was also observed in sediment cores collected from two drilling sites; 51 mg/kg in Condo K and 36 mg/kg in Quillacas. Physical and chemical weathering of volcanic rocks, limestone, carbonates and plagioclase minerals enhance the supply of Na+ and HCO3- into solution and as a consequence pH and alkalinity increase, which in turn, favor As desorption from solid mineral surfaces (especially Fe(III) oxyhydr- oxides) and therefore dissolved As in water is increased. / <p>QC 20150529</p>

The results of a solid-state 11B NMR study of a series of boronic acids, boronic esters, and boronic acid catechol cyclic esters with aromatic substituents are reported in this thesis. Boron-11 electric field gradient (EFG) and chemical shift (CS) tensors obtained from analyses of spectra acquired in magnetic fields of 9.4 T and 21.1 T are demonstrated to be useful for gaining insight into the molecular and electronic structure about the boron nucleus. It can be concluded that when adequate electronic variation is present in the compounds being studied, Ω is generally the most characteristic boron NMR parameter of the molecular and electronic environment for boronic acids and esters. Importantly, these data are only reliably accessible in ultrahigh magnetic fields. The experimental span values result from a delicate interplay of several competing factors, including hydrogen bonding, the value of the dihedral angle, and the type of aromatic ring system present.