Land application of biosolids has become common practice in the United States as an alternative to industrial fertilizers. Although nutrient rich, biosolids have been found to contain high concentrations of emerging contaminants (e.g. pharmaceuticals, personal care products) while containing a significant fraction of inorganic nano-scale colloidal materials such as oxides of iron, titanium, and aluminum. Given their reactivity and small size, there are many questions concerning the potential migration of these nano-sized colloidal materials through the soil column and into our surface and groundwater bodies. Transport of emerging pollutants of concern through the soil column, at minimum, is impacted by colloidal properties (e.g. chemical composition, shape, aggregation kinetics), solution chemistry (e.g. pH, ionic strength, natural organic matter), and water flow velocity. The purpose of this current research was to characterize the long-term transport behavior of aluminum oxide nanoparticles (Al2O3) through a natural porous media with changes in pH, aqueous-phase concentration, pore-water velocity and electrolyte valence. Additionally, deposition rates during the initial stages of deposition were compared to several models developed based on colloid filtration theory and DLVO stability theory. Benchtop column laboratory experiments showed that, under environmentally relevant groundwater conditions, Al2O3 nanoparticles are mobile through saturated porous media. Mobility increased under conditions in which the nanoparticles and porous media were of like charge (pH 9). Changes in linear pore water velocity, under these same high pH conditions, showed similar transport behavior with little mass retained in the system. Deposition is believed to be kinetically controlled at pH 9, as evidenced by the slightly earlier breakthrough as flow rate increased and was further supported by observed concentration effects on the arrival wave following several stop flows. While lower aqueous-phase concentrations resulted in significantly longer breakthrough times, the total mass retained in the system was found to be independent of concentration. Additionally, experimental deposition rate coefficients (kd), used to describe deposition kinetics under "clean bed" conditions, were similar across the aqueous-phase concentrations studied. The use of calcium chloride electrolyte solution in transport studies resulted in enhanced mobility relative to potassium chloride suggesting that changes in groundwater solution chemistry could impact mobility of contaminants associated with biosolids. Predicted deposition rate coefficients, using three different models, were found to under- or over-predict values relative to those experimentally determined values depending on the model. This current research has shown that nanocolloids associated with biosolids, specifically Al2O3, are mobile through saturated porous media. Given the ubiquity of nanocolloidal materials, particularly engineered nanomaterials, coupled with the expected increase in land-application of biosolids, a clear understanding of their transport and fate is prudent to understanding the potential impact these emerging pollutants may have on our surface and groundwater bodies.

Functional materials, particularly metal oxides, have been the focus of much attention in solid state chemistry for many years and impact every aspect of modern life. The approach adopted in this thesis to access desirable functionality for enhanced fundamental understanding is via modifying existing materials by deploying reducing synthetic procedures. This work spans several groups of inorganic crystalline materials, but is unified by the development of new properties within host compounds of particular relevance to solid oxide fuel cell technology, which allow interstitial oxide ion conduction at elevated temperatures. The Ca₁₂Al₁₄O₃₂e₂ electride was successfully synthesized by replacing the mobile extra-framework oxygen ions with electrons acting as anions. The high concentration of electrons in the C12A7 electride gives rise to an exceptionally high electronic conductivity of up to 245 S cm⁻¹ at room temperature. Making use of the high density of electrons in Ca₁₂Al₁₄O₃₂e₂ electride, the strong N-N bonds in N₂ was found to be broken when heating Ca₁₂Al₁₄O₃₂e₂ in a N₂ atmosphere. A reaction between silicate apatites and the titanium metal yielded another completely new electride material La₉.₀Sr₁.₀(SiO₄)₆O₂.₄e₀.₂ which was found to be a semiconductor. To fully understand the role of oxygen interstitials in silicate apatites, high-resolution transmission electron microscopy (HRTEM) was employed as the main technique in probing how the oxygen nonstoichiometry is accommodated at the atomic level. Atomic-resolution imaging of interstitial oxygen in La₉.₀Sr₁.₀(SiO₄)₆O₂.₅ proved to be a success in this thesis. Substitution of oxygen in 2a and interstitial sites with fluoride ions in La[subscript(8+y)]Sr[subscript(2- z)](SiO₄)₆O[subscript(2+(3y-2z)/2)] (0<y<2, 0<z<2) could be an approach to enriching the functionalities in the apatite structure. A wide range of fluoride substitution levels was tolerated in La[subscript(10-x)]Sr[subscript(x)](SiO₄)₆O[subscript(3-1.5x)]F[subscript(2x)] (x= 0.67, 1, 1.5, 2) and AC impedance measurements were found in support of a tentative conclusion that fluoride ions could be mobile in fluorinated apatites. The last part of this thesis was focused on a new class of fast oxide ion conductors based on Ge₅P₆O₂₅ whose performance was superior to both La₉.₀Sr₁.₀(SiO₄)₆O₂.₅ and Ca₁₂Al₁₄O₃₃ in the low temperature range.

The thesis consists of two parts. Part 1 deals with the preparation of thin films and sub-micron powders of complex metal oxides by nebulized spray pyrolysis (NSP) and Part 2 consists of Brillouin scattering studies of solid materials exhibiting interesting phase transitions. The simple technique of NSP has been employed to prepare thin films of A12O3, PbTiO3, Pb(Zr0.5Ti0.5)O3 (PZT) and PbZrO3 on single crystal substrate. The films were characterized by various techniques for their composition, structure, morphology and dielectric properties. Ferroelectric (FE) films of the configuration FE/LaNiO3/SiO2/Si (FE = PbTiO3 and PZT), wherein the LaNiO3 barrier electrode was also deposited on the SiO2/Si substrate by NSP, have been investigated. The films exhibit satisfactory ferroelectric properties. PbZrO3 films deposited on LaNiO3/SiO2/Si substrates show good features, including a reversible AFE ↔ FE transition. Sub-micron particles of TiO2, ZrO2, Pb(Zr0.5Ti0.5)O3, Al2O3, S1O2 and mullite have been prepared by NSP and characterized by various techniques. Brillouin scattering has been used, for the first time, not only to characterize the Peierls transition but also the incommensurate to commensurate transition in the one-dimensional blue bronze, K0.3M0O3. The charge density wave transition in NbSe2 has also been investigated by Brillouin scattering. The charge ordering and antiferromag-netic transitions in single crystals of the rare earth manganates, Nd0.5Ca0.5MnO3 and Pr0.63Ca 0.37MnO3, have been investigated by Brillouin scattering. It is noteworthy that the temperature variation of the Brillouin shift and intensity parallel to that of the magnetization, thereby throwing light on magnetic excitations in charge-ordered state. Brillouin scattering investigations of C60 and C70 films have yielded values of the elastic moduli.

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