Multiple sulfur isotope fractionations in inorganic aqueous systems

New constraints on isotope fractionation factors in inorganic aqueous sulfur systems based on theoretical and experimental techniques relevant to studies of the sulfur cycle in modern environments and the geologic rock record are presented in this dissertation. These include theoretical estimations of equilibrium isotope fractionation factors utilizing quantum mechanical software and a water cluster model approach for aqueous sulfur compounds that span the entire range of oxidation state for sulfur. These theoretical calculations generally reproduce the available experimental determinations from the literature and provide new constraints where no others are available. These theoretical calculations illustrate in detail the relationship between sulfur bonding environment and the mass dependence associated with equilibrium isotope exchange reactions involving all four isotopes of sulfur. I additionally highlight the effect of isomers of protonated compounds (compounds with the same chemical formula but different structure, where protons are bound to either sulfur or oxygen atoms) on isotope partitioning in the sulfite (S4+) and sulfoxylate (S2+) systems, both of which are key intermediates in oxidation-reduction processes in the sulfur cycle. I demonstrate that isomers containing the highest degree of coordination around sulfur (where protonation occurs on the sulfur atom) have a strong influence on isotopic fractionation factors, and argue that isomerization phenomenon should be considered in models of the sulfur cycle. Additionally, experimental results of the reaction rates and isotope fractionations associated with the chemical oxidation of aqueous sulfide are presented. Sulfide oxidation is a major process in the global sulfur cycle due largely to the sulfide-producing activity of anaerobic microorganisms in organic-rich marine sediments. These experiments reveal relationships between isotope fractionations and reaction rate as a function of both temperature and trace metal (ferrous iron) catalysis that I interpret in the context of the complex mechanism of sulfide oxidation. I also demonstrate that sulfide oxidation is a process associated with a mass dependence that can be described as not conforming to the mass dependence typically associated with equilibrium isotope exchange. This observation has implications for the inclusion of oxidative processes in environmental- and global-scale models of the sulfur cycle based on the mass balance of all four isotopes of sulfur. The contents of this dissertation provide key reference information on isotopic fractionation factors in aqueous sulfur systems that will have far-reaching applicability to studies of the sulfur cycle in a wide variety of natural settings.

UTILIZING ELECTRONIC NOSE AND GC-MS TO EXAMINE CRITICAL FACTORS INFLUENCING THE FORMATION OF ODOROUS VOC’S IN BIOSOLIDS.

Despite the efforts to better manage biosolids field application programs, biosolids managers still lack of efficient and reliable tools to apply large quantities of material while avoiding odor complaints. Objectives of this research were to determine the capabilities of an electronic nose in supporting process monitoring of biosolids production and, to compare odor characteristics of biosolids produced through thermal-hydrolysis anaerobic digestion (TH-AD) to those of alkaline stabilization in the plant, under storage and in the field. A method to quantify key odorants was developed and full scale sampling and laboratory simulations were performed. The portable electronic nose (PEN3) was tested for its capabilities of distinguishing alkali dosages in the biosolids production process. Frequency of recognition of unknown samples was tested achieving highest accuracy of 81.1%. This work exposed the need for a different and more sensitive electronic nose to assure its applicability at full scale for this process. GC-MS results were consistent with those reported in literature and helped to elucidate the behavior of the pattern recognition of the PEN3. Odor characterization of TH-AD and alkaline stabilized biosolids was achieved using olfactometry measurements and GC-MS. Dilution-to-threshold of TH-AD biosolids increased under storage conditions but no correlation was found with the target compounds. The presence of furan and three methylated homologues in TH-AD biosolids was reported for the first time proposing that these compounds are produced during thermal hydrolysis process however, additional research is needed to fully describe the formation of these compounds and the increase in odors. Alkaline stabilized biosolids reported similar odor concentration but did not increase and the ‘fishy’ odor from trimethylamine emissions resulted in more offensive and unpleasant odors when compared to TH-AD. Alkaline stabilized biosolids showed a spike in sulfur and trimethylamine after 3 days of field application when the alkali addition was not sufficient to meet regulatory standards. Concentrations of target compounds from field application of TH-AD biosolids gradually decreased to below the odor threshold after 3 days. This work increased the scientific understanding on odor characteristics and behavior of two types of biosolids and on the application of electronic noses to the environmental engineering field.

Effects of Gallium-Desferrioxamine Compounds on Bacteria

Over 70% of nosocomial infections in the United States are resistant to one or more traditional antibiotics, necessitating research for alternative treatment options. This study aims to chelate gallium (Ga) onto a bacterial siderophore, desferrioxamine (DFO), to retard bacterial growth. By exploiting natural bacterial pathways, metal-siderophore treatments are hypothesized to circumvent traditional resistance mechanisms. Additionally, the GaDFO complex will be tested against several bacterial species to determine the specificity of DFO uptake. This research aims to prove the feasibility of siderophore piracy as an alternative to antibiotics. In showing the feasibility of siderophore piracy mechanisms, this research will enable the development of future avenues for protecting against resistant nosocomial infections.