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.

Understanding Urban Stormwater Denitrification in Bioretention Internal Water Storage Zones

Free-draining bioretention systems commonly demonstrate poor nitrate removal. In this study, column tests verified the necessity of a permanently saturated zone to target nitrate removal via denitrification. Experiments determined a first-order denitrification rate constant of 0.0011 min-1 specific to Willow Oak woodchip media. A 2.6-day retention time reduced 3.0 mgN/L to below 0.05 mg-N/L. During simulated storm events, hydraulic retention time may be used as a predictive measurement of nitrate fate and removal. A minimum 4.0 hour retention time was necessary for in-storm denitrification defined by a minimum 20% nitrate removal. Additional environmental parameters, e.g., pH, temperature, oxidation-reduction potential, and dissolved oxygen, affect denitrification rate and response, but macroscale measurements may not be an accurate depiction of denitrifying biofilm conditions. A simple model was developed to predict annual bioretention nitrate performance. Novel bioretention design should incorporate bowl storage and large subsurface denitrifying zones to maximize treatment volume and contact time.