MULTI-UNIT ACCIDENT CONTRIBUTIONS TO U.S. NUCLEAR REGULATORY COMMISSION QUANTITATIVE HEALTH OBJECTIVES: A SAFETY GOAL POLICY ANALYSIS USING MODELS FROM STATE-OF-THE-ART REACTOR CONSEQUENCE ANALYSES

The U.S. Nuclear Regulatory Commission implemented a safety goal policy in response to the 1979 Three Mile Island accident. This policy addresses the question “How safe is safe enough?” by specifying quantitative health objectives (QHOs) for comparison with results from nuclear power plant (NPP) probabilistic risk analyses (PRAs) to determine whether proposed regulatory actions are justified based on potential safety benefit. Lessons learned from recent operating experience—including the 2011 Fukushima accident—indicate that accidents involving multiple units at a shared site can occur with non-negligible frequency. Yet risk contributions from such scenarios are excluded by policy from safety goal evaluations—even for the nearly 60% of U.S. NPP sites that include multiple units. This research develops and applies methods for estimating risk metrics for comparison with safety goal QHOs using models from state-of-the-art consequence analyses to evaluate the effect of including multi-unit accident risk contributions in safety goal evaluations.

Assessing the Oxidative History of Miller Range Martian Meteorites

Miller Range (MIL) Martian meteorites are oxidized nakhlites. Early studies attribute their oxidation to reduction-oxidation reactions involving assimilated sulfate. I utilize the sulfur isotope and major element composition of the MIL pairs to assess their oxidative history. MIL sulfides display an average sulfur isotope composition that is different from Nakhla sulfate and sulfide. The sulfur isotope differences produce a mixing array between juvenile sulfur and mass-independent sulfur signatures, indicating assimilation of anomalous sulfur into the melt. I estimate an fO2 of QFM (+3.5 ± 0.4) and a sulfur content of 360 ppm ± 12 – 1300 ppm ± 50. With these results, I test the hypothesis of sulfate assimilation through models of charge balance, isotope mixing, and degassing of sulfur bearing compounds. I conclude that sulfate assimilation was significant in the oxidation of the MIL pairs but, additional oxidants were assimilated.

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.